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10,529,344
ACCEPTED
Seed tape
A seed tape (1) includes successively arranged germinating units (2a, 2b, 2c) made of a plane material. These germinating units are coherent or secured to a carrier strip (3) of at least one layer of biodegradable material. Each germinating unit (2a, 2b, 2c) is intended to be bedded out in the ground (12) or a growth substrate and includes a mixture of carrier (7), at least one additive (9) and optionally adjuvants (8) in addition to one or more seeds (6). The additive or additives (9) include water-absorbing materials, such as superabsorbing polymers. Each germinating unit (2a, 2b, 2c) is provided with at least one narrow zone (5) of water-repellent material across its surface adjacent or at least up to the upper edge of said unit. The material of the narrow zone penetrates the plane material of the germinating unit (2a, 2b, 2c) throughout the entire thickness thereof. As a result, the seed tape is not easily subjected to a drying up due to sun and wind although the upper end of said tape should project slightly from the ground.
1. A seed tape (1) including successively arranged germinating units (2a, 2b, 2c) made of plane material and being coherent or secured to a carrier strip (3) of at least one layer of biodegradable material, and where each germinating unit (2a, 2b, 2c) intended to be vertically bedded out in the earth (12) or in a growth substrate and in addition to one or more seeds (6) includes a mixture of a carrier (7), at least one additive (9) and a filler and adjuvants (8), and where the additive or the additives (9) include water-absorbing materials, such as superabsorbing polymers, characterised in that each germinating unit (2a, 2b, 2c) is provided with at 10 least one narrow zone (5) of water-repellent material across said unit, adjacent or at least up to the upper edge of said unit, where the water-repellent material penetrates the plane material of the germinating unit throughout the entire thickness thereof. 2. A seed tape as claimed in claim 1, characterised in that the water-repellent material of the narrow zone (5) is silicone or silicone oil. 3. A seed tape as claimed in claim 1, characterised in that the narrow zone (5, 5′) of water-repellent material is of a height (h) of at least 1 mm. 4. A seed tape as claimed in claim 1, characterised in that the narrow zone (5, 5′) of water-repellent material is of a height of 3.5 to 10 mm. 5. A seed tape as claimed in claim 1, characterised in that the narrow zone of water-repellent material is of a height (h) of 5 to 10% of the height (H) of the germinating unit. 6. A seed tape as claimed in claim 1, characterised in that the plane material of the germinating units (2a, 2b, 2c etc.) is paper, of a weight of 30 to 60 g/m2 and that the carrier strip (1) is made of paper as well. 7. A seed tape as claimed in claim 1, characterised in that the water-repellent material of the narrow zone (5,51) is wax, stearin, paraffin or caoutchouc applied onto the plane material of the germinating unit as a hot melt and subsequently cured. 8. A seed tape as claimed in claim 1, characterised in that the water-repellent material of the narrow zone (5, 5′) is a plastic. 9. A seed tape as claimed in claim 1, characterised in that a narrow zone (5′) of water-repellent material is provided at or adjacent the lower edge (14) of each germinating unit (2a, 2b, 2c). 10. A seed tape as claimed in claim 1, characterised in that said tape is continuously manufactured as the germinating units (2a, 2b, 2c etc.) are manufactured by means of one or more paper ribbons (16,17) of a width twice the width of the completed seed tape, a zone (15) of water-repellent material of a double width being applied onto the centre of said paper ribbon, whereafter said paper ribbon or ribbons (16, 17) are slotted (o) through the centre of the water-repellent zone (15). 11. A seed tape as claimed in claim 1, characterised in that a deterrent is added to the water-repellent material of the narrow zone (5, 5′), said deterrent preferably being a substance affecting the sense of smell or taste of animals or birds. 12. A seed tape as claimed in claim 1, characterised in that at the upper edge (4) of the germinating unit, the narrow zone (5) of water-repellent material is extended slightly downwards (5a, 5b) along the vertical edges (18a, 18b) of said germinating unit (2a, 2b, 2c). 13. A seed tape as claimed in claim 1 further comprising a filter and adjuvants (8). 14. A seed tape as claimed in claim 4 wherein said height is 4 to 8. 15. A seed tape is claimed in claim 6 wherein said height is 5 mm. 16. A seed tape is claimed in claim 6 wherein said weight is 40 to 50 g/m2. 17. A seed tape as claimed in claim 8 wherein said plastic comprises a polyaeride (PLA). 18. A seed tape as claimed in claim 9 wherein said plastic comprises a polysaccharide.
TECHNICAL FIELD The invention relates to a seed tape including successively arranged germinating units made of plane material and being coherent or secured to a carrier strip of at least one layer of biodegradable material, and where each germinating unit is intended to be vertically bedded out in the earth or in a growth substrate and in addition to one or more seeds includes a mixture of carrier, at least one additive and optionally a filler and adjuvants, and where the additive or the additives include water-absorbing materials, such as superabsorbing polymers. BACKGROUND ART When the tape is to be vertically positioned, the bedding out of a seed tape is encumbered with the problem that said seed tape is not positioned sufficiently deeply in the earth. A small piece of the upper end of the tape projects from the earth, and long periods of windy weather or sunshine imply that the germinating units of the seed tape dry up because each germinating unit acts as a wick for the transport of the moisture to the surface of the ground, and accordingly the wind or sun dries up the germinating units through the projecting end of the seed tape. The latter is a rather unsatisfactory effect. BRIEF DESCRIPTION OF THE INVENTION The object of the invention is to provide a seed tape of the above type and which ensures that although a small piece of the seed tape projects from the ground then the germinating units are not easily dried up. The seed tape according to the invention is characterised in that each germinating unit is provided with at least one narrow zone of water-repellent material across said unit, adjacent or at least up to the upper edge of said unit, where the water-repellent material penetrates the plane material of the germinating unit throughout the entire thickness thereof. As a result, each germinating unit is provided with a water-repellent barrier or seal in the upward direction, said barrier or seal completely eliminating, optionally considerably reducing the moisture-evaporating tendency of the upper end of said germinating units. According to the invention the water-repellent material may be silicone or silicone oil which turned out to be particularly easy to apply and being very efficient in practice. Furthermore, the narrow zone of water-repellent material may according to the invention be of a height of at least 1 mm, which turned out to be particularly advantageous. In addition, the narrow zone of water-repellent material may according to the invention be of a height of 3.5 to 10 mm, preferably 4 to 8 mm, especially 5 mm. These widths turned out to be particularly advantageous. According to the invention, the narrow zone of water-repellent material may be of a height of 5 to 10% of the height of the germinating unit, which turned out to be a particularly advantageous embodiment. Moreover, the plane material of the germinating units may according to the invention be paper, preferably of a weight of 30 to 60 g/m2, especially 40 to g/m2, where the carrier strip maybe made of paper as well. The resulting seed tape is both inexpensive and efficient. According to the invention, the water-repellent material may be wax, stearin, paraffin or caoutchouc applied onto the plane material of the germinating unit as a hot melt and subsequently cured. These substances and this way of application turned out to provide a particularly efficient barrier on top of the individual germinating units. According to the invention, the water-repellent material may be plastics, such as polylactide (PLA), optionally polylactide (PLA) plus polysaccharides. In this manner the resulting water-repellent barrier is mechanically strong, and accordingly it presents an improved tolerance to animals or birds. Furthermore, a narrow zone of water-repellent material may be provided at or adjacent the lower edge of each germinating unit As a result, the water contained in each germinating unit is not immediately passed downwards into the ground in the situation where the seed tape is bedded out in particularly dry ground. In addition it is ensured that the lower portion of the seed tape ensures an improved water-air proportion at the lower portion of the germinating units while said seed tape is placed in a bedding out box. According to the invention, the tape maybe continuously manufactured as the germinating units maybe manufactured by means of one or more paper ribbons of a width twice the width of the completed tape, a zone of water-repellent material of a double width being applied onto the centre of said paper ribbon or ribbons, whereafter said ribbon or ribbons are subsequently slotted through the centre of the water-repellent zone. The resulting seed tape is particularly inexpensive. Moreover, a deterrent may according to the invention be added to the water-repellent material, said deterrent preferably being a substance affecting the sense of smell or taste of animals or birds. In this manner the tendency of animals or birds picking in and optionally damaging the seed tape has been reduced. Finally, the narrow water-repellent zone may according to the invention at the ends be extended a short distance downwards along the vertical edges of each germinating unit, such as for instance 2 to 5 mm. In this manner the tendency of water evaporating from the ends of the germinating units projecting beyond the ground has been further reduced. In the introduction to the description it is mentioned that each germinating unit includes a mixture of carrier, at least one additive and optionally adjuvants in addition to one or more seeds. The term “carrier” is here inter alia to be construed as one or more of the substances: silica, vermiculite, perlite, zeolite, cellulose materials, such as wood fibres and sphagnum, clay, optionally burned clay, mineral fibres, such as rock wool or the like substances, whereby it is possible to obtain a desired degree of water retaining capacity, water conveying capacity, ion exchanging properties etc. The term “adjuvants” are here in principle to be construed as all substances compatible with the remaining, selected substances, and as substances with a favourable effect on the storing, the germination and the growth of the seed and the later sprout. The adjuvants can for instance include: pesticides, including herbicides, insecticides, especially systemic insecticides, fungicides, virae, cultures of bacteria, cultures of fungi, such as Trichoderma, fungus spores, microencapsulated fungicides, eggs from useful. insects, such as predatory nematodes, insect eggs, fertilizers, hormones, enzymes, animal repellants, pH-adjusting agents, carbon, clay particles, trace elements, such as molybdenum, wood fibres or wood powder, kieselguhr, surfactants, silica and other additives with a favourable effect on the germination and the growth of plants, where several substances are available in microencapsulated form with the result that they are protected against biodegradation and a controlled release thereof can be carried out. The adjuvants can also include potassium nitrate and sodium chloride. These substances can optionally be joined by means of a binder, which for instance includes polyvinyl alcohol, polyethylene glycol or other plant-compatible binders, such as water or water containing polysaccharides or mixtures thereof. BRIEF DESCRIPTION OF THE DRAWINGS The invention is explained in detail below with reference to the drawing, in which FIG. 1 illustrates an embodiment of a seed tape according to the invention, FIG. 2 is a perspective view of a germinating unit including a zone of water-repellent material at the top, FIG. 3 is a perspective view of a portion of a seed tape bedded out in the ground, a small portion of said seed tape projecting beyond the surface of the ground, FIG. 4 is a perspective view of a germinating unit provided with a narrow zone of water-repellent material both at the top and at the bottom, FIG. 5 is a perspective view of a germinating unit, where the narrow zone of water -repellent material at the top has been carried a short distance downwards along the two vertical edges of the germinating unit, and FIG. 6 is a perspective view of a portion of a continuous length suited for the manufacture of the germinating unit according to the invention. BEST MODE FOR CARRYING OUT THE INVENTION The seed tape 1 shown in FIG. 1 includes successively arranged germinating units 2a, 2b, 2c etc., which can be coherent or secured to a carrier strip 3. The carrier strip 3 is formed by at least one layer of biodegradable material, and each germinating unit 2a, 2b, 2c is made of a plane material, preferably paper, in one or more layers. The seed tape and consequently each germinating unit are intended to be vertically bedded out in the ground or in a suitable growth substrate. In addition to one or more seeds 6, each germinating unit includes a mixture of carrier 7, at least one additive 9 and optionally adjuvants 8. All these substances encircle the seed 6. They can for instance be glued onto the germinating unit by means of a binder not shown. As illustrated in FIG. 2, each germinating unit 2a is provided with at least one narrow zone 5 of water-repellent material across said unit, adjacent or at least up to the upper edge 4 of said unit, where the narrow zone penetrates the plane material of the germinating unit throughout the entire thickness thereof. The narrow zone 5 can have a heighth of at least 1 mm. The heighth can also be in the range 3.5 to 10 mm The height his preferably 4 to 8 mm, especially 5 mm. h can also be 5 to 10% of the height H of the germinating unit. The plane material of the germninating units 2a, 2b, 2c etc. can be paper, preferably paper of a weight of 30 to 60 g/m2, especially 40 to 50 g/m2. The carrier strip 3 can also be made of paper. The water-repellent material of the narrow zone 5 can be silicone or silicone oil. The water-repellent material of the above zone can also be wax, stearin, paraffin or caoutchouc applied onto the plane material of the germinating unit as a hot melt and subsequently cured. In addition, the water-repellent material of the narrow zone 5 can be plastics, such as polylactide (PLA), optionally polylactide (PLA) plus polysaccharides. FIG. 3 shows how the upper end of a seed tape 1 bedded out can project slightly by mistake from the ground, i.e. Beyond the surface 12 of the ground. Without the above zone 5 of water-repellent material a risk applies of the moisture contained in the germinating unit penetrating upwards through said germinating unit so as to evaporate above the surface of the ground. The latter applies in particular to the situation where the bedding out site is subjected to much wind and/or where the sun is shining on the projecting portion of the seed tape. The zone 5 of water-repellent material prevents the disadvantageous evaporation of water from the germinating unit As illustrated in FIG. 4, each germinating unit 2a, 2b, 2c can be provided with a narrow zone 5′ of water-repellent material at its lower edge 14 as well with the result that the release of water to a dry ground below said germinating unit is considerably reduced. FIG. 6 shows how a seed tape can be manufactured by means of continuous webs of paper 16, 17. These webs are of a width corresponding to twice the height of a germinating unit. A zone 15 of water-repellent material is applied onto the centre of the web, said zone 15 being of a width which is equal to 2 h. When the webs 16, 17 are slotted at the centre, i.e. along the line o, the complete seed tape is almost obtained. A carrier strip 3 must, however, be glued onto the web, optionally after the separation of the individual germinating units 2a, 2b, 2c. In the latter situation, the germinating units present a predetermined mutual distance and are glued to the cairier strip 3. The water-repellent material of the zone 5, 5′ can be admixed a deterrent, preferably a substance affecting the sense of smell or taste of animals or birds. As illustrated in FIG. 5, the narrow zone 5 of water-repellent material can be extended at the ends a short distance downwards, cf. at 5a and 5b, whereby the zone extends slightly downwards along the vertical edges 18a and 18b of each germinating unit 2a. In connection with the additive or additives 9 included in the mixture of substances encircling the seed 6, cf. above, it should be noted that it is a question of one or more water-absorbing materials, such as superabsorbing polymers (SAP). These materials can for instance be cross-linked polyacrylic acids, cross-linked isobutylene-maleic acid-copolymer derivatives, salts of cross-linked starch-polyacrylic acid, salts of cross-linked polyvinylalcohol-polyacrylic acids, cross-linked polyvinylalcohol derivatives, cross-linked polyethylene-glycol derivatives and cross-linked carboxymethylcellulose derivatives. When watered, the water-absorbing materials can include large amounts of water of benefit to the seed 6. The purpose of the narrow zone 5 of water-repellent material is to avoid loss of water from the additive or the additives 9. The invention may be modified in many ways without thereby deviating from the scope of the invention.
<SOH> BACKGROUND ART <EOH>When the tape is to be vertically positioned, the bedding out of a seed tape is encumbered with the problem that said seed tape is not positioned sufficiently deeply in the earth. A small piece of the upper end of the tape projects from the earth, and long periods of windy weather or sunshine imply that the germinating units of the seed tape dry up because each germinating unit acts as a wick for the transport of the moisture to the surface of the ground, and accordingly the wind or sun dries up the germinating units through the projecting end of the seed tape. The latter is a rather unsatisfactory effect.
<SOH> BRIEF DESCRIPTION OF THE INVENTION <EOH>The object of the invention is to provide a seed tape of the above type and which ensures that although a small piece of the seed tape projects from the ground then the germinating units are not easily dried up. The seed tape according to the invention is characterised in that each germinating unit is provided with at least one narrow zone of water-repellent material across said unit, adjacent or at least up to the upper edge of said unit, where the water-repellent material penetrates the plane material of the germinating unit throughout the entire thickness thereof. As a result, each germinating unit is provided with a water-repellent barrier or seal in the upward direction, said barrier or seal completely eliminating, optionally considerably reducing the moisture-evaporating tendency of the upper end of said germinating units. According to the invention the water-repellent material may be silicone or silicone oil which turned out to be particularly easy to apply and being very efficient in practice. Furthermore, the narrow zone of water-repellent material may according to the invention be of a height of at least 1 mm, which turned out to be particularly advantageous. In addition, the narrow zone of water-repellent material may according to the invention be of a height of 3.5 to 10 mm, preferably 4 to 8 mm, especially 5 mm. These widths turned out to be particularly advantageous. According to the invention, the narrow zone of water-repellent material may be of a height of 5 to 10% of the height of the germinating unit, which turned out to be a particularly advantageous embodiment. Moreover, the plane material of the germinating units may according to the invention be paper, preferably of a weight of 30 to 60 g/m 2 , especially 40 to g/m 2 , where the carrier strip maybe made of paper as well. The resulting seed tape is both inexpensive and efficient. According to the invention, the water-repellent material may be wax, stearin, paraffin or caoutchouc applied onto the plane material of the germinating unit as a hot melt and subsequently cured. These substances and this way of application turned out to provide a particularly efficient barrier on top of the individual germinating units. According to the invention, the water-repellent material may be plastics, such as polylactide (PLA), optionally polylactide (PLA) plus polysaccharides. In this manner the resulting water-repellent barrier is mechanically strong, and accordingly it presents an improved tolerance to animals or birds. Furthermore, a narrow zone of water-repellent material may be provided at or adjacent the lower edge of each germinating unit As a result, the water contained in each germinating unit is not immediately passed downwards into the ground in the situation where the seed tape is bedded out in particularly dry ground. In addition it is ensured that the lower portion of the seed tape ensures an improved water-air proportion at the lower portion of the germinating units while said seed tape is placed in a bedding out box. According to the invention, the tape maybe continuously manufactured as the germinating units maybe manufactured by means of one or more paper ribbons of a width twice the width of the completed tape, a zone of water-repellent material of a double width being applied onto the centre of said paper ribbon or ribbons, whereafter said ribbon or ribbons are subsequently slotted through the centre of the water-repellent zone. The resulting seed tape is particularly inexpensive. Moreover, a deterrent may according to the invention be added to the water-repellent material, said deterrent preferably being a substance affecting the sense of smell or taste of animals or birds. In this manner the tendency of animals or birds picking in and optionally damaging the seed tape has been reduced. Finally, the narrow water-repellent zone may according to the invention at the ends be extended a short distance downwards along the vertical edges of each germinating unit, such as for instance 2 to 5 mm. In this manner the tendency of water evaporating from the ends of the germinating units projecting beyond the ground has been further reduced. In the introduction to the description it is mentioned that each germinating unit includes a mixture of carrier, at least one additive and optionally adjuvants in addition to one or more seeds. The term “carrier” is here inter alia to be construed as one or more of the substances: silica, vermiculite, perlite, zeolite, cellulose materials, such as wood fibres and sphagnum, clay, optionally burned clay, mineral fibres, such as rock wool or the like substances, whereby it is possible to obtain a desired degree of water retaining capacity, water conveying capacity, ion exchanging properties etc. The term “adjuvants” are here in principle to be construed as all substances compatible with the remaining, selected substances, and as substances with a favourable effect on the storing, the germination and the growth of the seed and the later sprout. The adjuvants can for instance include: pesticides, including herbicides, insecticides, especially systemic insecticides, fungicides, virae, cultures of bacteria, cultures of fungi, such as Trichoderma, fungus spores, microencapsulated fungicides, eggs from useful. insects, such as predatory nematodes, insect eggs, fertilizers, hormones, enzymes, animal repellants, pH-adjusting agents, carbon, clay particles, trace elements, such as molybdenum, wood fibres or wood powder, kieselguhr, surfactants, silica and other additives with a favourable effect on the germination and the growth of plants, where several substances are available in microencapsulated form with the result that they are protected against biodegradation and a controlled release thereof can be carried out. The adjuvants can also include potassium nitrate and sodium chloride. These substances can optionally be joined by means of a binder, which for instance includes polyvinyl alcohol, polyethylene glycol or other plant-compatible binders, such as water or water containing polysaccharides or mixtures thereof.
20050325
20070313
20051208
94134.0
0
PALO, FRANCIS T
SEED TAPE
SMALL
0
ACCEPTED
2,005
10,529,440
ACCEPTED
Information reproduction/i/o method using dot pattern, information reproduction device, mobile information i/o device, and electronic toy
The present invention proposes a dot pattern on which code information and x and y coordinate information can be defined even if the dot pattern is extremely small, and proposes an information reproducing method and an information reproducing device based on the dot pattern. More specifically, a medium such as a printed material on which is formed a dot pattern portion by arranging in accordance with a given rule dots generated by a dot code generating algorithm in order to recognize various kinds of multimedia information is scanned as image data by scanning means. Then, the image data is converted into code data. Multimedia information corresponding to the code data is read out of storing means to be reproduced.
1. An information reproducing method using a dot pattern, comprising the steps of: scanning a medium as image data by scanning means such as a printed material on which is formed a dot pattern portion, which formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm, in order to recognize various kinds of multimedia information; converting the image data of the dot pattern portion into code data; and reading multimedia information corresponding to the code data out of storing means to reproduce the multimedia information. 2. The information reproducing method using a dot pattern according to claim 1, wherein the medium is a printed material or a picture and the dot pattern portion is formed so as to recognize voice information corresponding to image of the medium. 3. The information reproducing method using a dot pattern according to claim 1 or 2, wherein the dot pattern portion includes a plurality of areas which are separately printed depending on image of the printed material. 4. The information reproducing method using a dot pattern according to claim 1 or 2, wherein the dot pattern portion is formed on a seal member which can be attached to the printed material or a card. 5. An information reproducing device using a dot pattern comprising: scanning means for scanning image data of a dot pattern portion formed on a medium such as a printed material, the dot pattern portion being formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm, in order to recognize various kinds of multimedia information, the information reproducing device; storing means for, after the image data is digitalized into numeric values, storing multimedia information corresponding to the dot pattern portion based on the numeric values; and outputting means for reproducing the multimedia information of the storing means. 6. An information reproducing device using a dot pattern comprising: a touch panel including a transparent film on which is formed a dot pattern portion that is formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm, in order to recognize various kinds of multimedia information; scanning means for, after the touch panel is set to display means of an electronic device, scanning image data of the dot pattern portion of the touch panel following instruction information displayed on the display means; and an electronic device for digitalizing the image data into numeric values and reading multimedia information corresponding to the dot pattern portion based on the numeric values out of storing means and reproducing the multimedia information. 7. The information reproducing device using a dot pattern according to claim 6, wherein an infrared cutoff filter is arranged between the touch panel and the display means. 8. The information reproducing device using a dot pattern according to claim 6 or 7, wherein the electronic device is a personal computer. 9. The information reproducing device using a dot pattern according to claim 6 or 7, wherein the electronic device is a PDA (personal digital assistant). 10. The information reproducing device using a dot pattern according to claim 6 or 7, wherein the electronic device is a portable phone. 11. An information reproducing device using a dot pattern comprising: a mouse pad on which is formed a dot pattern portion that is formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm, in order to recognize various kinds of multimedia information; scanning means which is housed in a case of a coordinate point inputting device in order to capture image data of the dot pattern portion of the mouse pad; and information processing means for digitalizing the image data into numeric values, reading multimedia information corresponding to the dot pattern portion based on the numeric values out of storing means and outputting the multimedia information. 12. An information reproducing device using a dot pattern comprising: scanning means housed in a pen type case to capture image data of a dot pattern portion that is formed on a medium surface by arranging in accordance with a given rule dots generated by a dot code generating algorithm in order to recognize various kinds of multimedia information; storing means for, after the image data is digitalized into numeric value, storing multimedia information such as a voice corresponding to a code or x and y coordinates of the numeric values, or a code which is defined in advance based on the x and y coordinates; and outputting means for outputting the multimedia information stored in the storing means. 13. An information inputting/outputting method by camera inputting comprising the steps of: printing on one surface of a printed material a dot pattern portion formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm in order to recognize various kinds of multimedia information and an information transfer portion which includes a text, an illustration or the like to be recognized as information content; capturing by a camera unit only image data of the dot pattern portion in the printed material and digitalizing the image data into numeric values; and based on the numeric values, outputting information and a program corresponding to the dot pattern portion from a storing portion and executing the information and the program. 14. The information inputting/outputting method by camera inputting according to claim 13, wherein the dot pattern portion and the information transfer portion of the text, the illustration or the like are printed on the one surface to be superimposed. 15. The information inputting/outputting method by camera inputting according to claim 13 or 14, wherein the dot pattern portion comprises x and y coordinate information and the x and y coordinate information is associated with description of the information transfer portion. 16. The information inputting/outputting method by camera inputting according to claim 13 or 14, wherein the dot pattern portion comprises code number information and the code number information is associated with content of the information transfer portion. 17. The information inputting/outputting method by camera inputting according to claim 15, wherein the dot pattern portion of the x and y coordinate information and the dot pattern information of the code number information are printed on a flat surface of the printed material. 18. The information inputting/outputting method by camera inputting according to claim 13 or 14, wherein in the step of capturing image data of the dot pattern portion by a camera unit, the dot pattern portion, which is printed with an ink that absorbs infrared light, is radiated with the infrared light. 19. The information inputting/outputting method by camera inputting according to claim 18, wherein the dot pattern portion is printed with a carbon ink. 20. The information inputting/outputting method by camera inputting according to claim 18, wherein the dot pattern portion is printed with a transparent ink. 21. The information inputting/outputting method according to claim 13 or 14, wherein in the step of capturing image data of the dot pattern portion, the dot pattern portion is radiated with ultraviolet light. 22. A portable information inputting/outputting device using a camera inputting method, comprising: a camera unit for scanning only image data of a dot pattern portion printed on the printed material, the dot pattern portion formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm in order to recognize various kinds of information and an information transfer portion which includes a text, an illustration or the like to be recognized as information content being printed on one surface of the printed material; an image processing portion for digitalizing the image data into numeric values; processing means for reading information of a storing portion corresponding to the dot pattern portion based on the numeric values obtained by the image processing portion; and outputting means for outputting the information read out by the processing means. 23. The portable information inputting/outputting device according to claim 22, further comprising an infrared light emitting portion for radiating the dot pattern portion in the printed material with infrared light. 24. The information portable inputting/outputting device according to claim 22, further comprising an ultraviolet light emitting portion for radiating the dot pattern portion in the printed material with ultraviolet light. 25. The portable information inputting/outputting device according to claim 22, wherein the camera unit is a C-MOS camera. 26. The portable information inputting/outputting device according to claim 22, wherein the camera unit is a CCD camera. 27. The portable information inputting/outputting device according to claim 22, wherein the camera unit is configured separated from the image processing portion, the storing portion, the processing means and the outputting means to carry out transmission via an interface portion. 28. The portable information inputting/outputting device according to claim 22, wherein the camera unit and the image processing portion is configured separated from the storing portion, the processing means and the outputting means to carry out transmission via an interface portion. 29. The portable information inputting/outputting device according to claim 22, further comprising a microphone as an inputting portion. 30. The portable information inputting/outputting device according to claim 22, wherein data of the numeric values of the dot pattern portion input by the camera unit is transmitted to a computer such as a server via a communication card. 31. The portable information inputting/outputting device according to claim 22, wherein data of the numeric values of the dot pattern portion input by the camera unit is transmitted to a computer such as a server via a communication card, and information and a program corresponding to the data is received. 32. The portable information inputting/outputting device according to claim 22, further comprising a GPS (global positioning system) unit for inputting position information. 33. The portable information inputting/outputting device according to claim 22, wherein the portable information inputting/outputting device is a portable phone. 34. The portable information inputting/outputting device according to claim 22, wherein the portable phone includes an integrally-configured camera. 35. A portable electronic toy comprising: a voice storing portion for storing a voice corresponding to a dot pattern portion formed on a medium including a book, a game card, a small article and a toy so as to recognize the voice; a camera for capturing image data of the dot pattern portion; a processing portion for processing the image data captured by the camera and reproducing by a speaker a corresponding voice out of the voice storing portion; and a case main body for housing the voice storing portion, the speaker and the processing portion. 36. The portable electronic toy according to claim 35, wherein the case main body includes a liquid crystal (LC) display. 37. The portable electronic toy according to claim 35, wherein the dot pattern portion is printed on a versus game card. 38. A portable electronic toy comprising: imaging means for scanning image of a dot pattern portion formed on a toy such as a figure or the like; and a processing portion for digitalizing image data scanned by the imaging means into numeric values, reading voice data corresponding to the numeric values from a voice storing portion and outputting the voice data by a speaker. 39. The portable electronic toy according to claim 38, further comprising lighting means for lighting the dot pattern portion. 40. A figure unit with an information outputting function by camera inputting, including a figure of a given shape, the figure unit comprising: a camera for scanning only image data of a dot pattern portion printed on a printed material, the dot pattern portion formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm in order to recognize information and an information transfer portion which includes a text, an illustration or the like to be recognized as information content being printed on one surface of the printed material; an image processing portion for digitalizing the image data into numeric values; and a processing portion and an outputting portion for outputting and executing information and a program of a storing portion corresponding to the dot pattern portion based on the numeric values processed by the image processing portion. 41. The figure unit by camera inputting according to claim 40, wherein the information and the program are stored by voice in the storing portion using a microphone. 42. The figure unit by camera inputting according to claim 41, wherein the figure is a stuffed toy made by stuffing an elastic material in an outer skin of a predetermined shape. 43. A figure unit with an information outputting function by camera inputting, the figure unit comprising: a camera unit configured by including in a figure of a given shape a camera for capturing only image data of a dot pattern portion printed on a printed material, the dot pattern portion formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm in order to recognize information and an information transfer portion which includes a text, an illustration or the like to be recognized as information content being printed on one surface of the printed material and an image processing portion digitalizing the image data into numeric values; an outputting unit including a processing portion and an outputting portion for outputting and executing information and a program of a storing portion corresponding to the dot pattern portion based on the numeric values processed by the image processing portion in the camera unit; and an interface portion for mediating communication between the camera unit and sand outputting unit. 44. The figure unit according to claim 43, wherein the outputting unit is a general-purpose personal computer. 45. A mouse pad on which is formed a dot pattern portion formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm in order to recognize various kinds of multimedia information. 46. A mouse comprising scanning means for scanning a medium on which is formed a dot pattern portion formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm in order to recognize various kinds of multimedia information. 47. An electronic information device comprising: scanning means for scanning a medium surface on which dots are arranged in accordance with a given rule by a dot code generating algorithm in order to recognize various kinds of multimedia information; storing means for, after image data of the scanned medium is converted into numeric values, storing multimedia information corresponding to the numeric values; and outputting means for reading the multimedia information stored in the storing means to output the multimedia information, the scanning means, the storing means and the outputting means being housed in a pen type case. 48. The electronic information device according to claim 47, further comprising inputting means for inputting the multimedia information into the storing means. 49. A tablet on which is formed a dot pattern portion formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm in order to recognize various kinds of multimedia information. 50. A computer executable program for registering a paper icon which has a dot pattern portion formed on a medium and code information associated with the paper icon by using a scanner connected to an information processing device, the program comprising the steps of: designating a display icon displayed on a display screen; setting allocation of the paper icon to a ON state by selection on the display screen; instructing the scanner about scanning processing of the paper icon on the display screen or by a voice data output while the ON state is kept; after the scanning processing is performed based on the step of instructing, extracting code information from image data obtained by the scanning processing; and associating the code information with the display icon designated in the step of designating. 51. The computer executable program according to claim 50, further comprising the steps of: deleting from the display screen the display icon corresponding to the paper icon registered; and executing a function of the display icon associated with the code information when the paper icon is scanned by the scanner.
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique of optically scanning dot pattern information formed on a printed material and reproducing various kinds of information corresponding to the dot pattern information. 2. Description of the Related Art Heretofore, there has been proposed a voice emitting toy for reading a barcode printed on a picture book or a game card using an optical sensor and emitting a particular voice. Such a voice emitting toy enables to read from a memory various kinds of voice information corresponding to a read barcode to reproduce the voice information. However, such a technique using a barcode requires a dedicated area on paper to be reserved for printing the barcode, and the barcode is only for an information processing system to read, and a code description of the barcode can not be visually understood by a reader of a book including a picture book. Since the barcode is printed on a limited paper space, a reader feels it unpleasant and the barcode sometimes may reduce a product value of a book including a picture book. Further, since the barcode, as mentioned above, can not be printed over letters, graphics or symbols printed on a paper sheet, when these letters, graphics, symbols and the like are used to reproduce voices, the barcode has to be printed near them, which presents a trouble such that it is difficult for a reader to intuitively know voice information or the like added on the letters or the like. Regarding this point, a “dot code” technique disclosed in the Japanese Laid-Open patent publication No. 10-261059 proposes a method for scanning code information printed by a dot pattern to reproduce information. In the related art, data is defined by way for arranging a dot pattern in a block field, and a marker is defined by a dot pattern which is different from the data dot pattern to serve as a synchronization signal. According to this technique, a dot pattern created by printing dots in the two-dimensional direction on a paper sheet in accordance with a predetermined rule is read by a pen type scanner, and the scanning speed and the scanning direction of this scanner is analyzed by an information processing device thereby to reproduce information including a voice which is associated therewith in advance. However, since such a dot code technique is based on the assumption that dots are dynamically scanned by a scanner, although it can reproduce voice information along letters printed on a paper sheet, it is not adequate to reproduce information only by statically abutting a scanning device to a picture book or the like on which a character and the like are freely arranged and printed. In other words, since this dot code technique requires to carry out more than a predetermined distance of scanning on the x and y coordinates in order to obtain significant code information, it is impossible to associate a minimum area with a dot code and to print the area. SUMMARY OF THE INVENTION The present invention proposes a dot pattern that allows to define code information or the x and y coordinates even if the dot pattern is an minimum area, and an information reproducing method and an information reproducing device based on the dot pattern A first aspect of the invention is configured to include the steps of: scanning as image data by scanning means (602) a medium such as a printed material (606) on which is formed a dot pattern portion (607), the dot pattern portion being formed by arranging in accordance with a given rule dots (605) generated by a dot code generating algorithm, in order to recognize various kinds of multimedia information; converting the image data of the dot pattern portion (607) into code data; and reading multimedia information corresponding to the code data out of storing means to reproduce the multimedia information. The multimedia information here may be any one of followings: voice information, image information, video information, and visible, audible and readable information such as a letter and a symbol. Further, the multimedia information may be digital data for another personal computer, a television system or a radio terminal to reproduce video/image information, text information and the like. Here, on the dot pattern portion (607), code information corresponding to voice data registered in the storing means may be defined or the x and y coordinates may be defined. Also, both of the code information and the x and y coordinates may be defined. In a header of the dot pattern portion (607), a flag may be registered to determine the dot pattern portion is code information or x and y coordinates. The medium may be a picture book or a photograph. The dot pattern portion (607) for recognizing voice information corresponding to image (606b) of the picture book or the like may be printed over the image (606b). The dot pattern portion (607) may be printed on a seal member. The dot pattern portion (607) may be formed on a transparent film (611). In this case, the transparent film may be arranged over a paper sheet, or the transparent film (611) may be attached to display means (613) of an electronic device as a touch panel. Then, the display means (613) is used to display instruction information so as to make a user to operate scanning means. Between the touch panel (612) and the medium such as the paper sheet or the display means (613), an infrared cutoff filter (614) may be arranged. In addition to the case that the touch panel is attached to the aforementioned display means (613), the touch panel may be attached on a book such as a picture book, a figure or the like. Here, the scanning means (602) may be configured separately from an electronic device including a personal computer (608), a PDA and a portable phone, and data communication may be established between them by wire communication, radio communication or optical communication. However, the scanning means (602) may be housed in the electronic device integrally. In this case, the electronic device may be configured by a pen type case or a mouse type case, in addition to the electronic devices. A second aspect of the invention is an information inputting/outputting method by camera inputting comprising the steps of: printing on one surface of a printed material (5) a dot pattern portion (6) formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm in order to recognize various kinds of multimedia information and an information transfer portion (7) which includes a text, an illustration or the like to be recognized as information content; capturing by a camera unit (2) only image data of the dot pattern portion(6) in the printed material (5) and digitalizing the image data into numeric values; and based on the numeric values, outputting information and a program corresponding to the dot pattern portion (6) from a storing portion (10) and executing the information and the program. The dot pattern portion (6) and the information transfer portion (7) comprising of the text or the illustration or the like may be printed on the one surface to be superimposed. The dot pattern portion (6) may be defined by x and y coordinate information and the x and y coordinate information may be associated with content of the information transfer portion (7). The dot pattern portion (6) may be defined by code numeric information and the code numeric information may be associated with content of the information transfer portion (7). The dot pattern portion (6) of the x and y coordinate information and the dot pattern portion (6) of the code numeric information are printed on a flat surface of the printed material (5). The dot pattern portion (6) may be printed with an ink that absorbs infrared light, a carbon ink or a transparent ink. When the camera unit (2) is used to capture image data of the dot pattern portion (6), the dot pattern portion (6) may be radiated with ultraviolet light. Information to be output may be digital data including a voice, image, video and text code. The configuration may be made to output a program in addition to the information of digital data. The information transfer portion (7) to be printed on one surface together with the dot pattern portion (6) may be a text or an illustration. The camera unit (2) may be an image pickup device such as a C-MOS camera or a CCD camera. Hereinafter, what is called “camera unit” may include any imaging means having such a configuration. In addition, the camera unit (2) may be configured separated from the image processing portion (12), the storing portion (10), the processing portion (9) and the outputting portion (15) to carry out transmission via an interface portion. Here, the interface portion may include both function means having an integrally-formed CPU and sound source memory in abstract terms and function means such as a connector for exchanging data. The camera unit (2) and the image processing portion (12) is configured separated from the storing portion (10), the processing portion (9) and the outputting portion (15) to carry out transmission and reception via an interface portion. Communication with the interface portion may be realized by wire communication, radio communication including wireless LAN and blue tooth, or optical communication such as infrared communication. The printed material (5) on which the dot pattern portion (6) is printed may be attached to various mediums via an adhesive agent. The storing portion (10) may store, in addition to information including a text, image and video, a program. Such information and program may be stored in the storing portion (10) via an inputting portion (17). Accordingly, a use can store any voice information as associated with a given dot pattern portion (6) in advance. This inputting portion (17) may be a microphone or a line-in interface. Further, the configuration may be made to mount a communication card (16). Then, the numeric data obtained by digitalizing a dot pattern (1) scanned by the camera unit (2) may be transmitted to a computer (23) such as a server via the communication card (16). This configuration may allow to store a huge amount of multimedia information in a server and reproduce various types of multimedia information via communication. More specifically, a network address (URL: Uniform Resource Locator) is defined on the dot pattern (1), the communication card (16) is used to establish communication to TCP/IP communication network (so-called Internet) and thereby voice data stored at the network address may be downloaded in the storing portion (10) to be reproduced. Here, other than the communication card (16), a GPS (Global Positioning System) receiver (24) maybe further provided. This makes it possible to reproduce multimedia information based on position information together with content scanned from the dot pattern (1) A third aspect of the invention is an information inputting/outputting device using a portable-phone camera, comprising: a camera unit (102) for scanning only image data of the dot pattern portion (6) printed on the printed material (5), the dot pattern portion (6) formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm in order to recognize various kinds of information and an information transfer portion (7) which includes a text, an illustration or the like to be recognized as information content being printed on one surface of the printed material; an image processing portion (112) for digitalizing the image data into numeric values; an interface portion (119) for transferring the digitalized numeric information so as to output from a portable phone (110) and execute information and a program corresponding to the dot pattern portion (6). Since such a camera equipped portable phone is used, the information reproducing device can be configured simply. Such a camera equipped portable phone may be an information-processing-device-integrated portable phone such as i-mode phone provided from NTT Docomo Inc. This information processing device includes a central processing unit, a storing device (memory), a liquid crystal display screen and the like. In the storing device (memory), a program, voice data, video data and text data can be stored. An operation system (OS) mounted on a portable phone may be Toron, Symbian, Windows CE available from Microsoft Corporation, LINUX, PALM-OS or the like. Such a camera equipped portable phone may be configured so that a memory card such as an SD card, a memory stick, a SIMM card can be mounted on the portable phone and further, content data is recorded in the memory card to be reproduced. A fourth aspect of the invention is a portable electronic toy comprising: a voice storing portion (804) for storing a voice corresponding to a dot pattern portion (803) formed on a medium (802) including a book, a game card, a small article and a toy, the dot pattern portion (803) on which numeric data or code information are recoded in order to recognize various voices; a camera (810) for capturing image data of the dot pattern portion (803); a processing portion (806) for processing the image data captured by the camera (810)and reading voice data corresponding the numeric data out of the voice storing portion (804) to output the voice data by use of a speaker (805); and a case main body (808) for housing the voice storing portion (804), the speaker (805) and the processing portion (806). This case main body (808) may be configured to be of organizer size. Besides, the case main body (808) may be provided with an LC display (812). Further, the dot pattern portion (803) can be printed on a versus game card. Or, the dot pattern portion (803) may be formed on a miniature figure (hereinafter referred to as “mini figure”) of an animation character on sale in convenience stores and the like as a candy toy or a seal on which the dot pattern portion (803) is printed may be attached to such a mini figure. Furthermore, in order to allow intercommunication between plural portable electronic toys (821), a connector for a connection cable may be provided on the case main body (823). In this case, the connector may be a USB connector or any connector in conformity with IEEE 1394. Further, communication may be used by Blue tooth, wireless LAN or infrared data communication. A fifth aspect of the invention provides a configuration with an information outputting function by camera inputting, in a figure (218) of a given shape, the configuration comprising: a camera (202) for scanning only image data of a dot pattern portion (6) printed on a printed material (5), the dot pattern portion (6) formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm in order to recognize information and an information transfer portion (7) which includes a text, an illustration or the like to be recognized as information content being printed on one surface of the printed material; an image processing portion (212) for digitalizing the image data into numeric values; and a processing portion (209) and an outputting portion (215) for outputting and executing information and a program of a storing portion (210) corresponding to the dot pattern portion (6) based on the numeric values processed by the image processing portion (212). Besides, a speaker (214) may be provided as an outputting portion (215) to output a voice. Further, the storing portion (210) maybe configured to store information and a program from the outside by use of a microphone (217). Further, the figure (218) may be configured to be a stuffed toy (231) made by stuffing an elastic material in an outer skin of a predetermined shape. Furthermore, the configuration with an information outputting function by camera inputting may include in a figure (218): a camera unit (A) configured by including a camera (202) for capturing only image data of a dot pattern portion (6) printed on a printed material (5), the dot pattern portion (6) formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm in order to recognize information and an information transfer portion (7) which includes a text, an illustration or the like to be recognized as information content being printed on one surface of the printed material and an main processor (209) digitalizing the image data into numeric values; an outputting unit (B) including a processing portion (9) and an outputting portion (15) for outputting and executing information and a program of a storing portion (10) corresponding to the dot pattern portion (6) based on the numeric values processed by the image processing portion (12) in the camera unit (A); and an interface portion for mediating communication between the camera unit (A) and sand outputting unit(B). BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1(a) and 1(b) are block diagrams each for illustrating a configuration of an information reproducing method using a dot pattern according to the present invention, and more specifically, FIG. 1(a) is an explanatory view of dot code generation and FIG. 1(b) of dot pattern recognition. FIG. 2 is an elevation view illustrating an example of the dot pattern. FIG. 3 is a functional block diagram for explaining a state of a picture-book and the information reproducing method. FIGS. 4(a) and 4(b) are block diagrams each illustrating another configuration of the information reproducing method using a dot pattern, and specifically, FIG. 4(a) is an explanatory view of dot code generation while FIG. 4(b) is of dot pattern recognition. FIG. 5 is an elevation view illustrating another example of dot pattern. FIG. 6 is an elevation view illustrating another example of dot pattern. FIG. 7 is an elevation view illustrating another example of dot pattern. FIG. 8 is an elevation view illustrating another example of dot pattern. FIG. 9 is an elevation view illustrating an example of a picture book on which a picture of and a text of a story are printed. FIG. 10 is an elevation view illustrating another example of a picture book on which pictures and story texts are printed. FIG. 11 is an elevation view illustrating still another example of a picture book on which pictures and story texts are printed. FIG. 12 is a perspective view for explaining a touch panel on which a dot pattern portion is formed. FIG. 13 is an exploded side view for explaining a touch panel on which a dot pattern portion is formed. FIG. 14 is a cross sectional view for explaining another embodiment including a mouse pad on which a dot pattern portion is formed and a mouse type camera. FIG. 15 is a plane view for illustrating a mouse type camera. FIGS. 16(a) and 16(b) are views each illustrating another embodiment of the mouse type camera and more specifically, FIG. 16(a) is a plane view and FIG. 16(b) is a side view. FIGS. 17(a) and 17(b) are views each illustrating yet another embodiment of the mouse type camera and more specifically, FIG. 17(a) is a plane view and FIG. 17(b) is a side view. FIG. 18 is a cross sectional view illustrating another embodiment of using as a tablet a printed surface on which a dot pattern portion is formed. FIG. 19 is a cross sectional view illustrating another embodiment in which a camera is mounted at an end of a pen member. FIG. 20 is a cross sectional view illustrating yet another embodiment in which a camera is mounted at an end of a pen member. FIGS. 21(a) and 21(b) are block diagrams each illustrating a configuration of an information inputting/outputting method by camera inputting according to the invention, and specifically, FIG. 21(a) is an explanatory view of dot code generation and FIG. 21(b) of dot pattern recognition. FIG. 22 is an elevation view illustrating an example of a dot pattern. FIG. 23 is an explanatory view for showing a dot pattern formed of x and y coordinates information. FIG. 24 is a view for explaining a method of recognizing and processing a dot pattern formed of x and y coordinates information. FIG. 25 is an explanatory view for showing a dot pattern formed of code numeric information. FIG. 26 is a view for explaining a method of recognizing and processing a dot pattern formed of code numeric information. FIG. 27 is an explanatory view for explaining a way of scanning by a camera only image data of a dot pattern portion printed with a carbon ink, separately from an information transfer portion, which include text and figures, printed with a con-carbon color ink by radiating a printed material with infrared light. FIG. 28 is a functional block diagram for explaining an embodiment of a portable information inputting/outputting device using an information inputting/outputting method by camera inputting. FIG. 29 is a functional block diagram for explaining an embodiment of a portable information inputting/outputting device using an information inputting/outputting method by camera inputting. FIG. 30 is a perspective view showing a portable information inputting/outputting device which is housed in a compact case. FIGS. 31(a) to 31(d) are views each showing a portable information inputting/outputting device which is housed in a compact case of another shape, and more specifically, FIG. 31(a) is a perspective view showing the whole case, FIG. 31(b) is a plane view, FIG. 31(c) is a side view and FIG. 31(d) is an elevation view. FIG. 32 is a functional block diagram for explaining an embodiment in which a camera unit and an outputting portion are configured separately. FIG. 33 is a functional block diagram for explaining an embodiment in which a camera unit and an outputting portion are configured separately. FIG. 34 is a perspective view showing a device in which a camera unit portion and an outputting-side main body are separated. FIGS. 35(a) to 35(d) are perspective views each showing another form of a camera unit portion, and more specifically, FIG. 35(a) shows a pen type camera unit, FIG. 35(b) shows a pen type camera unit, FIG. 35(c) shows a mouse type camera unit and FIG. 35(d) shows a stethoscope type camera unit. FIG. 36 is a functional block diagram for explaining an embodiment of an information inputting device using a camera for portable phone. FIG. 37 is a functional block diagram for explaining an embodiment of an information inputting device using a camera. FIG. 38 is an explanatory view showing an information inputting device using a camera for portable phone. FIG. 39 is an explanatory view showing an information inputting device using a camera for portable phone. FIG. 40 is an explanatory view for showing a portable phone in which an information inputting device is integrated. FIG. 41 is a functional block diagram of a portable electronic device according to the embodiment of using a dot pattern portion. FIG. 42 is an elevation view for showing an embodiment of a portable electronic device using a dot pattern portion. FIG. 43 is a right side view showing a portable electronic toy. FIG. 44 is a left side view showing a portable electronic toy. FIG. 45 is a bottom view showing a portable electronic toy. FIG. 46 is a perspective view for showing an embodiment of a portable electronic toy which emits a voice mainly corresponding to a mini figure. FIG. 47 is a functional block diagram of a portable electronic toy according to the embodiment. FIG. 48 is a perspective view showing a plurality of voice emitting toys being connected to a controller unit. FIG. 49 is an elevation view showing n embodiment of portable electronic toy which utilizes optical character recognition (OCR). FIG. 50 is a functional block diagram of a portable electronic toy showing an embodiment which utilizes a magnetic member. FIG. 51 is a functional block diagram of a portable electronic toy showing an embodiment which utilizes a shooting pen of a camera or the like. FIG. 52 is a functional block diagram for showing a figure unit having an information outputting function by camera inputting, in which a camera unit and an outputting unit are configured separately. FIG. 53 is a functional block diagram for explaining a modified example of the embodiment. FIG. 54 is a functional block diagram for showing a figure unit having an information outputting function by camera inputting, in which a camera unit and an outputting unit are configured separately. FIG. 55 is a functional block diagram for explaining a modified example of the embodiment. FIGS. 56(a) to 56(d) are perspective views each showing a figure with a camera unit and more specifically, FIG. 56(a) is a view of a doll, FIG. 56(b) is of a soccer ball, FIG. 56(c) is of a bicycle and FIG. 56(d) is of an animal. FIG. 57 is a perspective view showing figure units put on the center battle stage of a new simulation board game. FIG. 58 is a cross sectional view for explaining another embodiment of the invention in which a camera unit and an outputting unit are housed in a stuffed toy that is one form of the figure. FIG. 59 is a cross sectional view for explaining another embodiment in which a camera unit and an outputting unit are housed in a stuffed toy that is one form of the figure. FIG. 60 is a cross sectional view for explaining another embodiment of the invention in which a camera unit and an outputting unit are housed in a stuffed toy that is one form of the figure. FIG. 61 is a cross sectional view of a camera. FIG. 62 is a view for explaining an image pickup area of a camera. FIG. 63 is a perspective view for showing information dots of four blocks. FIG. 64 is a view for explaining the image-pickup center position of a camera and the input procedure of a sub block. FIG. 65 is a view for explaining the image-pickup center position of a camera and the input procedure of a sub block. FIG. 66 is a view for explaining the image-pickup center position of a camera and the input procedure of a sub block. FIG. 67 is a view for explaining the image-pickup center position of a camera and the input procedure of a sub block. FIG. 68 is a view for explaining a configuration of a pen type scanner. FIG. 69 is a view illustrating an example of use of the embodiment. FIG. 70 is a view illustrating an example of use of the embodiment. FIG. 71 is a view illustrating an example of use of the embodiment. FIG. 72 is a view illustrating an example of use of the embodiment. FIG. 73 is a view illustrating an example of use of the embodiment. FIG. 74 is a view illustrating an example of use of the embodiment. FIG. 75 is a view illustrating an example of use of the embodiment. FIG. 76 is a view illustrating an example of use of the embodiment. FIG. 77 is a view illustrating an example of use of the embodiment. FIG. 78 is a view illustrating an example of use of the embodiment. FIG. 79 is a view illustrating an example of use of the embodiment. FIG. 80 is a view illustrating an example of use of the embodiment. FIG. 81 is a view illustrating an example of use of the embodiment. FIG. 82 is a view illustrating an example of use of the embodiment. FIG. 83 is a view illustrating an example of use of the embodiment. FIG. 84 is a view illustrating an example of use of the embodiment. FIG. 85 is a view illustrating an example of use of the embodiment. FIG. 86 is a view illustrating an example of use of the embodiment. FIG. 87 is a view illustrating an example of use of the embodiment. FIG. 88 is a view illustrating an example of use of the embodiment. FIG. 89 is a view illustrating an example of use of the embodiment. FIG. 90 is a view illustrating an example of use of the embodiment. FIG. 91 is a view illustrating an example of use of the embodiment. FIG. 92 is a view illustrating an example of use of the embodiment. FIG. 93 is a view illustrating an example of use of the embodiment. FIG. 94 is a view illustrating an example of use of the embodiment. FIG. 95 is a view illustrating an example of use of the embodiment. FIG. 96 is a view illustrating an example of use of the embodiment. FIG. 97 is a view illustrating an example of use of the embodiment. FIG. 98 is a view illustrating an example of use of the embodiment. FIG. 99 is a view illustrating an example of use of the embodiment. FIG. 100 is a view illustrating an example of use of the embodiment. FIG. 101 is a view illustrating an example of use of the embodiment. FIG. 102 is a view illustrating an example of use of the embodiment. FIG. 103 is an explanatory view (1) of specifications of dot pattern according to an embodiment. FIG. 104 is an explanatory view (2) of specifications of dot pattern according to the embodiment. FIG. 105 is an explanatory view (3) of specifications of dot pattern according to the embodiment. FIG. 106 is an explanatory view (4) of specifications of dot pattern according to the embodiment. FIG. 107 is a view (1) for explaining a device configuration of means for scanning a dot pattern portion according to the embodiment. FIG. 108 is a view (2) for explaining a device configuration of means for scanning a dot pattern portion according to the embodiment. FIG. 109 is a view (3) for explaining a device configuration of means for scanning a dot pattern portion according to the embodiment. FIG. 110 is a view (4) for explaining a device configuration of means for scanning a dot pattern portion according to the embodiment. FIG. 111 is a view (5) for explaining a device configuration of means for scanning a dot pattern portion according to the embodiment. FIG. 112 is a view (6) for explaining a device configuration of means for scanning a dot pattern portion according to the embodiment. FIG. 113 is a view (7) for explaining a device configuration of means for scanning a dot pattern portion according to the embodiment. BEST MODE FOR CARRYING OUT THE INVENTION FIGS. 1(a) and 1(b) are block diagrams each showing a configuration of an information reproducing method using a dot pattern of the present invention and specifically, FIG. 1(a) explains generation of a dot code and FIG. 1(b) explains recognition of a dot pattern. FIG. 2 is an elevation view illustrating an example of a dot pattern and FIG. 3 is a functional block diagram for explaining a state of a picture book and the information reproducing method. The information reproducing method using a dot pattern of the invention includes generation of a dot pattern 601, recognition of the dot pattern 601 and reproducing of voice information corresponding to the dot pattern 601. Specifically, image data of the dot pattern 601 is scanned by a camera 602, which is scanning means, a distortion factor on the image is corrected, the image is converted into numeric values to be digitalized, the digitalized numeric values are divided into a first direction 603 and a second direction 604, its position is read, and voice information corresponding to the dot pattern 601 is then reproduced on a personal computer (hereinafter referred to as “PC”) 608, PDA, portable phone or the like. The camera 602 of FIG. 3 is configured by a pen type scanner, and an image pickup device such as CCD or C-MOS is integrated in the camera. However, the camera can be implemented by a digital camera or a camera mounted on a mobile terminal including a portable phone, as described later. Generation of the dot pattern 601 according to the invention is performed in such a manner that: in order to recognize voice information, small dots 605 are arranged, by a dot code generating algorithm, in a first direction line 603 in accordance with a predetermine rule, and arranged in a second direction line 604 perpendicular to this first direction line 603 in accordance with a predetermined rule. Then, a mapping table is also generated in a memory in the PC 608 or a memory provided in a camera 602. This first direction line 603 and the second direction line 604 are not limited to those perpendicular to each other, however, they can be crossed forming an angle of 60 degree, for example. Recognition of the dot pattern 601 includes correction of a distortion factor by a lens of the camera 602, correction of a distortion caused by tilt of the camera 602, reproducing of numeric information in the first direction 603 and reproducing of numeric information in the second direction 604. The image data of the dot pattern 601 is captured by using the camera 602 which has an image pickup device such as a C-MOS camera and a CCD camera. The pen type scanner may be replaced by a portable phone equipped with a camera or a camera connected to a portable phone. In the case of such portable phones, control of a JAVA program and the like downloaded in a memory of the portable phone is utilized to reproduce a voice as it is. The image data captured by the camera 602 is processed by an image processing algorithm to extract dots 605, which are subjected to correction of a distortion factor by a lens of the camera 602 by a distortion correcting algorithm. Or, distortion by tilt of the camera 602 with respect to the dot pattern 601 is corrected. The image data captured by the camera 602 is processed by a CPU (central processing unit) of the PC 608 using a predetermined image processing algorithm to extract dots 605. Since distortion caused by the camera 602 itself is corrected by the distortion correcting algorithm. Therefore, even when image data of the dot pattern 601 is captured by a common camera 602 equipped with a lens high in distortion factor, accurate recognition is possible. Also even when the dot pattern 601 is tilt with respect to the screen and scanned by the camera 602, the dot pattern 601 can be accurately captured. Reproducing of numeric information in the first direction 603 is carried out in such a manner that: two lines of the first direction 603 are extracted, dot information between the two lines of the first direction 603 is digitalized, a pattern thereof is recognized by a pattern recognizing algorithm and numeric information in the first direction 603 is reproduced using a mapping table. In reproducing, if line reading cannot be carried out accurately by smudges or noise, a next line is extracted and the same processing is performed. Its information is recorded as numeric correcting information, which is used in correcting when the numeric information is reproduced. Reproducing of numeric information in the second direction 604 is carried out in such a manner that: two lines of the second direction 604 is extracted, dot information between the lines of the second direction line 604 is digitalized, a pattern thereof is recognized by a pattern recognizing algorithm and numeric information in the second direction 604 is reproduced using a mapping table. In reproducing, if line scanning can not be carried out accurately by smudges or noise, a next line is extracted and the same processing is performed. Its information is recorded as numeric correcting information, which is used in correcting when the numeric information is reproduced. The aforementioned dot pattern 601 is configured of a dot pattern portion 607 printed on a printed material 606 such as a picture book and a text book. Image of this dot pattern portion 607 is recognized by the camera 602, corresponding voice information is read from a memory based on numeric data extracted from the image data, and corresponding voice and music are reproduced by outputting means such as a speaker 9 of the PC 608, a PDA or portable phone. FIGS. 4(a) and 4(b) are block diagrams each illustrating another configuration of an information reproducing method using a dot pattern and more specifically, FIG. 4(a) a view for explaining generation of a dot code and FIG. 4(b) is a view for explaining recognition of a dot pattern. FIGS. 5 through 8 are elevation views each showing another example of a dot pattern. As mentioned above, image data captured by a camera 602 is subjected to processing by image processing algorithm to extract dots 5. Since distortion caused by the camera 602 and distortion due to tilt of the camera 602 are corrected by the distortion correcting algorithm, accurate recognition is possible in capturing the dot pattern 601. In recognition of the dot pattern, first, a line composed by successive equally spaced dots 5 is extracted, and it is determined whether or not the extracted line is correct. If the line is not correct, another line is extracted. Next, one extracted line is assumed as a horizontal line. This horizontal line is used as a basis to extract a line which extends vertically from the horizontal line. A vertical line starts from a dot which consists in the horizontal line and the vertical direction is recognized from the fact that the next dot or the third dot is not on the line. Finally, an information area is extracted and information thereof is converted into numeric values to reproduce this numeric information. FIG. 9 is an elevation view illustrating an example of printing of pictures of a picture book and story texts. In such a page, an icon 606a at the upper left side of the page is scanned by the camera 602 and a switch is turned on. Next, a text portion 606c printed of the story corresponding to the picture 6b is scanned by the camera 602. Since dot pattern portions 607 are printed on the icon 606a and the text portion 606c, these dot pattern portions 607 are used to recognize of which area, on which page of the picture book the information is and to make PC 608 reproduce correspondingly-stored voice of the story. For example, dots 5 of the dot pattern portion 607 is printed with a carbon ink while the other portion is printed with a non-carbon color ink so as to be scanned by irradiation of infrared light. FIG. 10 is an elevation view illustrating another example of a picture book on which pictures and story texts are printed. FIG. 11 is an elevation view illustrating still another example of a picture book on which pictures and story texts are printed. The information reproducing method using a dot pattern according to the invention is not limited to a story based picture book, and can be applied to an educational material for teaching mathematics in an easily understood manner as shown in FIG. 10. Also as illustrated in FIG. 11, the information reproducing method according to the invention can be applied to an educational material for teaching music in an easily understood manner. Stored in a memory of a PC 608, a PDA or a portable phone is a content which can be utilized as a picture book emitting music and conversation of central characters and the like as well as pictures of a picture book. Also can be stored are a content which can be utilized an educational material emitting a voice in combination with a toy such as assembly blocks and a content for storing which can be used as a dictionary software for translating by tracing words and text in a foreign language. The information reproducing method using a dot pattern according to the invention can be further utilized in the following way. “Pop Picture Book Which Generates Voice” Taking advantage of a feature that the camera 602 has only to scan or abut on the dot pattern portion 607, the information reproducing method according to the invention can be combined in a “pop picture book” which makes a three-dimensional material appear when a page is opened. After the page is opened, the dot pattern portion 607 is attached to or printed on the inside of the three-dimensional material. When this dot pattern portion 607 is searched and an end of the camera 602 is abutted to the dot pattern portion 607, various voices are outputted, thereby producing a “pop picture book which outputs a voice”. For example, when the page is opened, a “horror house” is opened by pop-up. When a dot pattern portion 607 at a window is traced by the camera 602, a voice of scream of a woman such as “yipe” is reproduced. When a dot pattern portion 607 at a hall is traced by the camera 602, a voice of ominous footstep such as “tap tap” is reproduced. “Creative Picture Book (Creative Book)” A dot pattern portion 607 can be attached to a desired portion of a picture book which is a printed material 6. As the dot pattern portion 607 for a user himself to create content is attached, is can be used as a “creative picture book (creative book)” which is able to set a switch anywhere. For example, a user can create an original story by attaching a dot pattern portion 607 of a set of a picture book, a speech collection, a sound list, sound source data and the like a dot pattern portion 607 of voice or music as a user like to the picture book 6. Further, a seal of a sound source list or an icon seal with a dot pattern portion 607 formed thereon is prepared, a user draws a picture on a picture book which has nothing drawn in advance, and then the user attaches the seal to the picture book to create an original story. With this configuration, a user himself can create a picture book which outputs a voice. “Educational Material Which Outputs Voice” The invention can be used as an “educational material which outputs a voice” dedicated for children, adults, aged people in any generation. For example, an end of the camera 602 is abutted to a dot pattern portion 607 of a printed material 606 and the dot pattern portion 607 is scanned to reproduce a voice. With such a configuration, the invention can be used as language education such as English conversation, child education such as intellectual education and music and teaching aid such as a drill. Since the invention can be used as an input interface printed on a printed material 606 or the like, it is possible to manufacture an interface suitable for each content. Further, it is configured to download dot pattern data to the PC 608 via the general-purpose network such as Internet, when a user freely combines dot pattern data and prints a dot pattern on a paper sheet by a general-purpose printer, then, the user himself can create such a “picture book which outputs a picture” as mentioned above. Further, URL information can be defined on a dot pattern portion 607 of the printed material 606 or another medium. When the URL information is extracted from image data obtained by taking a picture of the dot pattern 607 by a camera 602, a browser program installed in the PC 608 accesses to the aforementioned URL to carry out a predetermined operation. FIG. 12 is a perspective view for explaining a touch panel with a dot pattern portion 607 formed thereon. FIG. 13 is an exploded lateral view for explaining a touch panel with a dot pattern portion 607 formed thereon. A conventional touch panel is configured to be arranged on a monitor screen such as an LCD (liquid crystal display) or a CRT (cathode-ray tube) so that position input to the touch panel is carried out by pushing from above by a finger, a pen or the like following the instruction on the screen seen through. This conventional touch panel has a pair of an upper electrode sheet and a lower electrode sheet, which have transparent electrodes of ITO or the like, arranged opposed to each other on a transparent film, for example, with a spacer which serves as an insulator between the electrodes. Then, a transparent maintaining plate composed of a resin is bounded on a lower surface of the lower electrode sheet via a transparent adhesive layer. However, this presents defects of high cost and difficulty in use due to curling of the surface caused by long-time use. Then, in order to avoid high cost, a touch panel 612 which has a transparent film 611 with a dot pattern portion 607 printed thereon and a popular camera 602 (pen type scanner) are only used. This touch panel 612 is arranged on a screen of a monitor 613 such as an LCD (liquid crystal display) or a CRT (cathode-ray tube) of a PC 608 or the like. Then, tracing by the camera 602 is performed following the instruction on the screen thereby to perform position inputting. Thus, the camera 602 is faced to the touch panel 612 attached onto the monitor screen to capture image data of the dot pattern portion 607. Information corresponding to the dot pattern 607 is recognized on the monitor screen of the PC 608, and various voices or the like stored in the PC are reproduced correspondingly. Dots 5 of the dot pattern portion 607 have a characteristic such that it easily absorbs light when the main component is a carbon. Unless a light beam from the monitor screen is cut off, the image data of the dot pattern portion 607 can not be accurately captured by the camera 602. Then, an infrared cutoff film 614 is arranged between the monitor screen and the touch panel 612 thereby to cut off infrared light emitted from the monitor screen. With this configuration, infrared light emitted from the inside of the camera is only treated as irradiation light, and light reflected from the dots 5 is easy to be recognized thereby facilitating recognition of the dot pattern portion 607, and it can be used as a touch panel of the PC 607. This touch panel 612 enables the camera 602 to be used as a pointer device. Further, by recognizing points successively, it can be used as a trace device. For example, if this touch panel 612 is arranged upward, it can be used as a conventional writing table for tracing. Here, the above-mentioned touch panel is explained as it is mounted on the monitor screen of the PC 608, however, it can be utilized on a display of a PDA, a screen of photographic seal distributor, a screen of an ATM terminal of a bank and the like. FIG. 14 is a cross sectional view illustrating another embodiment including a mouse type camera and a mouse pad with a dot pattern portion 607 formed thereon. FIG. 15 is an elevation view illustrating a mouse type camera. According to this embodiment, a camera 602 is integrated in a mouse-shaped case 615 and combined with a mouse pad 616. A semi-transparent mirror member 617 is mounted inside the mouse-shaped case 615 so as to recognize a surface of the mouse pad 616 via a lower surface 615a of the mouse-shaped case 615 and a dot pattern portion 607 with coordinate information printed on the mouse pad 16 is traced through an open window 618 mounted on the upper surface 615b of the case 615. A button 615c is provided near the window 618. The camera 602 in the mouse-shaped case 615 can be used, when recognizing a mouse pad 616, as an input device in place of a regular mouse. Specifically, the regular mouse can be used to input relative coordinates only, while the camera 602 further allows inputting of absolute coordinates. FIGS. 16(a) and 16(b) show another embodiment of a camera integrated mouse-shaped case. More specifically, FIG. 16(a) is a plan view thereof and FIG. 17(b) is a lateral view thereof. FIGS. 17(a) and 17(b) show yet another embodiment of a camera integrated mouse-shaped case. More specifically, FIG. 17(a) is a plan view thereof and FIG. 17(b) is a lateral view. According to this embodiment, as shown in FIGS. 16(a) and 16(b), the camera 602 is integrated in a protruding end 615d of the mouse-shaped case 615. Since the protruding end 615d is thus formed in the mouse-shaped case 615, it is possible to position the mouse-shaped case 615 at a predetermined position of the mouse pad 616 with ease and to push a button switch 615e, and thereby to recognize a surface of the mouse pad 616 via the lower surface 615a of the mouse-shaped case 615. Here, it is also possible to provide a button switch 615f at the lower surface 615a of the mouse-shaped case 615. Only if the mouse-shaped case 615 is positioned at the predetermined position on the mouse pad 616 and the mouse-shaped case 615 is pushed against the mouse pad surface, the button switch 615f can be turned on. FIG. 18 is a cross sectional view illustrating another embodiment which utilizes as a tablet a printed surface on which a dot pattern portion 607 is formed. According to this embodiment, the pen type member 619 including a camera 602 is combined with a table 620 (or trace table) to use as a tablet a printed surface on which a dot pattern portion 607 is formed. A paper sheet 621 on which a dot pattern portion 607 is printed (printed surface) 621 is set on the table 620, a picture and letters are traced with this pen type member 619, and the switch 622a is turned on thereby to capture data into the PC 608 or PDA. Further, an end of the pressure switch 622b protrudes from the end of the pen type member 619. This pen type member 619 is used to write letters or draw a picture on a paper sheet on hand as is usually done. Then, without looking at a display, written letters and drawn picture can be inputted to the PC 608 or PDA as the camera 602 recognizes information of voices and the like thereof. Accordingly, this pen type member 619 can be used for illustration, drawing, and also trace. Conventionally it was necessary to look at a display when tracing by the mouse. However, this need is eliminated thereby to reduce burden in inputting. It is further possible to easily perform an operation which conventionally can be realized only by a coordinate inputting device called tablet. FIG. 19 is a cross sectional view illustrating another embodiment a camera mounted at an end of a pen type member. FIG. 20 is a cross sectional view illustrating yet another embodiment a camera mounted at an end of a pen type member. The camera 602 mounted at the end of the pen type member 619 can be mounted swingingly thereon, as shown in FIG. 19. Since the camera 602 is thus swingingly configured, the camera 602 can be always placed vertically to a printed surface of the dot pattern portion 607, and there is no need to consider distortion caused by tilt of the camera 602 (pen type member 619). FIG. 20 is a cross sectional view illustrating another embodiment of the pen type member with a pressure switch mounted at the end thereof. The switch 622 does not always have to be mounted on the pen type member 619. As shown in FIG. 20, the switch 622 can be mounted at the swingingly mounted camera 602. With this configuration, the switch 622 of the camera 602 has only to be pushed against a printed surface of the dot pattern portion 607 in order to turn on the button switch 622. Accordingly, the invention enables operation of the PC 608 instead of using a keyboard or a mouse regularly provided on the PC, and everyone can easily operate the PC 608 only by pushing. Then, the invention serves as an interface which has a high affinity for human. Beside, the invention can be manufactured with a simple configuration and with low cost as compared with an inputting pad. However, the invention is not limited to the above-described embodiments. When the invention is configured to recognize a dot pattern portion 607 on a printed material 606 or a transparent film 611 (touch panel 612) and to reproduce predetermined information and voices thereby to enables various ways of use, the invention is not limited to the above-described embodiments. Besides, the invention can be modified without departing from the description of the invention. FIGS. 21(a) and 21(b) are block diagrams each illustrating an information inputting/outputting method by camera inputting according to the invention, and more specifically, FIG. 21(a) explains generation of a dot code and FIG. 21(b) explains recognition of a dot pattern. FIG. 22 is an elevation view illustrating an example of a dot pattern. The information inputting/outputting method by camera inputting of the invention includes generation of a dot pattern 1, recognition of the dot pattern 1 and means for outputting information and a program corresponding to the dot pattern 1. In other words, a camera unit 2 is used to scan image data of the dot pattern 1. First, key dots 3 are extracted and then, information dots 4 are extracted. The extracted dots are digitalized to extract an information area, and thereby to be converted into numeric values. The numeric information is based to output information and a program corresponding to the dot pattern 1. Generation of the dot pattern 1 according to the invention is performed in such a manner that small dots (key dot (KD) 3a, lattice dots (LD) 3b and information dots 4) are arranged in accordance with a predetermined rule by a dot code generating algorithm in order to recognize information. Recognition of dot pattern 1 includes correction of distortion rate by a lens of the camera unit 2, correction of distortion due to tilt of the camera unit 2 and reproducing of numeric information of a key dot 3a (KD) and information dots 4. Image data of the dot pattern 1 is captured by the camera unit 2 which includes an image pickup device such as a C-MOS camera and CCD camera. The above-described dot pattern 1 consists in a dot pattern portion 6 by printing at a wide variety of the printed material 5. Specifically, in the invention, the dot pattern portion 6 is printed on the same surface of the printed material 5 together with an information transfer portion 7 represented by letters, illustrations or the like of which people is usually able to recognize information content visually, which is shown in FIG. 23. The information transfer portion 7 is preferably printed using a non-carbon ink. On the other hand, dots of the dot pattern portion 6 are preferably printed with a carbon ink. In the information inputting/outputting method according to the invention, first, when the camera unit 2 is used to capture image data of the dot pattern portion 6, the dot pattern portion 6 is radiated with infrared light and thereby the dot pattern portion 6, of which the dots are printed in a carbon ink, is only scanned accurately separately from the information transfer portion 7 printed in a non-carbon color ink. In other words, since information data of the dot pattern portion 6 is only captured from the printed material of which the information transfer portion 7 expressed by letters or figures and the dot pattern portion 6 are printed to be superimposed on the same surface, information of the dot pattern portion 6 can be only extracted. FIG. 23 is a view for explaining a dot pattern composed of x and y coordinate information. FIG. 24 is a view explaining a method of recognizing and processing a dot pattern composed of x and y coordinate information. The dot pattern portion 6 of the invention is created by x and y coordinate information, and the x and y coordinate information and a content of the information transfer portion 7 can be associated with each other. Regarding the dot pattern portion 6, image data of the dot pattern portion 6 is captured using the camera unit 2 as explained above, and the image information is digitalized to be converted into numeric values. The numeric values are expressed by the x and y coordinate information, which is then brought into correspondence with either position of the information transfer portions indicated by the round portion A, the square portion B and the triangular portion C. At this time, using a reference table 1 on FIG. 24, the x and y coordinates are associated with each of the information transfer portions 7. In other words, correspondence is made between an x and y coordinate range and either content of the information transfer portions 7. This is followed by referring a reference table 2 on FIG. 24 to output information or a program corresponding to the dot pattern portion 6. With the dot pattern portion 6 being made of the x and y coordinate information, only if the printed material 5 on which the dot pattern 1 is printed in advance is prepared and the information transfer portion 7 is printed to be superimposed on the printed material 5, it is possible to associate, for a certain content, the x and y coordinate range with information and a program of a voice or the like. In other words, since there is no need to create a new dot pattern portion 6 for a content of the information transfer portion 7, its versatility becomes extremely high. FIG. 25 is a view explaining a dot pattern made of code numeric information. FIG. 26 is a view explaining the procedure of recognition and processing of a dot pattern formed of code numeric information. The dot pattern portion 6 according to the invention makes it possible to create code numeric information instead of the aforementioned x and y coordinate information and to associate the code numeric information with content of an information transfer portion 7. For example, the dot pattern portion 6 is printed out which includes code numeric information corresponding to the content of either of the information transfer portion 7 of the round portion A, the information transfer portion 7 of the square portion B and the information transfer portion 7 of the triangular portion C. The dot pattern portion 6 also has image data captured by the camera unit 2, as described above, which image information is digitalized into numeric values (code numeric information). Then, by referring to a reference table on FIG. 26, information and a program corresponding to the dot pattern portion 6 is outputted. According to the dot pattern portion 6 with the code numeric information, a code number and content of the information transfer portion 7 are in direct correspondence with each other. Accordingly, as shown in FIG. 26, it is enough to make only one reference table. In addition, since only one reference table needs to be created, it is possible to shorten information processing time. Here, it is needless to say that a dot pattern portion 6 including x and y coordinate information and a dot pattern portion 6 including code numeric information can be printed on the same surface. FIG. 27 is an explanatory view explaining a state of image data of a dot pattern portion printed with a carbon ink being only captured by a camera separated from an information transfer portion of letters, figures or the like printed with a non-carbon color ink. As shown in FIG. 27, formed on a printed material 5 of white paper is an information transfer portion 7 printed with an ink which is transparent at infrared wavelengths but forms a color at visible light wavelengths, for example a non-carbon ink (dye ink). Next, formed on this printed material 5 is a dot pattern portion 6 printed with an ink which forms a color at infrared wavelengths, for example, a carbon ink such as a toner, infrared light ink, transparent ink or the like. These information transfer portion 7 and dot pattern portion 6 are superimposed to be printed on the same surface, which is then shot by a camera unit 2. At this time, an infrared light filter 2a cuts visible light wavelengths and makes only infrared light wavelengths pass. The camera can obtain information of the dot pattern 1 only. On the other hand, it is also possible to first print the dot pattern portion 6 before to print the information transfer portion 7. This camera unit 2 recognizes at these dot pattern portions dots printed in accordance with a given-rule, which dots are digitalized to be converted into numeric values. Then, the numeric information is read, and information or a program area on the printed material 5 corresponding to the dot pattern portion 6 is recognized. This is followed by outputting and executing various information and program correspondingly stored in a memory. For example, information and program corresponding to the dot pattern portion 6 can be outputted by a text and image or a voice. The way of radiating a dot pattern portion 6 with infrared light can be adopted to capture only image data of a dot pattern portion 6 in the printed material 5 by the camera unit 2. According to the above-described method of the invention it is possible to output and execute various types of voice information via a medium of a printed material 5. The invention can be applied to various printed materials 5, for example, a picture book, a pop-out book a photograph itself, questions, a text, a exercise book, a magazine, a newspaper, a card, a member card, a photo stand, an adhesive coated picture, explanation of a showpiece in a museum, card game, board game, pamphlet, catalog of mail order and the like. Thus, it is possible to recognize both of visual information of the information transfer portion 7 including letters and illustrations in the printed material 5 and voice information from the dot pattern portion 6. FIG. 28 is a functional block diagram for explaining a first embodiment of a portable information inputting/outputting device using the information inputting/outputting method by camera inputting. The portable information inputting/outputting device includes: a sensor portion 8 consists of a camera unit 2; and a main body processing portion 11 which has a processing portion 9 and a storing portion (memory) 10. This sensor portion 8 includes the camera unit 2 which captures only image data of a dot pattern portion 6 on a printed material 5, and an information processing portion 12 for digitalizing the image data into numeric values. Provided in the vicinity of this camera unit 2 is an infrared light emitting portion 13 for radiating the printed material 5 with infrared light. The main body processing portion 11 includes the processing portion 9 for outputting and executing information and a program stored in advance in the storing portion (memory) 10 and corresponding to the dot pattern portion 6 based on the numeric values obtained by image processing at the image processing portion 12. This main body processing portion 11 includes an outputting portion 15 such as a speaker 14, earphones or an LC monitor 25. This outputting portion 15 can output, in addition to the voices, voice output (line), image to TV monitor or to a PC. The storing portion 10 can store information and a program not only in advance but also can store them later. For example, the storing portion 10 can store information and a program from voices obtained by a microphone 17a as an inputting portion 17. In addition to the microphone 17a, this inputting portion 17 can be connected to a voice input terminal, an image input terminal, a PC and the like to store information and a program. In this way, since voices can be input later by using a microphone 17a, for example, the portable information inputting/outputting device is allowed to store voices of a user himself or acquaintances related to the printed material 5 such as a picture book stored via the microphone 17, and later, the portable information inputting/outputting device can scan the printed material 5 so as for other people to listen to voice information corresponding to a content of the printed material. For example it can be used as a “family message device” or an “adhesive coated picture with voice message”. The main body processing portion 11 can output or execute information and a program from the outside by being equipped with a communication card 16. For example, a dot pattern 1 scanned by a camera unit 2 is converted into numeric values, which data then can be transmitted to a computer 23 such as a server via the communication card 16. In addition, a dot pattern 1 scanned by the camera unit 2 is converted into numeric values, which data then can be transmitted to a computer 23 such as a server by using the communication card 16 before the main body processing portion 11 can receive information and a program corresponding to the data. The main body processing portion 11 can input data of numeric values into which the dot pattern 1 scanned by the camera unit 2 is converted, and receive corresponding voices. The communication card 16 is mounted on the main body processing portion 11 to store information and a program in the storing portion 10. Since the communication card 16 is thus used, it becomes easy to transmit and receive information and a program. For example, the portable information inputting/outputting device is used to reply to questionnaires by voices and then the voice information is transmitted to the computer 23 such as a server. Or, information of voices replying to questions or a test can be transmitted to the computer 23 such as a server thereby to carry out a pronunciation test or have responses to the questions or test corrected. Further, URL information is embedded in the dot pattern portion 6 of the printed material 5 or another medium so that when the URL information is scanned, connection to a side of the URL information is established automatically. Or, the connection being established, a particular action can be set to be performed. Or, a published matter which makes sound can be created. Voice information can be input in a post card or a letter later. For example, this printed material 5 can be added BGM (back ground music), SE (sound effect) or the like, later. The main body processing portion 11 is further provided with a GPS 24 so as to display information of a current position easily. FIG. 29 is a functional block diagram for explaining an embodiment of the portable information inputting/outputting device using the information inputting/outputting method by camera inputting. According to the portable information inputting/outputting device of this embodiment, since a sensor portion 8 only includes a camera unit 2, the sensor portion 8 can be realized in a compact size. However, the invention is not limited to the embodiment shown on the figure. The invention can be applied to any configuration which enables various ways of use by recognizing only a dot pattern portion 6 in the printed material 5 to reproduce given information and voices. Modifications may be made in the invention without departing from the scope of the invention. FIG. 30 is a perspective view of a portable information inputting/outputting device housed in a compact case body. FIGS. 31(a) to 31(d) each shows a portable information inputting/outputting device housed in a compact case body, and specifically, FIG. 31 (a) is a perspective view of the whole device, FIG. 31(b) is a plan view, FIG. 31(c) is a lateral view and FIG. 31(d) is an elevation view. The portable information inputting/outputting device of the invention is configured in the body case 18 which one can hold in one's hand, and includes a main body processing portion 11 as mentioned above, a camera unit 2 provided downward at the body case 18 and a speaker 14 or an earphone terminal 19 provided laterally. A button switch 20 is provided at the upper side of the body case 18, and a USB terminal 21 and a memory card slot 22 as the storing portion 10 are provided at the front side thereof. The portable information inputting/outputting device of the invention is further provided with an LC monitor 25, an earphone jack 19, a TV monitor output terminal 26 and the like. Further, the body case 18 is provided with a microphone 17a, a shooting button 27, a recording button 28 a program selecting button 29, an output lump 30, a GPS 24, a voice input terminal 31, the USB terminal 21 and a memory card slot 22 of the storing portion 10. The body case 18 is formed to be round totally, as shown in FIG. 31, so that one can hold the body case 18 in one's hand. By this configuration, it becomes easy to capture image data of the dot pattern portion 6 of the printed material 5. The shape of the body case 18 is limited to the shape shown in the figures. Modification may be made without departing from the scope of the invention. FIGS. 32 and 33 are functional block diagrams each for explaining an embodiment of a camera and an outputting portion configured separately. In this embodiment, the camera unit 2 can be configured to be separated from the abovementioned image processing portion 12, the storing portion 10, the processing portion 9 and the outputting portion 15 and to enable transmission via an interface portion. Transmission via this interface portion can be performed by wired communication or radio communication. Transmitting by radio communication can be performed by a radio transmitting portion 32 and a radio receiving portion 33 of the interface portion, which is shown in the figures. The sensor portion 8 in FIG. 33 includes the camera unit 2 only. By this configuration, the sensor portion 8 can be of compact size. FIG. 34 is a perspective view illustrating a device having a camera unit portion and an output main body separated. In the example in FIG. 34, the camera unit portion and the output-side main body are separated and connected by a wired cable 34. Since they are thus separated, the camera unit 2 can be easily abutted on a printed material 5, which makes it possible to use a portable information inputting/outputting device on the table. This camera unit 2 is configured with a ring switch 35 around the camera. With this configuration, only if the camera unit 2 is pushed against the printed material 5, a switch can be turned on, which presents easy operability by one hand. FIGS. 35(a) to 35(d) are perspective views each illustrating another embodiment of the camera unit portion and specifically, FIG. 35(a) shows a pen type camera unit, FIG. 35(b) shows a pen type camera unit, FIG. 35(c) shows a mouse shaped camera unit and FIG. 35(d) shows a stethoscope shaped camera unit. The pen type camera unit 2 shown in FIG. 35(a) is connected to an end of a pen 36 movably by a bayonet 37. This is also provided with a button switch 38 at the pen axis. The pen type camera unit 2 shown in FIG. 35(b) is connected to an end of a pen 36 movably by a bayonet 37 and is further provided with a ring switch 39 around the camera. With this configuration, the switch is turned on only by pushing the camera unit 2 against the printed material 5. The mouse shaped camera unit 2 shown in FIG. 35(c) is provided in a mouse shaped main body 40 which takes form of a mouse. This is provided with a button switch 38 at the upper surface of the mouse shaped main body 40. Since the mouse shaped camera unit 2 is of size one can hold in his hand, it can be operated on the printed material 5 like a PC mouse. The stethoscope shaped camera unit 2 shown in FIG. 35(d) is provided in a main body 41 which can be held by fingers such as a stethoscope. This is also provided with a button switch 38 so that one can operate the camera unit 2 by picking up the camera unit 2 by the fingers. FIG. 36 is a functional block diagram for explaining an information inputting device using a camera for a portable phone. The information inputting device 118 includes a sensor portion 108 which has a camera unit 102 and a main body processing portion 111 which includes a processing portion 109. This sensor portion 108 includes the camera unit 102 for capturing image data of only a dot pattern portion 6 (refer to FIG. 27) on a printed material 5 and an image processing portion 112 for digitalizing image data into numeric values. An infrared light emitting portion 113 for radiating the printed material 5 with infrared light is provided in the vicinity of this camera unit 102. The main body processing portion 111 includes the processing portion 109 for outputting and executing information and program stored in advance in a storing portion (memory) of the portable phone 10, corresponding to the dot pattern portion 6, based on the numeric values obtained by image processing at the image processing portion 112. This main body processing portion 111 is further provided with a GPS (not shown) so as to easily display information of a current position. The storing portion (memory) of the portable phone 110 can store information and a program not only in advance, but later. For example, the storing portion of the portable phone 111 can be configured to store information and a program by voice, image and letter information using a microphone, a camera (not shown) or the like. FIG. 37 is a functional block diagram for explaining an embodiment of the information inputting device using a camera. An information outputting device according to the embodiment includes a sensor portion 108. Since the sensor portion 108 only includes a camera unit 102, it can be configured to be compact. FIG. 38 is a view for explaining an information inputting device using a camera for a portable phone. The aforementioned information inputting device 118 can be used by being mounted on the portable phone 110. Since the information inputting device 118 is thus mounted on the portable phone 110, information and a program corresponding to the dot pattern portion 6 captured by the camera unit 102 can be output and executed by the portable phone 110. FIG. 39 is a view for explaining an information inputting device using a camera for a portable phone. The aforementioned information inputting device 118 can be used mounted on the portable phone 110 via an interface portion 19. Since the information inputting device is thus mounted on the portable phone 110 via the interface portion 19, the information inputting device 118 can be only moved freely. This information inputting device 118 mounted on the portable phone 110 is utilized in the following manner. That is, it is possible to recognize voice information associated with the dot pattern portion 6 together with visual information from the information transfer portion 7 made of letters or illustrations on the printed material 5. At this time, it is possible to display, other than the voice information, image, text and the like simultaneously on the portable phone 110. The printed material 5, a educational material, a text, questions, a magazine, a newspaper, a photograph itself, a card, a member card, a photo stand, an adhesive coated picture, an explanation of a showpiece in a museum, a card game, a board game, a pamphlet, a wish book and the like. Here, means for mounting the information inputting device 118 on the portable phone 110 is not limited to those shown in the figures, and it is needless to say that modification thereof can be made without departing from the scope of the invention. FIG. 40 is a view for explaining a portable phone which includes an information inputting device therein. The information inputting device 118 of the invention can be embedded in the portable phone 110. Then, by integrating the portable phone 110 and the information inputting device 118, it is possible to present a more compact information inputting/outputting device. The portable phone 110 can store information and a program in a storing portion from the outside using its communication function and transmit the stored information and program. This configuration makes it possible to transmit information and programs easily. For example, a dot pattern 1 input by the camera unit 102 is converted into numeric values, which can be transmitted to a computer 123 via the communication function of the portable phone 110. Further, image data of the dot pattern 1 scanned by the camera unit 102 is converted into numeric values, which can be transmitted to a computer 123 via the communication function of the portable phone 110 and then, the portable phone 110 can receive information and programs corresponding to the data. Numeric data of the dot pattern portion 1 input by the camera unit 102 is input and corresponding voices, text an image are input. With this configuration, it is possible to output and execute using a dot pattern a conventionally-provided enormous amount of content for portable phones. Further, since the communication function of the portable phone 110 is thus used, it is possible to transmit and receive information and programs easily. This configuration can be used to transmit voice information of responses by voice to questionnaire to a computer 123 such as a server. Or, voice responses to questions or a test can be transmitted to the computer 123 such as a server so as to test pronunciation and correct a response. The portable phone 110 is further provided with a GPS to display information of a current position easily. FIG. 41 is a functional block diagram of a portable electronic toy according to an embodiment using a dot pattern of the invention. FIG. 42 is an elevation view showing a portable electronic toy according to the embodiment. FIG. 43 is a right side view showing a portable electronic toy according to the embodiment. FIG. 44 is a left side view showing a portable electronic toy according to the embodiment and FIG. 45 is a bottom view showing a portable electronic toy according to the embodiment. A portable electronic toy 801 according to the embodiment is a toy for outputting various voices and music relating to a book, a game card, a small article, a toy or the like which is a medium 802. This portable electronic toy 801 includes a dot pattern portion 803 for recognizing records of a book or the like and a voice relating thereto, a voice storing portion 804 for storing various voices, a processing portion (CPU) 806 for controlling a speaker 805 to reproduce the voice and a voice reproducing LSI 807, which are housed in a case main body 808. This case main body 808 is connected by a cable 809 to a pen type camera 810 for capturing image data of the dot pattern portion 803. The voice storing portion 804 housed in the case main body 808 of the portable electronic toy 801 stores voices to be reproduced based on information of the dot pattern portion 803 for recognizing the records of the book and its relating voices. This voice storing portion 804 can not only be used as an internal memory but also be used to capture latest contents by using an external memory. For example, the voice content can be updated by down loading a program from the outside, which enables one portable electronic toy 801 to be used repeatedly. The camera 810 is configured to capture image data of the dot pattern portion 803 attached to a book, a game card, a small article or a toy, or image data of the dot pattern portion 803 which includes a number, a letter or the like as a recognition signal printed directly on the book or the like. Since the image data of the dot pattern portion 803 captured by the camera 810 is subjected processing by the image processing algorithm to extract dots and distortion due to the camera 810 is then corrected by the distortion correction algorithm, even when the image data of the dot pattern portion 803 is captured by a popular camera 810 of higher distortion ratio, accurate recognition can be achieved. This camera 810 recognizes information of the dot pattern portion 803, and a voice and a music corresponding thereto is reproduced by the voice reproducing LSI 807 to be outputted via the speaker 805. The case main body 808 of the portable electronic toy 801 according to the invention is of portable size of “a personal organizer” having a height of 13 cm×a width of 18 cm. Then, one can hold the portable electronic toy 801 in the hand and carry it in a bag. Further, an LC display portion 812 provided at the case main body 808 is used to display other information than voices at a time. Display of this LC display 812 is implemented by an image reproduce LSI 13. Since other information than music can be also obtained at the same time, a portable electronic toy 801 according to the invention presents a wide range of application. In this portable electronic toy 801, when a switch 14 at the lateral face of the case main body 808 is turned on, a pilot lamp 15 is lighted on. The voice storing portion 804 may utilize a storing medium 816 including a flash memory, a compact flash, a smart media, storing IC card, a memory stick, and the like, thereby facilitating change of a stored voice. The voice storing portion 804 stores, for example, content data that is usable as an educational material for teaching pronunciation of a foreign language by voice (voice data, image data, moving image data, character code data of letters, symbols and the like). In addition, the voice storing portion 804 stores content usable as a picture book for creating music or a band with figures, a content as an educational material for emitting voices in combination with toys such as assembly blocks, content usable as a picture book for emitting music and conversation of a central character and the like as well as pictures of the picture book as a “sound picture book”, and a content usable as a dictionary software for translating a foreign language by tracing a word or text as a “sound dictionary”. Further, the invention can be used as a versus game or an RPG software in combination with versus game cards, as a pamphlet for explaining by voice features of a product and company profile as a “sales promoting tool”, or an electronic device for explaining by voice establishment of a museum and the like or notable sights of a sightseeing area. The camera 810 can be housed in a side surface of the case main body 808 so that after the camera being used the portable electronic toy 801 can be taken along. Light (not shown) is provided in the vicinity of the camera 810 and the dot pattern portion 803 is lighted on, thereby achieving accurate recognition of the dot pattern portion 803 even in the dark. The portable electronic toy 801 according to the invention can be realized in the following various ways when being used by combining the dot pattern portion 803 with a medium 802 including a book, a game card, a small article and a toy. <Sound Educational Material> The portable electronic toy 801 according to the invention can be used as an educational material of miniature size book which can be set on the bottom of the case main body 808. The invention utilizes an advantage of excellent portability to present a “sound educational material” which can be used in studying anywhere at any time, for users in any generation, from children to adults or the aged. For example, letters in a book is traced to reproduce a voice. Using this configuration, the portable electronic toy 801 according to the invention can be used as a supplemental educational material of language education such as English conversation, child education including intellectual education and music, drill or the like. <Versus Card Game> The portable electronic toy 801 according to the invention can be used as a “versus card game”. It is configured that when a “special seal and data collection” corresponding to the versus card game is created and a dot pattern portion 803 corresponding to each card is attached, a character of the card can start to speak in a vivid manner from the speaker 805 of the portable electronic toy 801. Besides, explanation is given by the voice of character, or tricks are introduced, the invention can be utilized as an item for extending the card function. Or, if “special seal and data collection” corresponding to a famous film card is created, it is configured to output voice or music of the film by attaching a dot pattern portion 803 corresponding to the card. Or, if “special seal and data collection” corresponding to an idol card of an idol who has fixed fan base is created, it is configured to output a voice of the idol by attaching a dot pattern portion 803 corresponding to each card. Here, this can be utilized for tie-up development such that one phrase of a song is flowed for each card and all the song is flowed if all cards are collected. The portable electronic toy 801 according to the invention can be used with enjoyment by attaching a dot pattern portion 803 to various materials near at hand to made sound. “Special seal and data collection” is created mischievously. Then, if a dot pattern portion 803 is attached to a material near at hand and the dot pattern portion 803 is traced by a camera 810, it can make sound. For example, for boys, the invention is combined with their favorite mini car kits and “special seal and data collection” is created to form a road that makes sound. A dot pattern portion 803 is attached to a road kit for mini cars including a cross over and buildings, so that when a car comes near the cross over, it clangs like “kan kan kan” or when a car goes away from the road, it sounds like “kikee (eg. sound of car slipping due to sudden braking)! Look!”, thereby to enhance presence. The portable electronic toy 801 according to the invention can present a new way of use such that a T-shirt is produced with many dot pattern portions 803 printed thereon to enjoy wearing it. The portable electronic toy 801 according to the invention is usable as a “fortune-teller device”. A user can enjoy himself with the portable electronic toy, and also, the portable electronic toy can be used in an entertainment of a party such as a welcome party for freshmen or an year end party. For example, when letters written on a “dedicated letter plate” (dot pattern portion 803) are traced in a sequential order by a camera 810, an interesting comment is outputted at random. By inputting a name using the letter plate, it can be used for “name-based fortune teller”. A comment such as “today's fortune” is outputted. For example, the following weak comment can be made: “love fortune, job fortune and health fortune are all horrible, but, animal fortune is only great. If you go out, you may fall in love with a walking dog.” <Treasure Hunting Game> The portable electronic toy 801 according to the invention can be utilized as a “treasure hunting game”. Portable electronic toys 801 according to the invention corresponding in number to participants are prepared and dot pattern portions 803 are invisibly attached to various areas in advance. After that, the participants start at the staring point (eg. entrance) all together, look for the hidden dot patterns portion 803 while following the instruction to go to the next place such as “look for the corridor”. Then, one who is the first to have found the dot pattern portion 803 at the goal will win the game. <Foreign Language Translator> A portable electronic toy 801 according to the invention can be utilized as a “foreign language translator”. When a user encounters an unknown word while reading English newspaper or a foreign magazine, he traces the word (dot pattern portion 803) by a camera 810 and then, the toy translates the word into Japanese and reads it aloud. A USB connector (not shown) can be provided at the case main body 808 so that a plurality of portable electronic toys 801 can be connected in a network. Cables to USB connectors are connected to each other and also to PCs and the like so as to be networked. FIG. 46 is a perspective view showing an embodiment of a portable electronic toy which generates voices corresponding mainly to a mini figure. FIG. 47 is a perspective view showing a plurality of voice emitting toys being connected to a controller unit. A portable electronic toy 821 is a toy which generates a voice corresponding mainly to a mini figure. This portable electronic toy 821 include a dot pattern portion 803 which records code information for generating voice information corresponding to a character of mini FIG. 822, a voice storing portion 804, housed in a case main body 823, which stores a voice, a camera 810, a processing portion (CPU) 806 for making a speaker 805 to output a voice, and a voice reproducing LSI 807. The dot pattern portion 803 is configured by a round sheet member that can be attached to a table 824 of the mini FIG. 822 or the inner ceiling of a bottle cap, and one surface of the dot pattern portion is coated with an adhesive agent and the dot pattern portion 803 is displayed on the other surface of the sheet member. However, instead of using the sheet member, the dot pattern portion 803 can be printed on the mini FIG. 822, itself. The voice storing portion 804 housed in the case main body 823 of the portable electronic toy 821 can not only be used as an internal memory but also capture latest content data by use of an external memory. For example, a program or data is input from the outside or downloaded via a network to update the substance of the voice, thereby enabling one portable electronic toy 821 to be used repeatedly. Preferably, there is light provided as lighting means in the vicinity of the camera 810 at the center of the case main body 823. With this configuration, the dot pattern portion 803 is lightened up and thereby the image data of the dot pattern portion 803 can be recognized accurately even in the dark. FIG. 48 is a functional block diagram illustrating a portable electronic toy according to the embodiment. Each case main body 823 is provided with a USB connector (not shown) so that a plurality of portable electronic toys 821 can be connected corresponding to a network environment. A cable connected to the USB connector is coupled to a PC or the like to be networked. FIG. 49 is a functional block diagram illustrating a portable electronic toy of an embodiment that utilizes an optical character recognition (OCR) according to the invention. This embodiment employs, in place of the camera 810 and the dot pattern portion (recognition seal) 3 of the above-described embodiment, an OCR sensor pen 831 and a voice recognition signal portion 832. In other words, by utilizing OCR, the portable electronic toy 801 is a toy for emitting a various voice and music relating to a book, a game card, a small article, a toy or the like which is a medium 802. This portable electronic toy 801 includes a voice recognition signal portion 832 for recognizing records of a book or the like and its relating voice, a voice storing portion 804 for storing various voices, a processing portion (CPU) 806 for making a speaker 805 to output the voice, and a voice reproducing LSI 807, which are housed in a case main body 808. Connected to this case main body 808 is an OCR sensor pen 831 by a cable 809. The OCR sensor pen 831 is a pen for tracing an icon seal (voice recognition signal portion 832) attached to a book, a game card, a small article, a toy or the like or the voice recognition signal portion 832 on which a number, letters or the like as a recognition signal of the book or the like are directly printed. In other words, the OCR sensor pen 831 recognizes a number, a simple mark or the like added on the voice recognition signal portion 832 and corresponding voice and music are reproduced by the voice reproduce LSI 807 to be outputted by the speaker 805. FIG. 50 is a functional block diagram of a portable electronic toy, showing an embodiment which utilizes a magnetic member. This embodiment employs, in place of the camera 810 and the dot pattern portion (recognition seal) 3, a magnetic scanning sensor pen 841 and a magnetic recording portion 42. In other words, this portable electronic toy 801 employs the magnetic recording portion 42 for recognizing a voice corresponding to a medium or the like, the voice storing portion 804 for storing the voice corresponding to the magnetic recording portion 842, and the magnetic scanning sensor pen 841 for scanning the magnetic recording portion 842. This magnetic scanning sensor pen 841 is used to scan the magnetic recording portion 842 and the voice reproducing LSI 807 reads a corresponding voice from the voice storing portion 804 to reproduce the voice via a speaker 805. In this embodiment, in addition to reproducing a voice and music corresponding to the medium 802, it is possible to readily change recorded data of the magnetic recording portion 842 attached to the medium 802. Then, a user is allowed to change the voice into his favorite voice. FIG. 51 is a functional block diagram illustrating a embodiment which utilizes a shooting pen of a camera or the like. In this embodiment, the dot pattern portion (recognition seal) 803 of the above described embodiment is replaced with a voice recognition seal. In other words, the portable electronic toy of the embodiment includes a voice storing portion 804 for storing a voice corresponding to each shape or color printed on the medium 802, a shooting pen 851 such as a CCD camera for shooting a shape or the like printed on the medium 802, and a processing portion 806 for reading from the voice storing portion 804 a voice corresponding to a color or shape shot by the shooting pen 851 and image relating to the color to output the voice via a speaker 805. According to this embodiment, it is possible to reproduce a voice and music corresponding to a shape and color printed on the medium 802 without employing the dot pattern portion 803, the voice recognition signal portion (recognition seal) 832 or the magnetic recording portion (magnetic sheet) 842. Here, light (not shown) is further provided in the vicinity of the shooting pen 851 such as a CCD camera. With this configuration, the medium 802 is lighten up thereby to shoot a shape thereof accurately even in the dark. Further, provision of the shooting pen 851 such as a CCD camera makes it possible to generate various voices and music corresponding to the medium 802 by use of the voice recognition seal 852. For example, it is configured to include a voice recognition seal 852 which can be attached to the medium 802 and recognizes a voice corresponding to the medium 802 or the like, a voice storing portion 804 for storing a voice corresponding to the voice recognition seal 852, a shooting pen 851 for shooting the voice recognition seal 852 and a processing portion 806 for reading from the voice storing portion 804 a voice corresponding to a number, letter or the like as a recognition signal of the voice recognition seal 852 shot by the shooting pen 851 to output the voice from the speaker 805. Here, the invention is not limited to the above described embodiments. The configuration of the invention needs only to recognize a medium 802 such as a book itself and reproduce a given voice by the voice reproducing LSI 807 via the speaker 805, and is not limited to the shape of the case main body 808 shown in the figures. Further, it is needless to say that various modifications of the invention can be made without departing from the scope of the invention. FIGS. 52 and 53 are functional block diagrams of a figure unit having an information outputting function by camera inputting, in which embodiment a camera and an outputting portion are integrally formed. The figure unit according to the embodiment includes a sensor portion 208 which has a camera 202 and an image processing portion 212, a main body processing portion 211 which has a processing portion 209 and a storing portion (memory 210). The camera 202 of the sensor portion 208 captures only image data of a dot pattern portion 803 on a printed material and the image processing portion 212 digitalizes this image data into numeric values. In the vicinity of this camera 202 there is provided an infrared light emitting portion 213 for radiating the printed material 5 with infrared light. The processing portion 209 of the main body processing portion 211 is for outputting and executing information and a program stored in advance in the storing portion (memory) 210, corresponding to a dot pattern portion 803 based on the numeric values obtained by the image processing at the image processing portion 212. This main body processing portion 211 includes an outputting portion 15 such as a speaker 14. The storing portion 10 can store information and programs not only in advance, but also later. For example, the storing portion 10 is capable of storing information and programs which are inputted later by a microphone 17. FIG. 53 is a modification of the embodiment on FIG. 52, in which the sensor portion 208 includes only a camera 202. By this configuration, it is possible to configure a compact sensor portion 208. FIGS. 54 and 55 are functional block diagrams illustrating a figure unit which has an information outputting function by camera inputting, in which embodiment a camera unit and an outputting unit are provided separately. The figure unit of this embodiment includes a camera unit A and an outputting unit B. The camera unit A includes: a sensor portion 208 which has a camera 202 and an image processing portion 212; and a radio transmitting portion 21 which an interface portions. The camera 202 of the sensor portion 208 capture only image data of a dot pattern portion 803 in a printed material 5, and the image processing portion 212 digitalizes the image data into numeric values. In the vicinity of the camera 202 an infrared light emitting portion 213 is provided for radiating the printed material 5 with infrared light. The outputting unit B includes: a radio receiving portion 22; a main body processing portion 211 having a processing portion 209 and a storing portion (memory) 210; and an outputting portion 15 such as a speaker 14. The processing portion 209 of the main body processing portion 211 is for outputting and executing information and programs stored in advance in the storing portion (memory) 210, corresponding to the dot pattern portion 803, based on the numeric values obtained by the image processing by the image processing portion 212. The radio transmitting portion 21 and the radio receiving portion 22, which are interface portions, communicate by using infrared light. This outputting unit B can use a PC directly. FIG. 55 is a modification of the embodiment on FIG. 54, in which the sensor portion 208 only includes a camera 202. This configuration makes it possible to configure a compact sensor portion 208. FIG. 56(a) to FIG. 56(d) are perspective views each illustrating a figure with a camera unit. More specifically, FIG. 56(a) is an example of a doll, FIG. 56(b) is an example of a soccer ball, FIG. 56(c) is an example of a car and FIG. 56(d) is an example of an animal. Each of the examples in the figures shows a figure unit including a camera unit A of a FIG. 218 with a camera 202. When this FIG. 218 is put on a printed material 5 and image data of a dot pattern portion 803 is captured, this dot pattern portion 803 is radiated with infrared light thereby to scan only the dot pattern portion 803, which is printed with a carbon ink, separately from an information transfer portion 7 printed with a non-carbon color ink. Here, the shape of a FIG. 218 is not limited to those in the figures, and various modifications can be made without departing from the scope of the invention. In a figure unit of the invention as described above, it is possible to output and execute various types of voice information via a medium such as the printed material 5. Examples of how to use a figure unit are described below. <Usage as a piece of “SUGOROKU” or “board game”>A FIG. 218 of the present invention can be used as a piece of a “SUGOROKU” or a “board game”. When the FIG. 218 is put on the “SUGOROKU” or “board game”, a camera 202 of the FIG. 218 is used to output a certain voice of a dot pattern 803 on a printed material 5 so as to provide instructions by voice. Then, it is possible to extend the range of the way of playing “SUGOROKU” and “board game”. <Usage as a Piece of “Japanese Military Chess” (Military Shogi)> A FIG. 218 of the invention can be used as a piece of a Japanese military chess. When this FIG. 218 is put on a chase board (printed material 5) of “Japanese military chess”, a camera 202 of the FIG. 218 is used to scan a dot pattern portion 803 on the base (printed material 5) of the board game thereby to output a given voice. Since instructions can be notified by voice, this game can be developed as a game that has been never seen and has a new aspect. For example, a processing program of the main body is used to provide match of pieces (FIG. 218) with contingency and time axis. Such added values contribute, as essential factors, to realistic reproduction of a battle area and production of new strategies that have never seen in the normal Japanese military chess, and thereby people can enjoy playing the game. FIG. 57 is a perspective view of a figure unit of the invention being put on a central battle stage of a new simulation board game. <Usage as a Piece of “New Simulation Board Game”> A figure unit of the invention can be used as a piece of a “board game”. When a base (printed material 5) and a FIG. 218 are set up, the figure can be put on the base (printed material 5) to play a game. In match, FIGS. 218 are arranged face to face with each other on a central battle stage (printed material 5). On the stage, a dot pattern portion 803 and an information transfer portion 7 are printed. This dot pattern portion 6 is scanned by a scanner 202 of a FIG. 218, and based on an inside processing program, a complicated versus game can be developed. Thus, since the figure unit of the present invention can be used as an input interface printed on the printed material 5 or the like, an interface suitable for each content can be manufactured. Besides, if a paper interface is downloaded in PDF or the like and outputted by a printer and a program corresponding thereto is downloaded to be installed in a PC or the like, the interface can be supplied via a network. FIG. 58 is an explanatory cross sectional view illustrating another embodiment of the invention in which a camera unit and an outputting unit are integrated in a stuffed toy as one type of figure. The camera unit A and the outputting unit B of the invention can be integrated in a stuffed toy 231, which is one type of the above-described FIG. 218 and created by stuffing an elastic material such as a cotton or a sponge in an outer skin of predetermined shape. For example, a lens portion of camera units A are arranged at eye boll portions 232 of the stuffed toy 231 and an outputting unit B is housed in a body 233 of the stuffed toy 231 in such a manner that the outputting unit B can be freely put in and out. By this configuration, a favorite stuffed toy 231 itself can be used as a device for reproducing given information and voice. FIGS. 59 and 60 are explanatory cross sectional view illustrating another embodiments of a stuffed toy as one type of figure in which a camera unit and an outputting unit are integrated. Regarding a camera unit A housed in a stuffed toy 231, it is not always necessary to arrange camera units A at eye ball portions 232 of the stuffed toy 231. For example, camera units A can be arranged at hands 34 of the stuffed toy 231, instead of the eye ball portions 232 of the stuffed toy 231, which is shown in FIG. 59. A camera unit A can no doubt be arranged at another desired position, for example, at the bottom portion, the chest portion, or at the legs. The position where the camera unit A is arranged is determined depending on the kind of a stuffed toy 231, its size or the way of enjoying with the stuffed toy. However, the invention is not limited to the above-described embodiments. The invention can adopt any configuration that enables various ways of use by recognizing only a dot pattern portion 6 on a printed material 5 to reproduce given information and voice. Modifications of the invention can be made without departing from the scope of the invention. Next description is made about specifications of a dot pattern in the invention with reference to FIGS. 103 to 106. A dot pattern 601 is configured of lattice-arranged dots, as shown in FIG. 105. Lattice lines in the longitudinal and horizontal directions are shown only for explaining the position of dots, and they do not exist on the printed material in fact. Then, 4×4 lattice area is called a data block or lattice block, a lattice dot LD is arranged at each of four corners of this lattice block (intersections of lattice lines). A spacing between two lattice dots (LDs) is in the range of 0.35 mm to 1.0 mm, preferably around 0.5 mm. Besides, the diameter of a dot is preferably 8 to 10% of the spacing between lattice dots. A Key dot (KD) is arranged in order to show from which block to which block one data ranges. The KD is at the position shifted from a LD. In other words, a lattice dot is fundamentally arranged on a lattice point, while a KD is arranged shifted from the LD. Here, shift of a KD from a lattice point is preferably about 20%. An area surrounded with KDs or an area having a KD as its center consists in one data piece. Arrangement of the data is made sequentially from the upper left to the downward direction, as shown in FIG. 104. The data can be, as shown in FIG. 103, defined by how far a dot 605 is shifted from the center point in a lattice block. In FIG. 103, eight points are defined as equally 45 degree shifted from the center, and thereby, eight kinds, or 3 bits data can be expressed in a single lattice block. Further, the distance from the center point is changed to define further eight points. Accordingly, as sixteen points are totally defined, four bit data can be expressed. A dot pattern of the invention has a feature in that lattice consisting in one data block can be defined freely. That is, since a KD defines a range of data area as mentioned above, if arrangement of KDs is changed, a lattice block group of any variable length can be treated as a data storing area. Besides, according to the invention, dot pattern portions can have different meanings by changing shift of a KD even if they are at the same position. In other words, a KD functions as a KD if the KD is shifted from the lattice point. If the way of shifting is changed so that KDs are equally 45 degree shifted from the lattice point, eight patterns of KDs can be defined. Here, when a dot pattern portion is shot by shooting means such as a C-MOS, the shot data is recorded in a frame buffer of the shooting means. If the shooting means is at the position rotated around the vertical axis (shooting axis) on paper, or the position (shifted position) turned around the shooting axis, the shifted amount (angle of camera) around the shooting axis of the shooting means is seen from the positional relationship between shot lattice dots and KD. The principle being applied, even if the same area is shot by a camera, it presents an angle as a parameter of another dimension. Therefore, even when the same area at the same position is scanned, other information can be output per angle. So to speak, angular parameter enables hierarchical information to be arranged in one area. Applications of this principle are shown in FIGS. 74, 76 and 78. In FIG. 74, a scanner portion 1105 provided at the bottom of a mini FIG. 1101, and the mini FIG. 1101 is turned by 45 degree on a base. Then, different-angle information as well as scanned information of a dot pattern portion can be obtained thereby to output eight types of voices. In the invention a dummy dot (DD) can be set. This DD is defined as a dot arranged at the right center of four lattice dots (LDs) (refer to FIG. 106(a)). Such a DD is suitable for a picture book or the like in which a boundary is defined in every mask area. As shown in FIG. 106(c), a DD is arranged at the boundary between mask 1 and mask 2. Such arrangement of a DD area at a mask area prevents simultaneous scanning of code information defined at mask areas. FIG. 106(d) shows arrangement of DDs. Preferably, an empty dot in which no dot is arranged at the center of lattice dots is arranged in a background portion of a picture of the like. Since an empty dot is small in number of dots compared with normal data dot on which information is recorded, it is possible to print with indistinctive dots. In addition, since successive empty dots prevent patterning, they are suitable for whole-colored back ground. Further, according to the invention, it is necessary to analyze data of one block including shooing center. However, lattice data (information data) at several blocks in the vicinity of shooting center can be set as scanning data. In this case, data corresponding to information data lacked in one original block is read from another adjacent block, with which original one block data can be complemented to complete input. Regarding a data pattern which define x and y coordinates, a block different from the block at the shooting center is utilized to read information dots composing corresponding x and y coordinates, which is then subjected to correction to be x and y coordinates at the shooting center. The invention has a feature of not being affected much by shooting conditions since a dot pattern using lattice dots are utilized as described above. In other words, when the whole dot pattern is distorted due to the shooting conditions (distorting of lens of a camera, shooting angle of camera, change in shape of paper), position shift of a shape formed of four lattice dots and information dots are equally made, relative position from the lattice dots are not changed and if correction calculation is performed on the basis of these lattice dots, the real position of each information dots and key dots can be known. That is, a dot pattern using lattice dots according to the invention is resistant to distortion. FIGS. 61 to 67 are views for explaining a method for scanning a dot pattern corresponding to one block composed of sub blocks by a camera using a preferred embodiment of the invention of a dot patter inputting method by a camera of the invention. As shown in FIG. 61, a camera includes: an LED for radiating an object with light; an LED acrylic filter for filtering light output from the LED; and a visible light filter (infrared transparent filter) for filtering reflected light from the object. A tube housing the camera is approximately 10 mm in the longitudinal direction. If the diameter of the imaging area of a dot patter is 10 mm, when one block of 4 mm×4 mm dot pattern (I1 to I16) is scanned, an imaging area of 2r=2'4√2=11.28 mm at the maximum is required (refer to FIG. 62). In order to solve this, sixteen information dots to be arranged around a key dot of one block are not scanned sequentially, but they are scanned by four information dots (¼ block (sub block)) having information independent from other information dots. With this configuration, instead of information dots in ¼ block out of the imaging area, corresponding information dots (¼ block) in another block in the imaging area are input thereby enable one block information to be input within the imaging are of the diameter of 10 mm. When there occurs an error in either ¼ block input by the above-described method, corresponding information dots in another block (¼ block) are input to correct the error. In FIG. 64, the imaging center of a camera is I8 in B1 block, and [I1 to I16] in B1 block nearest the center of the camera are input. In FIG. 65, the imaging center of a camera is I8 in B1 block, and [I1, I2, I3, I4] and [I5, I6, I7, I8] in B1 block and [I9, I10, I11, I12] and [I13, I14, I5, I16] in B2 block nearest the center of the camera are input. In FIG. 66, the imaging center of a camera is I6 in B1 block, and [I5, I6, I7, I8] in B1 block, [I9, I10, I11, I12] in B2 block, [I13, I14, I5, I16] in B3 block and [I1, I2, I3, I4] in B4 block nearest the center of the camera are input. In FIG. 67, the imaging center of a camera is I7 in B1 block, and [I5, I6, I7, I8] and [I9, I10, I11, I12] in B1 block and [I1, I2, I3, I4] and [I13, I14, I5, I16] in B4 block nearest the center of the camera are input. In FIGS. 64 to 67, when there occurs an error in input dot pattern, there are eight ¼ block dot patters at the maximum that can be input alternatively. A dot pattern according to the invention as described above is printed on a printed material such as a picture book, a text and the like, the dot patter is captured as image data by the camera, and image data is digitalized into numeric values thereby outputting information and a program corresponding to the numeric values by a PC, an information outputting device, a PDA, a portable phone or the like. Next, the principle for scanning dots and a configuration of a device therefor are described with reference to FIGS. 107 to 113. Reflection of light includes specular reflection and diffuse reflection that occur at a given ratio on the surface of an object by characteristic of the surface. The specular reflection is, as shown in right figure of FIG. 110, reflection of light incident on a flat and smooth surface of an object in such a manner that the incident angle and the reflection angle are the same. Particularly, when the surface is smooth, a specular reflection factor is increased, reflection of light is heavy, and there occurs a highlight. The diffuse reflection is as shown in left figure of FIG. 110, such that light incident on a minutely rough surface is diffused in every direction and reflected. In this diffuse reflection, light at a given wavelength determined by a characteristic of the object surface is absorbed. Accordingly, when a paper surface is rough like bond paper or mat paper, a carbon ink included in a printed dot 605 absorbs incident light by the LED 2022 and the light is not reflected. Then, the dot 605 is mapped by a C-MOS camera 202 (refer to left figure of FIG. 111,). However, when dots are printed on paper of a flat and smooth surface such as coat paper or art paper, a film, plastic or the like, or the surface of printed dots is coated or covered with a transparent film, there occurs specular reflection. In this case, a carbon ink does not absorbs light of the LED 2022 and becomes a highlight, and accordingly, the dot 605 is not imaged by the C-MOS camera 202 (refer to right figure of FIG. 111,) In other to avoid this, as shown in FIG. 107, the LED 2022 is arranged at the position at which direct light from the LED 2022 is not specular-reflected to be input to the C-MOS camera 202, that is, the position near the C-MOS camera, and light from the LED 2022 is reflected against the inner wall 2021 not to occur a highlight. Also, as shown in FIG. 108, light from the LED 2022 is made to pass a filter 2023 such as an acrylic filter to diffuse the light equally on the paper, thereby to present highlight from occurring. Further, as shown in FIG. 2023, an acrylic filter 2023 may be mounted to coat around an LED 2022. FIGS. 112 and 113 a reviews each for explaining inner configuration of an end portion of a pen type scanner which realizes such ideal arrangement of C-MOS camera and an LED 1122. In FIG. 112, a nose portion 1125 with a long tapered end is engaged with a tube case 1124. The nose portion is movable in the axial direction, and movement of the nose portion is biased by an elastic member 1121 such as a spring or rubber provided on a protruding wall on the inner surface of the nose portion 1125. The protruding wall is equipped with a C-MOS camera, a lens 1126 mounted on the center of the C-MOS camera is arranged to see through an opening of the end of the nose portion so that the camera can image reflected light passing through the opening. At the lens 1126 side, an LED 1123 (2022) equipped with a filter 2023 is provided, as shown in FIG. 109. This LED 1123 is provided at the back of lens face of the lens 1126 in the tube case 1124 so that light from the LED 1123 is not input directly to the lens face. The protruding wall is provided with a switch 1123 for electrically conducting to an electric circuit by pressure. When the nose portion 1125 moves in the direction of the tube case 1124 against biasing of the elastic member 1121, a base portion of the nose portion 1125 pusses the switch 1123 to start operation. By actuation of the switch 1123, the LED 1123 is brought into an irradiating state thereby to start scanning processing by the C-MOS camera. Since the end of a pen type scanner is configured as shown in FIG. 112, assembly is completed only by inserting the nose portion 1123 to the tube case 1124 thereby improving assembly efficiency. Further, FIG. 113 shows another configuration of an end of a pen type scanner. In the configuration on FIG. 113, the nose portion 1125 is connected via the rubber (elastic member) 1132 by an adhesive agent. Further, the switch 1123 is arranged at a given position inside of the rubber 1132 so that the base portion of the nose portion 1125, which is biased to be moved against elastic force, pushes the switch 1123. Furthermore, LEDs 1131 are arranged via respective acrylic filters 1133 near the lens 1125 of the C-MOS camera. When the switches 1123 are actuated, radiated light of the LEDs 1131 is outputted via the acrylic filters 1133, through the opening of the nose portion 1125 to the outside. FIG. 68 to FIG. 111 show further modifications of the embodiments. FIG. 68 is a view of a camera which is housed in a pen shaped case (device main body) 1015 as a pen type scanner 1001. The case 1015 includes a battery 1016, a speaker 1007 and a circuit board 1017, which are mounted therein. A central processing unit (CPU) and a memory are implemented on the circuit boar 1017 in such a manner that their surfaces are fully attached to the board. A microphone (not shown) may be integrated. In addition, at the rear end of the case 1015 (upper right side of the figure), a memory cartridge 1014 is inserted detachably. This memory cartridge 1014 is configured to register a program, existing voice data or the like. The memory cartridge 1014 is provided replaceably, can be replaced with a ROM cartridge, a micro unit cartridge or the like. On the surface of the case 1015 buttons 1130a to 1130c are provided for controlling start of scanning, start of recording, voice reproducing and the like. Among the buttons, when the recording button is pushed, a microphone (not shown) can be used to record voices. The recorded voice data is stored in the memory cartridge 1014. At this time, when the dot pattern portion is scanned while the recording button being pushed, recorded voice data is allocated to the dot pattern portion. When the dot pattern portion is scanned while the deleting button being pushed, allocation of the voice data to the dot pattern portion can be cancelled. Then, the voice data may be left stored in the memory cartridge 1014. In the figure, in the end of the case 1015 (lower left side of the figure), as the case 1015 is abutted on a medium surface while being inclined by about 45 degree, a C-MOS camera unit, a spring 1121 and a tapered nose portion 1125 are provided along the vertical axis of the medium surface. When the case 1015 is pushed in the direction of the medium surface, the nose portion 1125 moves backward against biasing of the spring 1121 and then the switch 1123 is pushed on. Inside the nose portion 1125, a lens 1126 of the C-MOS camera unit is mounted to command the inside of the nose portion 1125 so that the lens 1126 can take an image of a window of the end of the nose portion. Inside the nose portion 1125, an irradiation tube 1127 is provided which has two crank-shaped 45-degree bent portions. The irradiation tube 1127 is configured of a cylindrical member of transparent resin and an end face thereof is faced with an LED 1122 so that a radiated light beam from the LED 1122 is input into the irradiation tube. Inside the irradiation tube, a diffused component of the radiated light beam (an optical component of which the angle with respect to the optical axis is larger than 45 degree) passes the inner surface of the irradiation tube to be output to the outside. On the other hand, a straight-traveling component of the radiated light (an optical component of which the angle with respect to the optical axis is smaller than 45 degree) is reflected on the inner surface of the irradiation tube to proceed in the tube. In the radiated light, only a component approximately parallel to the optical axis in the irradiation tube is output from the end face toward the opening of the nose portion 1125. Since the radiated light passes through the crank-shaped irradiation tube made of transparent resin to become focused light parallel to the optical axis, it is possible to provide an even amount of light over the whole area of the opening of the nose portion 1125. Thus, according to the present embodiment, there does not occur peripheral darkness in the case of diffused light, thereby enhancing the accuracy of scanning the dot pattern portion 607. FIG. 69 shows such a pen type scanner being connected to a device main body 1002. In FIG. 69, the device main body 1002 includes a memory card slot 1003. A memory card 1004 in which voice data and/or a program are registered can be inserted into the memory card slot 1003. The device main body 1002 is also connected to a microphone 1005 so that voice data from the outside can be registered in the memory inside the device main body. The voice data can be output from a speaker 1007 mounted on the device main body 1002 or a speaker 1006 connected to the device main body 1002. In FIG. 69, the pen type scanner 1001 and the device main body are connected by a cable. However, a radio interface is built in the pen type scanner so that the pen type scanner can connected with the device main body 1002 by radio communication. FIG. 71 shows a modification of a pen type scanner. As shown in FIG. 71, the pen type scanner 1001a includes a battery 1010 and a speaker 1007 and is also configured to receive a memory card 1004 including an SD card, a memory stick and a smart media. FIG. 72 shows the invention applied to a board game. A mini FIG. 1101 as a piece is moved along circles 1103 marked on the board 1102 and the number of circles the min FIG. 1001 passes is determined by dice or a speaker 1104. On the bottom of the mini FIG. 1101, a scanning device such as a CCD or a C-MOS is mounted. A dot pattern portion is formed on each of the circles of the board 1102. When the mini FIG. 1401 is put on a circle, voice information corresponding to the circle can be output from the speaker 1104 connected by a cable. This enables necessary information for game proceeding such as instructions to move to the next circle to be output. FIG. 73 shows a mini FIG. 1101 and a device main body 1102 which are separated. A scanner portion 1105 mounted on the bottom surface of the mini FIG. 1101 is used to scan a sot pattern portion so that a signal corresponding to the dot pattern portion is transmitted to the device main body 1102 by radio communication. The device main body 1102 includes a speaker 1007 so that voice information corresponding to the signal is read out of a memory card 1004 to be output. Here, with this configuration, in order to reduce communication traffic, a decoder is provided in the mini FIG. 1101, and image data of scanned dot pattern is decoded to be converted into several digit code information. Then, the code information is only transmitted as a scanned signal to the device main body 1102. FIG. 74 shows a modification in which a scanner portion 1105 provided on the bottom of a mini FIG. 1101 is used to scan a dot pattern portion formed on the surface of the seat 1110. According to the present embodiment, it is possible to change a scanned portion depending on the position of the scanner portion 1105 with respect to the dot pattern. For example, when the mini FIG. 1101 is inclined from the standing axis of the mini FIG. 1101 by a given angle with respect to the dot pattern, a scanned signal can be changed so that the voice data to be output can be changed depending on the direction the mini figure is oriented. Description of the method of changing voice data by changing the angle of the mini figure with respect to the dot pattern portion was made above and is omitted now. FIG. 75 shows another configuration example of a mini FIG. 1101. In this embodiment, the mini FIG. 1101 includes, in addition to the scanner portion 1105, a battery 1010 and a speaker 1007. Further, a memory card 1004 can be inserted into the mini figure. A program or voice data is changed by changing memory cards 1004 so that the game or the mini FIG. 1101 can be changed into completely different game or character. The mini figure 1101 shown in the figure is described using a doll shape which is simple in terms of drawings. However, it is needless to say that the mini figure can be any animation character, a small animal such as a pet, a fictional animal, a model of a person. FIG. 76 shows a dot pattern portion 1122 formed on a card 1121. This is a toy such that when the card 1121 is arranged horizontally turned by a given angle on a sear 1123 in which a scanner is mounted for scanning the dot pattern portion 1122, voice data or display data are used to output a score. FIG. 78 shows an example of a pen type scanner 1001 which is used to work a crossword puzzle 1132 printed on a magazine or the like. A dot pattern portion 1122 of the invention is formed in a white space 1133 of the crossword puzzle 1132 paper. When the end of the pen type scanner 1001 is abutted on a given blank space 1133, a hint of a word in a down word line or a across word line is displayed on an LC display 1131 of the pen type scanner 1001. In this case, when the end of the pen type scanner 1001 is abutted on the white space of which a hint is desired, a dot pattern formed in the white space is scanned and the hint of the word can be displayed on the LC display 1131. Then, if the scanner is abutted on one white blank, a hint in the down word line, a hint of the across word line or a hint in the oblique word line can be displayed depending on the angle of the pen type scanner 1001 being abutted. In this time, as described above, since tilt of a camera (shift in the rotational direction of the image pickup device with the vertical axis of paper as the center) can be calculated when a shift from a lattice point of a key dot with respect to a lattice point is calculated by the CPU, the vertical, horizontal and oblique direction of the crossword puzzle can be recognized depending on the tilt of the camera. Accordingly, a hint corresponding thereto can be read to be displayed and/or output from the speaker 1007. Here, when the pen type scanner 1001 is moved two cells in the vertical(down) direction, horizontal (across) direction or oblique direction, movement in the x and y coordinates is detected (detecting method is described above) thereby to display a word hint in the direction on the display 1131 and/or output by voice information from the speaker 1007. FIG. 80 shows a scanner portion 1005 mounted on the stomach of a self-advancing cat stuffed toy 1141. When the stuffed toy 1141 runs on a dot pattern portion 1122 formed on the floor in a house or a board of seal or the like, the dot pattern portion 1122 is captured, thereby to transmit the captured signal to the device main body 1102. FIG. 81 shows a scanner portion 1105 mounted on the bottom surface of a self-running or radio-controlled car toy 1151. The scanner portion 105 captures a dot pattern portion 1122 formed on a bard or a floor by seal or the like to send a scanned signal to the device main body. Thereby the device main body 1102 can output voice information corresponding to the dot pattern portion 1122 from the speaker 1007. For example, a sheet on which city roads are printed is prepared. When the car toy runs on the sheet, seals on which dot pattern portion 1122 are formed are attached to positions in front of street crossing and railroad crossing on the sheet. When the car toy approaches the street crossing or railroad crossing, voice information for urging the car to stop can be output from the speak 1007 of the device main body 1102. FIG. 82 shows an explanatory view showing that the invention is applied to a versus card game. As shown in FIG. 82, a pair of card slots are provided on a device main body 1102, when cards 1121, 1121 of two players are inserted into the card slot like one card into one slot, superiority between the parameters set on the cards 1121, 1121 is judged. On the surface of each of the cards 1121, a dot pattern portion 1122 is provided as explained on FIG. 77, and when this dot pattern portion 1122 is scanned by the scanner portion 1105 of the device main body 1102, the parameter corresponding to the dot pattern portion 1122 is read out of a memory card 1004 thereby to judge a winner. Here, an LC display screen can be mounted on the device main body 1102 so that a winning result can be displayed. FIG. 83 shows an example of the device main body into which only one card 1102 can be inserted. FIG. 84 shows an embodiment in which the device main body 1102 is a simple card reader and the device main body 1102 is connected to a personal computer. FIG. 85 shows an example of a device main body 1102 for sequentially scanning postcard-sized sheets 1161 on which dot pattern portions are formed. For example, the device main body is suitably configured to scan return postcards from users on which dot pattern portions are formed. FIG. 86 shows an example of a device main body 1102 which can be utilized in a POS register or the like. A scanner portion 1105 arranged under a glass face 1171 is used to scan a dot pattern portion 1122 attached to an article which passes on the glass face 1171, thereby enabling goods management, sales management and so on, just like a barcode. In this case, according to the invention, since it is possible to form a dot pattern portion on a printed face of a wrapping paper sheet or a wrapping box in such a manner that the dot pattern portion is superimposed on the printed face, it is possible to avoid awkward occupation of a barcode on a surface of an article like in the barcode system. FIG. 87 shows an example of a device main body consisting of a seat 1102 which is combined with a mini figure 1110. According to this embodiment, a glass plate 1171 is arranged on the upper face of the seat 1102 and a scanner portion 1105 is provided under the glass plate 1171. Then, when the mini FIG. 1101 on which a dot pattern portion 1122 is formed on the bottom is deposed on the seat 1102 the dot pattern portion 1122 is scanned by the scanner portion 1105 and thereby voice data corresponding to code number read from the dot pattern portion 1122 is read out of a memory card 1004 to be output from a speaker 1007. FIG. 88 shows an example of the device main body 1102 connected to a TV monitor 1171. An image signal and a voice signal from the device main body 1102 is to be output via a pin plug to the TV monitor 1171. The voice signal and the image signal are stored in a memory card 1004 or a built-in memory of the device main body 1102. The motion data corresponding to a dot pattern portion 1122 captured by a pen type scanner 1001 is divided into voice data and image data, which are input to the TV monitor 1171 to be output from a screen and speaker of the TV monitor 1171. FIG. 89 shows a photo-stand-type device main body 1102. A dot pattern portion 1122 is formed at the back side of a picture 1181. A scanner portion (no shown) is provided at a back surface of the stand portion of the device main body 1102. Voice information corresponding to a code number of the scanned dot pattern portion 1122 is read out of a memory built in the device main body 1102 or a memory card to be output from a speaker 1007. According to this embodiment, since a voice corresponding to a dot pattern portion 1122 can be registered in a built-in memory or a memory card 1004 in advance for each picture 1181, a comment at the time of taking the picture or a voice message like “happy birthday” can be reproduced from the speaker 1007. In addition to the speaker 1007, a microphone 1005 is mounted. Voice data is registered in a built-in memory or a memory card 1004 and may be associated with a dot pattern portion 1122 attached in advance to a back surface of a picture 1181. Further, the photo-stand-type device main body 1102 in FIG. 89 has a LC display 1131. Data such as a shooting date, message text or the like is associated with a dot pattern portion 1122 and the data are also associated with the picture 1181 to be displayed on the LC display 1131. FIG. 90 shows a pen type scanner 1001 connected to a PC 1201 via a USB cable. Connection between the pen type scanner 1001 and the PC 1201 may be realized using, other than the USB interface, RS-232C serial interface, a LAN interface, IEEE1394 interface or the like. Further, a radio interface card 1209 is mounted on a PC and the PC can be connected to the pen type scanner 1001 by radio communication. The radio interface can be a blue tooth, wireless LAN or the like. Further, connection between the pen type scanner 1001 and the PC 1201 can be realized by an optical interface such as infrared data communication other than radio interface. FIG. 91 shows a pen type scanner 1001 connected to a PDA 1202 by a cable. Connection between the PDA 1202 and the pen type scanner 1001 can be realized by wired connection, radio connection or optical communication connection. FIG. 92 shows a scanner integrated mouse 1301 connected to a PC 1201. The mouse 1301 is usually connected to the PC 1201 by a cable. However, connection can be realized by radio connection or optical communication connection. FIGS. 93 and 94 show a mouse 1301 having a digitalizer function. In this mouse a scanner portion 1105 is mounted, and a transparent window made of a glass member 1302 is provided at the end of the mouse 1301. With this window, it is possible to have in one's sights a target of the dot pattern portion 1122 to be scanned by the scanner portion 1105. FIG. 95 shows a configuration of a scanner portion 1105 which is provided in the main body of PDS 1202, and FIG. 96 shows a configuration of a scanner portion 1105 which is provided in a PC main body 1201. As shown in FIG. 95, when the scanner portion 1105 is mounted on the PDA 1202 main body, the scanner portion 1105 of the PDA 1202 main body is held over a dot pattern portion 1122 on paper or the like and the dot pattern portion 1122 can be scanned. On the other hand, as shown in FIG. 96, when the scanner portion 1105 is provided in the PC main body 1201, the scanner portion 1105 is held over a dot pattern portion 1122 formed on a business card or card 1121 (see FIG. 77) thereby to scan the dot pattern portion 1105. As shown in FIGS. 97 and 99, a scanner portion 1105 may be mounted on a portable phone 1401 main body or game machine main body (not shown). FIG. 98 shows a pen type scanner 1001 connected to a connector of a portable phone 98. In this configuration, a scanned signal scanned by the pen type scanner 1001 corresponding to a dot pattern portion can be processed by a program downloaded in advance-in the portable phone 1401 displayed on the display of the portable phone or output by voice. Also, result data, which has accessed to the server by the program and processed at the server by sending the scanned signal can be received by the portable phone 1401. FIG. 100 is a view for explaining a configuration of a pen type scanner 1001 provided with a LC (liquid crystal) display 1131 and a speaker 1007. The pen type scanner 1001 according to the present embodiment has a writing material 1601 such as a ball pen, mounted at the end thereof and a scanner portion 1105 is provided around the writing material. As an example of use of such pen type scanner 1001, a dot pattern portion 1122 is formed at a menu of a restaurant or the like and the menu and the pen type scanner 1001 are handed to a client when he comes in the restaurant. The client selects from the menu and checks a square box of the selected article by the writing material 1601. At this time, a dot pattern portion 1122 corresponding to the selected article is scanned by the scanner portion 1105. Thus, processing by the central processing unit inside the pen type scanner 1001 makes letter information corresponding to the selected article to be read from a memory to be displayed on the LC display 1131. In FIG. 100, displayed on the LC display 1131 is the article name selected by the client “Japanese chopped steak plate set”, its calorie “864 kcal” and its price “1,250 yen”. In this way, since a client himself selects from a menu and confirms its selection by use of a pen type scanner 1001, a staff can complete order processing only by collecting the pen type scanner 1001. FIG. 101 is a view showing a configuration of a pen type scanner 1001 provided with a microphone 1005 and a speaker 1007. In this embodiment, a dot pattern portion 1122 formed on a surface of a picture 1181 is scanned by a scanner portion 1105, after scanning is completed, a microphone 1005 is used to input a voice corresponding to the dot pattern portion 1122. The input voice data is registered in a memory (not shown) in the pen type scanner 1001. The voice at this time includes a description and greeting informing that the picture 1181 has been taken. Here, if a dot pattern portion 1122 is formed all over the picture surface, in the case of a group photo, a description for each person in the group photo can be registered. Next, an end (scanner portion 1105) of the pen type scanner 1001 is abutted on a portion on the surface of the picture 1181 of which explanation is desired. Then, voice data can be reproduced from a speaker 1007. In addition to the picture 1181, a dot pattern 1122 is formed on each seal. Then, a pen type scanner 1001 is abutted on the seal surface to input the voice data. FIG. 102 is a view showing an example of an organizer 1701 and a pen type scanner 1001 which are combined to be used. In FIG. 102, a dot pattern portion 1122 is formed in advance in a schedule section 1702 of the organizer 1701. In registering a schedule in the schedule section 1702, if a person can not afford recording letters on the way, an end (scanner portion 1105) of the pen type scanner 1001 is abutted on the schedule section 1702 of the date at which the schedule is input, and a schedule of the date is input by voice from a microphone (not shown). In checking the schedule on the organizer 1701, the pen type scanner 1001 (scanner portion 1105) is abutted on the schedule section 1702 of the checked date to scan the dot pattern portion 1122. Thereby, the schedule input by voice corresponding to the date is reproduced from the speaker 1007. Here, the pen type scanner 1001 is configured to be connectable to a PC 1201 by a USB interface or the like and establishes data like (synchronized) with a schedule managing system in the PC 1201 (for example, Outlook of Microsoft Corporation, Lotus Note or the like) Then, when the pen type scanner 1001 is used to scan the dot pattern portion 1122 of the date section (schedule section 1702), the schedule corresponding to the date is set to be displayed on the LC display 1131 with text data as shown in FIG. 102. When the pen type scanner 1001 may be connected to the PC 1201 and the dot pattern portion formed on the surface of the organizer 1701, an ID card, a license card or the like to control inputting of the PC 1201. Such a control of the PC 1201 is called “paper icon”, an icon on the screen of the PC 1201 can be replaced with an external medium on which a dot pattern portion 1122 (seal attached to the organizer 1701, ID card). In other words, the pen type scanner 1001 is used to scan the dot pattern portion 1122 on the medium, and only if code information scanned from the dot pattern portion 1122 matches code information stored in the PC 1201, access to the PC 1201 is permitted. The dot pattern portion 1122 may be printed on a seal, as a paper icon which is attached to a surface of the organizer 1701, an ID card or a license card. Or, a user may print it by a printer connected to the PC 1201 and hold printed seal. Here, a paper icon on which the dot pattern portion is formed is used to control access to the PC 1201. However, it can be used to input an ID or password in starting a particular application or accessing to a particular internet site. Such paper icon can be managed by an application program for paper icon installed on the OS of the PC. Specifically, management is configured of three steps of “icon registration on PC”, “paper icon registration” and “icon deletion”. <Registration of Normal Icon> An application program for paper icon on a PC has an editor thereby to create and set a paper icon on a screen. When, in the icon editor, an icon for executing a predetermined function on the PC is registered on the editor, first, icon allocation (ALLOCATE) is turned “ON”. Next, a desired icon on the PC screen is designated by a mouse, and the icon is registered on the editor. The icon thus registered on the editor is set in an initial state in which display is “ON” and Executable state (active) is “ON”. In this state, on the editor, when the display is turned “OFF”, the icon is erased from the display. When the executable state (active) is turned “OFF”, designation and execution of the icon on the PC and execution of keyboard inputting are inabled. <Registration of Paper Icon> In the editor, allocation of paper icon (ALLOCATE) is turned “ON”. Next, the icon on the display is turned “ON” to scan a medium of the paper icon, which is desired to be registered, by a pen type scanner or the like. By the above-described operation, a code of a dot pattern of the scanned paper icon is registered on a selected icon (allocated). In the initial state of the paper icon, the executable state (activate) is “ON” and a password can be inputted. Then, the password is inputted, the password is encoded by an editor program and registered. In this state, when the executable state (active) is turned “OFF”, even if the paper icon is scanned by the pen type scanner, a function defined on the icon can not be executed. <Deletion of Icon> When a deletion flag (DELETE) is turned “ON”, an executable state (active) is simultaneously turned “OFF” Then, the icon image flag is designated in this sate, the icon is deleted and no longer recovered. <Deletion of Paper Icon> Also in deletion of paper icon, when a deletion flag (DELETE) is turned “ON”, an executable state (active) is simultaneously turned “OFF”. Then, code number assigned to a paper icon is designated in this state, a password is required to be inputted. When the password is input, a link to the paper icon on an editor is deleted and no longer recovered. The dot pattern portion 1122 can include, in addition to a medium of a picture book described in the embodiment, a normal book, a greeting card, a newspaper, a wish book, a pamphlet, a paper craft, an origami and a recipe. For example, a dot pattern portion is formed on a wish book. Then, the dot pattern portion is scanned by a scanner portion to output explanation of goods or to start an order program registered in a memory in a PC. Further, a dot pattern portion is formed a paper craft or an origami. Then the dot pattern portion is scanned by a scanner portion to explain fabrication process of the paper craft and the origami via a speaker. Further, a dot pattern portion is formed on a recipe of cooking or the like, and the recipe can be output by voice. Furthermore, a dot pattern portion according to the invention is used to provide a picture book for coloring. Specifically, areas (mask areas) shown in FIGS. 106(b) and 106(c) can be colored with different colors by crayon, felt pen, water-color pigment or the like. In this case, even if a non-carbon water-color pigment, crayon, felt pen or the like is used to color the paper on which the dot pattern portion is formed, as infrared light is capable of passing through the colored layer, the dot pattern portion can be scanned. Furthermore, the dot pattern portion and a barcode reader can be superimposed to be printed. In this case, a barcode is printed on a medium such ash paper with a non-carbon ink, and on the printed barcode, the dot pattern portion is printed with a carbon ink. A normal barcode reader is capable of reading a barcode accurately even a small dot is on the barcode. Next, a pen type scanner according to the invention is used to input only a reading information code of the dot pattern portion. Further, a barcode is printed with a ink which absorbs “(A) visible light+infrared light or ultraviolet light close in wavelengths to the visible light” or “(B) infrared light or ultraviolet light close in wavelengths to the visible light”, while dots are printed with a ink which absorbs “(C) infrared light or ultraviolet light different in wavelengths from the infrared light or ultraviolet light used in the barcode”. In this case, a visible light cut-off filter is mounted on a C-MOS camera, a first LED for emitting light with the same wavelength as that of the above-mentioned (A) or (B) is made to emit light so as to read a barcode. Next, a second LED for emitting light with the same wavelength as that of the above-mentioned (C) is made to emit light so as to read only a dot pattern portion and input information code. In this way, since information from the dot pattern portion is arranged on the barcode, convoluted information (barcode and code from the dot pattern portion) can be acquired. INDUSTRIAL APPLICABILITY A dot pattern portion of the present invention is usable by being formed on publications including a book and a picture book, a picture seal, a seal with a dot patter for inputting formed on, a picture seal, a game board, character goods including a figure and a stuffed toy and touch panel of a monitor screen of a personal computer, television or the like. A reading system of a dot pattern portion can be utilized as an inputting system of a toy computer area for children and a general purpose computer. Further, the system is housed in a case to be used as a stand-alone scanner in an electronic device, a voice recorder and the like.
<SOH> BACKGROUND OF THE INVENTION <EOH>1. Field of the Invention The present invention relates to a technique of optically scanning dot pattern information formed on a printed material and reproducing various kinds of information corresponding to the dot pattern information. 2. Description of the Related Art Heretofore, there has been proposed a voice emitting toy for reading a barcode printed on a picture book or a game card using an optical sensor and emitting a particular voice. Such a voice emitting toy enables to read from a memory various kinds of voice information corresponding to a read barcode to reproduce the voice information. However, such a technique using a barcode requires a dedicated area on paper to be reserved for printing the barcode, and the barcode is only for an information processing system to read, and a code description of the barcode can not be visually understood by a reader of a book including a picture book. Since the barcode is printed on a limited paper space, a reader feels it unpleasant and the barcode sometimes may reduce a product value of a book including a picture book. Further, since the barcode, as mentioned above, can not be printed over letters, graphics or symbols printed on a paper sheet, when these letters, graphics, symbols and the like are used to reproduce voices, the barcode has to be printed near them, which presents a trouble such that it is difficult for a reader to intuitively know voice information or the like added on the letters or the like. Regarding this point, a “dot code” technique disclosed in the Japanese Laid-Open patent publication No. 10-261059 proposes a method for scanning code information printed by a dot pattern to reproduce information. In the related art, data is defined by way for arranging a dot pattern in a block field, and a marker is defined by a dot pattern which is different from the data dot pattern to serve as a synchronization signal. According to this technique, a dot pattern created by printing dots in the two-dimensional direction on a paper sheet in accordance with a predetermined rule is read by a pen type scanner, and the scanning speed and the scanning direction of this scanner is analyzed by an information processing device thereby to reproduce information including a voice which is associated therewith in advance. However, since such a dot code technique is based on the assumption that dots are dynamically scanned by a scanner, although it can reproduce voice information along letters printed on a paper sheet, it is not adequate to reproduce information only by statically abutting a scanning device to a picture book or the like on which a character and the like are freely arranged and printed. In other words, since this dot code technique requires to carry out more than a predetermined distance of scanning on the x and y coordinates in order to obtain significant code information, it is impossible to associate a minimum area with a dot code and to print the area.
<SOH> SUMMARY OF THE INVENTION <EOH>The present invention proposes a dot pattern that allows to define code information or the x and y coordinates even if the dot pattern is an minimum area, and an information reproducing method and an information reproducing device based on the dot pattern A first aspect of the invention is configured to include the steps of: scanning as image data by scanning means ( 602 ) a medium such as a printed material ( 606 ) on which is formed a dot pattern portion ( 607 ), the dot pattern portion being formed by arranging in accordance with a given rule dots ( 605 ) generated by a dot code generating algorithm, in order to recognize various kinds of multimedia information; converting the image data of the dot pattern portion ( 607 ) into code data; and reading multimedia information corresponding to the code data out of storing means to reproduce the multimedia information. The multimedia information here may be any one of followings: voice information, image information, video information, and visible, audible and readable information such as a letter and a symbol. Further, the multimedia information may be digital data for another personal computer, a television system or a radio terminal to reproduce video/image information, text information and the like. Here, on the dot pattern portion ( 607 ), code information corresponding to voice data registered in the storing means may be defined or the x and y coordinates may be defined. Also, both of the code information and the x and y coordinates may be defined. In a header of the dot pattern portion ( 607 ), a flag may be registered to determine the dot pattern portion is code information or x and y coordinates. The medium may be a picture book or a photograph. The dot pattern portion ( 607 ) for recognizing voice information corresponding to image ( 606 b ) of the picture book or the like may be printed over the image ( 606 b ). The dot pattern portion ( 607 ) may be printed on a seal member. The dot pattern portion ( 607 ) may be formed on a transparent film ( 611 ). In this case, the transparent film may be arranged over a paper sheet, or the transparent film ( 611 ) may be attached to display means ( 613 ) of an electronic device as a touch panel. Then, the display means ( 613 ) is used to display instruction information so as to make a user to operate scanning means. Between the touch panel ( 612 ) and the medium such as the paper sheet or the display means ( 613 ), an infrared cutoff filter ( 614 ) may be arranged. In addition to the case that the touch panel is attached to the aforementioned display means ( 613 ), the touch panel may be attached on a book such as a picture book, a figure or the like. Here, the scanning means ( 602 ) may be configured separately from an electronic device including a personal computer ( 608 ), a PDA and a portable phone, and data communication may be established between them by wire communication, radio communication or optical communication. However, the scanning means ( 602 ) may be housed in the electronic device integrally. In this case, the electronic device may be configured by a pen type case or a mouse type case, in addition to the electronic devices. A second aspect of the invention is an information inputting/outputting method by camera inputting comprising the steps of: printing on one surface of a printed material ( 5 ) a dot pattern portion ( 6 ) formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm in order to recognize various kinds of multimedia information and an information transfer portion ( 7 ) which includes a text, an illustration or the like to be recognized as information content; capturing by a camera unit ( 2 ) only image data of the dot pattern portion( 6 ) in the printed material ( 5 ) and digitalizing the image data into numeric values; and based on the numeric values, outputting information and a program corresponding to the dot pattern portion ( 6 ) from a storing portion ( 10 ) and executing the information and the program. The dot pattern portion ( 6 ) and the information transfer portion ( 7 ) comprising of the text or the illustration or the like may be printed on the one surface to be superimposed. The dot pattern portion ( 6 ) may be defined by x and y coordinate information and the x and y coordinate information may be associated with content of the information transfer portion ( 7 ). The dot pattern portion ( 6 ) may be defined by code numeric information and the code numeric information may be associated with content of the information transfer portion ( 7 ). The dot pattern portion ( 6 ) of the x and y coordinate information and the dot pattern portion ( 6 ) of the code numeric information are printed on a flat surface of the printed material ( 5 ). The dot pattern portion ( 6 ) may be printed with an ink that absorbs infrared light, a carbon ink or a transparent ink. When the camera unit ( 2 ) is used to capture image data of the dot pattern portion ( 6 ), the dot pattern portion ( 6 ) may be radiated with ultraviolet light. Information to be output may be digital data including a voice, image, video and text code. The configuration may be made to output a program in addition to the information of digital data. The information transfer portion ( 7 ) to be printed on one surface together with the dot pattern portion ( 6 ) may be a text or an illustration. The camera unit ( 2 ) may be an image pickup device such as a C-MOS camera or a CCD camera. Hereinafter, what is called “camera unit” may include any imaging means having such a configuration. In addition, the camera unit ( 2 ) may be configured separated from the image processing portion ( 12 ), the storing portion ( 10 ), the processing portion ( 9 ) and the outputting portion ( 15 ) to carry out transmission via an interface portion. Here, the interface portion may include both function means having an integrally-formed CPU and sound source memory in abstract terms and function means such as a connector for exchanging data. The camera unit ( 2 ) and the image processing portion ( 12 ) is configured separated from the storing portion ( 10 ), the processing portion ( 9 ) and the outputting portion ( 15 ) to carry out transmission and reception via an interface portion. Communication with the interface portion may be realized by wire communication, radio communication including wireless LAN and blue tooth, or optical communication such as infrared communication. The printed material ( 5 ) on which the dot pattern portion ( 6 ) is printed may be attached to various mediums via an adhesive agent. The storing portion ( 10 ) may store, in addition to information including a text, image and video, a program. Such information and program may be stored in the storing portion ( 10 ) via an inputting portion ( 17 ). Accordingly, a use can store any voice information as associated with a given dot pattern portion ( 6 ) in advance. This inputting portion ( 17 ) may be a microphone or a line-in interface. Further, the configuration may be made to mount a communication card ( 16 ). Then, the numeric data obtained by digitalizing a dot pattern ( 1 ) scanned by the camera unit ( 2 ) may be transmitted to a computer ( 23 ) such as a server via the communication card ( 16 ). This configuration may allow to store a huge amount of multimedia information in a server and reproduce various types of multimedia information via communication. More specifically, a network address (URL: Uniform Resource Locator) is defined on the dot pattern ( 1 ), the communication card ( 16 ) is used to establish communication to TCP/IP communication network (so-called Internet) and thereby voice data stored at the network address may be downloaded in the storing portion ( 10 ) to be reproduced. Here, other than the communication card ( 16 ), a GPS (Global Positioning System) receiver ( 24 ) maybe further provided. This makes it possible to reproduce multimedia information based on position information together with content scanned from the dot pattern ( 1 ) A third aspect of the invention is an information inputting/outputting device using a portable-phone camera, comprising: a camera unit ( 102 ) for scanning only image data of the dot pattern portion ( 6 ) printed on the printed material ( 5 ), the dot pattern portion ( 6 ) formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm in order to recognize various kinds of information and an information transfer portion ( 7 ) which includes a text, an illustration or the like to be recognized as information content being printed on one surface of the printed material; an image processing portion ( 112 ) for digitalizing the image data into numeric values; an interface portion ( 119 ) for transferring the digitalized numeric information so as to output from a portable phone ( 110 ) and execute information and a program corresponding to the dot pattern portion ( 6 ). Since such a camera equipped portable phone is used, the information reproducing device can be configured simply. Such a camera equipped portable phone may be an information-processing-device-integrated portable phone such as i-mode phone provided from NTT Docomo Inc. This information processing device includes a central processing unit, a storing device (memory), a liquid crystal display screen and the like. In the storing device (memory), a program, voice data, video data and text data can be stored. An operation system (OS) mounted on a portable phone may be Toron, Symbian, Windows CE available from Microsoft Corporation, LINUX, PALM-OS or the like. Such a camera equipped portable phone may be configured so that a memory card such as an SD card, a memory stick, a SIMM card can be mounted on the portable phone and further, content data is recorded in the memory card to be reproduced. A fourth aspect of the invention is a portable electronic toy comprising: a voice storing portion ( 804 ) for storing a voice corresponding to a dot pattern portion ( 803 ) formed on a medium ( 802 ) including a book, a game card, a small article and a toy, the dot pattern portion ( 803 ) on which numeric data or code information are recoded in order to recognize various voices; a camera ( 810 ) for capturing image data of the dot pattern portion ( 803 ); a processing portion ( 806 ) for processing the image data captured by the camera ( 810 )and reading voice data corresponding the numeric data out of the voice storing portion ( 804 ) to output the voice data by use of a speaker ( 805 ); and a case main body ( 808 ) for housing the voice storing portion ( 804 ), the speaker ( 805 ) and the processing portion ( 806 ). This case main body ( 808 ) may be configured to be of organizer size. Besides, the case main body ( 808 ) may be provided with an LC display ( 812 ). Further, the dot pattern portion ( 803 ) can be printed on a versus game card. Or, the dot pattern portion ( 803 ) may be formed on a miniature figure (hereinafter referred to as “mini figure”) of an animation character on sale in convenience stores and the like as a candy toy or a seal on which the dot pattern portion ( 803 ) is printed may be attached to such a mini figure. Furthermore, in order to allow intercommunication between plural portable electronic toys ( 821 ), a connector for a connection cable may be provided on the case main body ( 823 ). In this case, the connector may be a USB connector or any connector in conformity with IEEE 1394. Further, communication may be used by Blue tooth, wireless LAN or infrared data communication. A fifth aspect of the invention provides a configuration with an information outputting function by camera inputting, in a figure ( 218 ) of a given shape, the configuration comprising: a camera ( 202 ) for scanning only image data of a dot pattern portion ( 6 ) printed on a printed material ( 5 ), the dot pattern portion ( 6 ) formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm in order to recognize information and an information transfer portion ( 7 ) which includes a text, an illustration or the like to be recognized as information content being printed on one surface of the printed material; an image processing portion ( 212 ) for digitalizing the image data into numeric values; and a processing portion ( 209 ) and an outputting portion ( 215 ) for outputting and executing information and a program of a storing portion ( 210 ) corresponding to the dot pattern portion ( 6 ) based on the numeric values processed by the image processing portion ( 212 ). Besides, a speaker ( 214 ) may be provided as an outputting portion ( 215 ) to output a voice. Further, the storing portion ( 210 ) maybe configured to store information and a program from the outside by use of a microphone ( 217 ). Further, the figure ( 218 ) may be configured to be a stuffed toy ( 231 ) made by stuffing an elastic material in an outer skin of a predetermined shape. Furthermore, the configuration with an information outputting function by camera inputting may include in a figure ( 218 ): a camera unit (A) configured by including a camera ( 202 ) for capturing only image data of a dot pattern portion ( 6 ) printed on a printed material ( 5 ), the dot pattern portion ( 6 ) formed by arranging in accordance with a given rule dots generated by a dot code generating algorithm in order to recognize information and an information transfer portion ( 7 ) which includes a text, an illustration or the like to be recognized as information content being printed on one surface of the printed material and an main processor ( 209 ) digitalizing the image data into numeric values; an outputting unit (B) including a processing portion ( 9 ) and an outputting portion ( 15 ) for outputting and executing information and a program of a storing portion ( 10 ) corresponding to the dot pattern portion ( 6 ) based on the numeric values processed by the image processing portion ( 12 ) in the camera unit (A); and an interface portion for mediating communication between the camera unit (A) and sand outputting unit(B).
20050325
20110628
20060713
61090.0
A63H328
1
HESS, DANIEL A
INFORMATION REPRODUCTION/I/O METHOD USING DOT PATTERN, INFORMATION REPRODUCTION DEVICE, MOBILE INFORMATION I/O DEVICE, AND ELECTRONIC TOY
SMALL
0
ACCEPTED
A63H
2,005
10,529,545
ACCEPTED
Backlight unit and liquid crystal display unit using backlight unit
To compensate for uneven brightness in the longitudinal direction of fluorescent lamps of a backlight unit and achieve a display screen with an even brightness, a reflection unit of the backlight unit, the fluorescent tube surface of the fluorescent lamps or a diffusion unit is used to either reduce the reflectance, transmittance, or radiation brightness of the high-voltage side of the fluorescent lamps or increase the reflectance, transmittance, or radiation brightness of the low-voltage side thereof so as to compensate for uneven brightness of the illumination light and thereby ensure an even brightness. For example, dot pattern regions D1, D2 and D3, i.e., the regions whose density increases in stages, are imparted to the portion of a reflection layer 13 of the backlight unit with a relatively high brightness. As for the display device, on the other hand, the display image data supplied to a liquid crystal panel or the aperture ratio of the liquid crystal panel is controlled, for example, to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps and ensure an even brightness.
1. A backlight unit operable to illuminate the target with fluorescent lamps, the backlight unit comprising brightness compensation means adapted to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. 2. The backlight unit of claim 1 comprising a reflection portion adapted to emit the light from the fluorescent lamps in a specific direction, wherein the brightness compensation means are provided on the reflection unit and control the reflectance of the reflection portion to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. 3. The backlight unit of claim 2, wherein the brightness compensation means have regions with relatively high and low reflectances in the reflection portion and take advantage of the difference in reflectance to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. 4. The backlight unit of claim 3, wherein the brightness compensation means have a reflectance gradient that causes the reflectance of the reflection portion to decline gradually or in stages and take advantage of the reflectance gradient to reduce the brightness of the portion with a relatively high brightness in the longitudinal direction of the fluorescent lamps. 5. The backlight unit of claim 3 or 4, wherein the brightness compensation means have a reflectance gradient that causes the reflectance of the reflection portion to increase gradually or in stages and take advantage of the reflectance gradient to increase the brightness of the portion with a relatively low brightness in the longitudinal direction of the fluorescent lamps. 6. The backlight unit of any one of claims 2 to 5, wherein the brightness compensation means are a dot pattern provided on the reflection portion and take advantage of the dot pattern to control the reflectance of the reflection portion. 7. The backlight unit of claim 6, wherein the reflectance of the reflection portion provided with the dot pattern is controlled by one or a plurality of the reflectance of the group of small dots making up the dot pattern, the dot density, the dot shape, and the dot color. 8. The backlight unit of claim 1 comprising a reflection portion adapted to emit the light from the fluorescent lamps in a specific direction, wherein the reflection portion is made up of first and second reflection layers having given optical reflectance and transmittance levels, wherein the reflection portion is configured with a first region having the first and second reflection layers stacked one above another in the direction of incidence of light and a second region made up only of the first reflection layer, and wherein the reflectance of the reflection portion is controlled using the first region with a relatively high reflectance and the second region with a reflectance lower than that of the first region. 9. The backlight unit of claim 1, wherein the brightness compensation means are provided on a glass tube of the fluorescent lamps and control the transmittance of the glass tube to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. 10. The backlight unit of claim 1 comprising a diffusion portion adapted to diffuse the light from the fluorescent lamps, wherein the brightness compensation means are provided on the diffusion portion and control the transmittance of the diffusion portion to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. 11. The backlight unit of claim 9 or 10, wherein the brightness compensation means have regions with relatively high and low transmittances in the glass tube or the diffusion portion and take advantage of the difference in the transmittance to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. 12. The backlight unit of claim 11, wherein the brightness compensation means have a transmittance gradient that causes the transmittance to decline gradually or in stages and take advantage of the transmittance gradient to reduce the brightness of the portion with a relatively high brightness in the longitudinal direction of the fluorescent lamps. 13. The backlight unit of claim 11 or 12, wherein the brightness compensation means have a transmittance gradient that causes the transmittance to increase gradually or in stages and take advantage of the transmittance gradient to increase the brightness of the portion with a relatively low brightness in the longitudinal direction of the fluorescent lamps. 14. The backlight unit of any one of claims 9 to 13, wherein the brightness compensation means are a dot pattern provided on the glass tube of the fluorescent lamps or the diffusion portion and take advantage of the dot pattern to control the transmittance. 15. The backlight unit of claim 14, wherein the transmittance of the glass tube or the diffusion portion provided with the dot pattern is controlled by one or a plurality of the reflectance of the group of small dots making up the dot pattern, the dot density, the dot shape, and the dot color. 16. The backlight unit of claim 1, wherein the brightness compensation means are provided on the glass tube of the fluorescent lamps and control the tube surface brightness of the glass tube to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. 17. The backlight unit of claim 16, wherein the thickness of the fluorescent substance formed inside the glass tube of the fluorescent lamps as the brightness compensation means is changed correspondingly with the longitudinal position of the fluorescent lamps to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. 18. A liquid crystal display device comprising the backlight unit of any one of claims 1 to 17 and a liquid crystal panel illuminated by the backlight unit. 19. A liquid crystal display device operable to apply an illumination light from a backlight unit having fluorescent lamps to a liquid crystal panel to display images, the liquid crystal display device comprising brightness compensation means adapted to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. 20. The liquid crystal display device of claim 19, wherein the brightness compensation means have a gradation conversion portion operable to carry out a given gradation conversion process of input image data and a control portion operable to switch between gradation conversion characteristics of the gradation conversion portion based on a synchronizing signal of the input image data, and wherein the control portion switches from one gradation conversion characteristic to another in the gradation conversion portion based on the screen position to display the image data to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. 21. The liquid crystal display device of claim 19, wherein the liquid crystal panel is configured to have, as the brightness compensation means, an aperture ratio that changes correspondingly with the display screen position, and wherein the aperture ratio is changed to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps.
TECHNICAL FIELD The present invention relates to a backlight unit operable to illuminate a target from the rear side and a liquid crystal display device using the backlight unit. BACKGROUND OF THE INVENTION A backlight unit is used to illuminate the target such as an LCD display panel. An LCD display device employs either one of two types of backlight configurations as a backlight unit; the direct type and the edge light type (light guide plate type). With the direct type, fluorescent tubes, i.e., a light source, are arranged directly below the liquid crystal panel to be illuminated. This allows fluorescent tubes to be increased with the change in the display screen size, thus achieving a sufficient brightness. In this case, however, the backlight unit is prone to an uneven brightness between areas having a fluorescent lamp and others not. Moreover, the direct type backlight unit must be built with sufficient strength. For example, the backlight case is fabricated with a metal plate. Then, a reflective sheet is affixed to the inner surface of the backlight, with a plurality of straight tube lamps arranged thereabove. With the edge light type, on the other hand, a fluorescent lamp is arranged at the edge of a light guiding body made, for example, of a clear acrylic plate. This type of backlight unit takes advantage of multireflection in the light guiding body to use one surface thereof as an area light source. The edge light type has a reflector at the back of the straight tube lamp and L-shaped lamp. Although the display device using the edge light type backlight unit can be reduced in thickness, the light guiding body of the large-size model becomes excessively heavy. Besides, upsizing of the device makes it difficult to secure sufficient screen brightness. The aforementioned features are the reasons why, in general, the direct type backlight unit is used for a large-screen liquid crystal display device, whereas the edge light type backlight unit is used for those with a small screen. The fluorescent lamps used for the backlight unit as described above are driven by a high voltage of 1 KV at a high frequency of 50 to 70 KHz to achieve even and high brightness. At this time, the fluorescent lamps develop uneven brightness, i.e., uneven brightness, in the form of a brightness gradient between the high- and low-voltage sides as a result of a leak current. This problem is caused by the following reason. The fluorescent lamps are driven by a high voltage at a high frequency. This causes the air layer to act as a stray capacitance and leads to a leak current flowing from the fluorescent lamps to the lamp reflector and the surrounding metal objects. As a result, the current flowing into the low-voltage side of the fluorescent lamps diminishes. This causes the low-voltage side to illuminate relatively less brighter than the high-voltage side. Therefore, if the fluorescent lamps are long, the leak current rises proportionally to the length thereof. In the presence of a large leak current, the farther the fluorescent lamps are from the drive circuit, the darker they become. This constitutes the cause of uneven brightness. That is, the larger the liquid crystal display device, the more likely the difference in brightness occurs between the high- and low-voltage sides of the lamps. It can be said that the technique allowing the realization of a backlight unit with minimal uneven brightness is essential. FIG. 18 is an explanatory view of the brightness characteristic of fluorescent lamps, illustrating an example of the brightness distribution in the longitudinal direction (i.e., in the direction of voltage application) of the fluorescent lamps generally used for a backlight type liquid crystal display device. As shown in FIG. 18, the fluorescent lamps have a brightness gradient whose relative brightness diminishes from a high-voltage side H to a low-voltage side L. The brightness drop is particularly noticeable near the edge of the low-voltage side L. The brightness distribution curve itself also varies depending on the shape of the fluorescent lamps, the length of the fluorescent tube, the drive voltage or the drive frequency. Basically, however, the fluorescent lamps develop uneven brightness in the form of relatively low brightness at the low-voltage side L as compared with the high-voltage side H. FIG. 19 is a graph showing the brightness distribution characteristic in the longitudinal direction (in the direction of voltage application) of the fluorescent lamps having the brightness gradient shown in FIG. 18 when the drive voltage is further raised. In the example of FIG. 19, the brightness of the fluorescent lamps at the center and low-voltage side L is roughly equal. However, the brightness is relatively higher near the edge at the high voltage side H. For example, assuming that the brightness is 100 at the center and the low-voltage side, the brightness is relatively higher or 115 to 125 at the high-voltage side H. The brightness, highest at the edge of the high-voltage side H, gradually declines toward the center of the fluorescent lamps. The display screen also develops uneven brightness due to uneven brightness developed by the fluorescent lamps in the longitudinal direction as described above. As a technique to reduce such uneven brightness in the display screen, the liquid crystal display device using a backlight is known as shown below. FIGS. 20A and 20B are explanatory views of an example of the liquid crystal display device having a conventional direct type backlight unit. FIG. 20A illustrates a side cross-sectional schematic configuration of the LCD device, whereas FIG. 20B illustrates a plan schematic configuration of the fluorescent lamps, i.e., the light source of the backlight unit. As shown in FIGS. 20A and 20B, the backlight unit has a plurality of fluorescent lamps 101, reflectors 102 adapted to reflect the light from the fluorescent lamps 101 and an optical diffusion unit 103 provided at the front of the fluorescent lamps 101 and adapted to diffuse the light directly incident from the fluorescent lamps 101 or that reflected by the reflectors 102. The backlight unit is used to illuminate a liquid crystal panel 104 provided at the front (surface side) thereof through the optical diffusion unit 103. With the aforementioned backlight unit, the fluorescent lamps 101 are arranged in sets of two such that the high-voltage side of one lamp is adjacent to the low-voltage side of the other to compensate for uneven brightness in the lamps 101 and achieve a display screen with even brightness. That is, as shown in FIGS. 20A and 20B, the backlight unit is provided with a plurality of sets (S1, S2, S3 and beyond) of the two fluorescent lamps 101, with the high-voltage side H of one lamp adjacent to the low-voltage side L of the other lamp. Such a configuration cancels out uneven brightness resulting from each fluorescent lamp, thus eliminating uneven brightness on the display screen and achieving an even display. A liquid crystal display device in Patent Document 1 is disclosed as an example with the high- and low-voltage sides H and L arranged adjacent to each other. Further, the technique as shown in FIGS. 21A and 21B is available that is associated with the liquid crystal display device operable to improve the reflectance of the light from the backlight. FIGS. 21A and 21B illustrate another example of the backlight unit in a conventional liquid crystal display device. FIG. 21A illustrates a side cross-sectional schematic configuration of the backlight unit, whereas FIG. 21B illustrates a plan schematic configuration of the inside of the unit, with the optical diffusion sheet, provided on the backlight unit surface, removed. In FIGS. 21A and 21B, reference numeral 201 denotes linear fluorescent lamps, 202 optical diffusion sheets, 203 a reflection sheet and 204 a reflection layer and 205 an enclosure. The backlight unit shown in FIGS. 21A and 21B has the reflection layer 204, made of a high reflectance material such as aluminum, on the inner surface at the bottom of the enclosure 205 further at the back of the reflection sheet 203 provided at the back of the linear fluorescent lamps 201 to efficiently enhance the brightness. Here, of the light incident on the reflection sheet 203, the fraction that passes through the sheet 203 without being reflected is reflected again by the reflection layer 204 back toward the reflection sheet 203, rather than disappears or becomes diffused at the back of the reflection sheet 203. This ensures efficient use of the light passing through the sheet 203 from the back, thus enhancing the brightness. In general, a foamed PET (Poly Ethylene Terephthalate) sheet is often used for the direct type reflection unit (equivalent to the reflection sheet 203 described above). The foamed PET reflection sheet is manufactured by foaming PET to produce fine air bubbles within the sheet. The light incident on the foamed PET sheet is refracted by the air bubbles to regress and emerge again from the incident side. Such a light reflection takes advantage of the refraction characteristic between the PET material and the air in the air bubbles, thus minimizing light loss and achieving a high reflectance reflection unit, despite the use of an inexpensive member. In addition to the above, other materials may be alternatively used including those coated on the surface with a high reflectance material such as silver or aluminum. For example, while the reflection sheet 203, formed with a foamed PET sheet as described above, achieves a high reflectance, part of the incident light from the light source passes through the foamed PET sheet to the rear side (back side opposite to the light source). This leads to reduced light utilization efficiency. To improve these points for enhanced light utilization efficiency, the reflection layer 204 made of a high reflectance material such as aluminum is provided on the inner surface of the enclosure 205 at the back of the reflection sheet 203 to reflect the light passing through the reflection sheet 203 with the reflection layer 204. Part of the reflected light from the reflection layer 204 passes again through the reflection sheet 203 and emerges on the front side (light source side). This ensures improved light utilization efficiency. An edge light type backlight device using a light guide plate is disclosed, for example, in Patent Document 2 as the backlight device having another reflection layer stacked at the back of the reflection sheet as described above. Further, Patent Document 3 discloses a technique that changes the leak current flowing between the high- and low-voltage sides of the fluorescent tube in an edge light type backlight unit to suppress the uneven brightness of the screen. With this backlight unit, the fluorescent lamp is shaped to have straight tube portions in one piece; the one portion running along one of the longer sides of the light guide plate and the other portions each running along one of the shorter sides of the plate. The reflector, provided on the straight tube portion at the high-voltage side of the fluorescent lamp, i.e., one of the tube portions running along the shorter sides of the light guide plate, is formed with a white reflecting member, whereas the reflector at the low-voltage side is deposited on the inside with silver. Such a configuration changes the leak current flowing between the high- and low-voltage sides, thus securing a proper fluorescent lamp length to generate necessary brightness over the rectangular screen and minimizing the difference in brightness between the left and right sides of the screen. Further, the problem here derives from the driving at a high frequency. Therefore, the method is under consideration to drive the fluorescent lamp at the lowest possible frequency for increased the impedance of the stray capacitance and reduced leak current, thus eliminating uneven brightness. Description will be given next of the problems associated with the conventional techniques described above. With the liquid crystal display device described in Patent Document 1, the fluorescent lamps are arranged parallel with each other in sets of two such that the high-voltage side H of one lamp is adjacent to the low-voltage side L of the other. At this time, because of the proximity between the high-voltage side terminal of one fluorescent lamp and the low-voltage side terminal of the other lamp adjacent thereto, discharge may occur between the two electrodes. This renders the stable discharge of the fluorescent lamps itself extremely difficult and possibly deteriorates the reliability of the device. Moreover, the high- and low-voltage terminals of the fluorescent lamps are disposed separately on both sides of the display screen. This requires two inverter power circuits, resulting in higher cost. Further, the thinner and larger the display device, the more difficult it is to make wiring connections to the fluorescent lamps. As a result, additional measures are required to ensure wiring safety and prevent the current leak. With the backlight device of Patent Document 2, on the other hand, if the brightness distribution of the fluorescent lamp is not uniform in the longitudinal direction, the entire display screen may develop uneven brightness as a result of the uneven brightness of the fluorescent lamp. This makes it difficult to control the brightness distribution. In particular, the GND side (low-voltage side) is prone to current leak from the fluorescent lamp. This results in high brightness only at the high-voltage side of the fluorescent lamp and low brightness at the GND side. In the case of Patent Document 3, provision of the white reflector only on one of the shorter sides of the fluorescent lamp alone cannot compensate for the brightness gradient inherently present in the fluorescent lamps. The fluorescent lamp invariably develops a brightness gradient at least along its longer sides. This results in uneven brightness in the liquid crystal display device. If the fluorescent lamp is longer as a result of the upsizing of the liquid crystal display device, the aforementioned problem becomes more noticeable. Further, while the method of lighting the lamps at a lower drive frequency could be possible to the extent that thermal runaway does not occur in the transformer, an excessively low frequency design could degrade the reliability. Besides, lowering the drive frequency will result in larger components such as the transformer. In light of the foregoing, the present invention was conceived and the object thereof is to provide a backlight unit operable to compensate for the brightness difference between the high- and low-voltage sides of the fluorescent lamps, provided as a light source, and to ensure an even brightness of the outgoing light, and a liquid crystal display device operable to ensure an even brightness over the entire display screen. Patent Document 1: Japanese Laid-Open Patent Publication No. H11-295731 Patent Document 2: Japanese Laid-Open Patent Publication No. H08-335048 Patent Document 3: Japanese Laid-Open Patent Publication No. H10-112213 DISCLOSURE OF THE INVENTION The first technical measure of the present invention is characterized by a backlight unit operable to illuminate the target with fluorescent lamps, the backlight unit comprising brightness compensation means adapted to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. The second technical measure of the present compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. The third technical measure of the present invention is characterized by the backlight unit of the second technical measure, wherein the brightness compensation means have regions with relatively high and low reflectances in the reflection unit and take advantage of the difference in reflectance to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. The fourth technical measure of the present invention is characterized by the backlight unit of the third technical measure, wherein the brightness compensation means have a reflectance gradient that causes the reflectance of the reflection unit to decline gradually or in stages and take advantage of the reflectance gradient to reduce the brightness of the portion with a relatively high brightness in the longitudinal direction of the fluorescent lamps. The fifth technical measure of the present invention is characterized by the backlight unit of the third or fourth technical measure, wherein the brightness compensation means have a reflectance gradient that causes the reflectance of the reflection unit to increase gradually or in stages and take advantage of the reflectance gradient to increase the brightness of the portion with a relatively low brightness in the longitudinal direction of the fluorescent lamps. The sixth technical measure of the present invention is characterized by the backlight unit of any one of the second to fifth technical measures, wherein the brightness compensation means are a dot pattern provided on the reflection unit and take advantage of the dot pattern to control the reflectance of the reflection unit. The seventh technical measure of the present invention is characterized by the backlight unit of the sixth technical measure, wherein the reflectance of the reflection unit provided with the dot pattern is controlled by one or a plurality of the reflectance of the group of small dots making up the dot pattern, the dot density, the dot shape, and the dot color. The eighth technical measure of the present invention is characterized by the backlight unit of the first technical measure, comprising a reflection unit adapted to emit the light from the fluorescent lamps in a specific direction, wherein the reflection unit is made up of first and second reflection layers having given optical reflectance and transmittance, wherein the reflection unit is configured with a first region having the first and second reflection layers stacked one above another in the direction of incidence of light and a second region made up only of the first reflection layer, and wherein the reflectance of the reflection unit is controlled using the first region with a relatively high reflectance and the second region with a reflectance lower than that of the first region. The ninth technical measure of the present invention is characterized by the backlight unit of the first technical measure, wherein the brightness, compensation means are provided on a glass tube of the fluorescent lamps and control the transmittance of the glass tube to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. The tenth technical measure of the present invention is characterized by the backlight unit of the first technical measure, comprising a diffusion unit adapted to diffuse the light from the fluorescent lamps, wherein the brightness compensation means are provided on the diffusion unit and control the transmittance of the diffusion unit to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. The eleventh technical measure of the present invention is characterized by the backlight unit of the ninth or tenth technical measure, wherein the brightness compensation means have regions with relatively high and low transmittances in the glass tube or diffusion unit and take advantage of the difference in the transmittance to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. The twelfth technical measure of the present invention is characterized by the backlight unit of the eleventh technical measure, wherein the brightness compensation means have a transmittance gradient that causes the transmittance to decline gradually or in stages and take advantage of the transmittance gradient to reduce the brightness of the portion with a relatively high brightness in the longitudinal direction of the fluorescent lamps. The thirteenth technical measure of the present invention is characterized by the backlight unit of the eleventh or twelfth technical measure, wherein the brightness compensation means have a transmittance gradient that causes the transmittance to increase gradually or in stages and take advantage of the transmittance gradient to increase the brightness of the portion with a relatively low brightness in the longitudinal direction of the fluorescent lamps. The fourteenth technical measure of the present invention is characterized by the backlight unit of any one of the ninth to thirteenth technical measures, wherein the brightness compensation means are a dot pattern provided on the glass tube of the fluorescent lamps or the diffusion unit and take advantage of the dot pattern to control the transmittance. The fifteenth technical measure of the present invention is characterized by the backlight unit of the fourteenth technical measure, wherein the transmittance of the glass tube or the diffusion unit provided with the dot pattern is controlled by one or a plurality of the reflectance of the group of small dots making up the dot pattern, the dot density, the dot shape, and the dot color. The sixteenth technical measure of the present invention is characterized by the backlight unit of the first technical measure, wherein the brightness compensation means are provided on the glass tube of the fluorescent lamps and control the tube surface brightness of the glass tube to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. The seventeenth technical measure of the present invention is characterized by the backlight unit of the sixteenth technical measure, wherein the thickness of the fluorescent substance formed inside the glass tube of the fluorescent lamps as the brightness compensation means is changed correspondingly with the longitudinal position of the fluorescent lamps to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. The eighteenth technical measure of the present invention is characterized by a liquid crystal display device comprising the backlight unit of any one of the first to seventeenth technical measure and a liquid crystal panel illuminated by the backlight unit. The nineteenth technical measure of the present invention is characterized by a liquid crystal display device operable to apply an illumination light from a backlight unit having fluorescent lamps to a liquid crystal panel to display images, the liquid crystal display device comprising brightness compensation means adapted to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. The twentieth technical measure of the present invention is characterized by the liquid crystal display device of nineteenth technical measure, wherein the brightness compensation means have a gradation conversion unit operable to carry out a given gradation conversion process of input image data and a control portion operable to switch between gradation conversion characteristics of the gradation conversion unit based on a synchronizing signal of the input image data, and wherein the control portion switches from one gradation conversion characteristic to another in the gradation conversion unit based on the screen position to display the image data to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. The twenty-first technical measure of the present invention is characterized by the liquid crystal display device of the nineteenth technical measure, wherein the liquid crystal panel is configured to have, as the brightness compensation means, an aperture ratio that changes correspondingly with the display screen position, and wherein the aperture ratio is changed to compensate for uneven brightness in the longitudinal direction of the fluorescent lamps. BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1A and 1B are explanatory views of an embodiment of a backlight unit according to the present invention; FIG. 2 is an explanatory view of a layout example of fluorescent lamps in a backlight unit applied to the present invention; FIG. 3 is an explanatory view of an example of a dot pattern imparted to a reflection layer; FIGS. 4A and 4B are expanded views of the dot pattern of the reflection layer shown in FIG. 3; FIG. 5 is an explanatory view of another embodiment of the backlight unit according to the present invention; FIG. 6 is an explanatory view of still another embodiment of the backlight unit according to the present invention; FIGS. 7A and 7B are explanatory views of still another embodiment of the backlight unit according to the present invention; FIG. 8 is an explanatory view of still another embodiment of the backlight unit according to the present invention; FIGS. 9A to 9D are explanatory views of still another embodiment of the backlight unit according to the present invention; FIG. 10 illustrates an example of the relationship between the film thickness of a fluorescent substance and the tube surface brightness at that time; FIG. 11 is an explanatory view of still another embodiment of the backlight unit according to the present invention; FIGS. 12A and 12B illustrate a configuration example of the edge light type backlight unit according to the present invention; FIG. 13 is an explanatory view of an embodiment of a liquid crystal display device according to the present invention; FIG. 14 is a block diagram of the major components illustrating a schematic configuration of another embodiment of the liquid crystal display device according to the present invention; FIG. 15 is an explanatory view of the display screen region of the liquid crystal display device of FIG. 14; FIG. 16 illustrates gradation conversion characteristics (input/output characteristics) of a gradation conversion unit in the liquid crystal display device of FIG. 14; FIG. 17 is an explanatory view of the aperture ratio control in a liquid crystal panel; FIG. 18 is an explanatory view of an example of the relative brightness distribution characteristic in the longitudinal direction (in the direction of voltage application) of the fluorescent lamps; FIG. 19 is a graph illustrating the relative brightness characteristic in the longitudinal direction (in the direction of voltage application) of the fluorescent lamps when a drive voltage, applied to the fluorescent lamps having the brightness gradient shown in FIG. 18, is further raised; FIGS. 20A and 20B are explanatory views of an example of the liquid crystal display device having a conventional direct type backlight unit; and FIGS. 21A and 21B illustrate another example of the backlight unit in the conventional liquid crystal display device. PREFERRED EMBODIMENT OF THE INVENTION As described above, the fluorescent lamps of the backlight unit develop a non-uniform brightness (uneven brightness) due to the relatively higher brightness at the high-voltage side. The present invention imparts, to the backlight unit or the liquid crystal display device, brightness compensation means operable to compensate for the uneven brightness in the longitudinal direction of the fluorescent lamps so as to compensate for the uneven brightness inherently present in the lamps and achieve a display screen with an even brightness. To ensure an even brightness, the brightness compensation means imparted to the backlight unit provide: (1) the reflection means intended to reflect the light of the fluorescent lamps and direct it in a single direction with means to reduce the reflectance of the high brightness portion of the fluorescent lamps (high-voltage side) or increase the reflectance of the low brightness portion of the fluorescent lamps (low-voltage side); (2) the glass tube surface of the fluorescent lamps with means to reduce the transmittance of the high brightness portion of the fluorescent lamps (high-voltage side) or increase the transmittance of the low brightness portion of the fluorescent lamps (low-voltage side); (3) the glass tube surface of the fluorescent lamps with means to reduce the radiation brightness of the high-voltage side of the fluorescent lamps or increase the radiation brightness of the low-voltage side of the fluorescent lamps; or (4) the diffusion sheet with means to reduce the transmittance of the high brightness portion of the fluorescent lamps (high-voltage side) or increase the transmittance of the low brightness portion of the fluorescent lamps (low-voltage side). The above means may be used in combination to ensure an even brightness. To ensure an even brightness, on the other hand, the brightness compensation means imparted to the display device control: (1) the image data supplied to the liquid crystal panel to compensate for the uneven brightness in the longitudinal direction of the fluorescent lamps; or (2) the aperture ratio of the liquid crystal panel to compensate for the uneven brightness in the longitudinal direction of the fluorescent lamps. Description will be given below of the embodiments of the present invention that can accomplish the aforementioned brightness compensation means. It is to be noted that the same reference numerals are used to denote the elements, components or portions with similar functions throughout the drawings for describing the embodiments, and duplicated description is omitted. Embodiment 1 In the present embodiment, the reflection layer in the backlight unit is provided with the brightness compensation means adapted to compensate for the brightness in the longitudinal direction of the fluorescent lamps so as to compensate for the uneven brightness of such lamps and evenly illuminate the target such as the liquid crystal display device. The brightness compensation means in the present embodiment are designed to control the reflectance of the light from the fluorescent lamps. FIGS. 1A and 1B are explanatory views of an embodiment of the direct type backlight unit according to the present invention. FIG. 1A is a plan schematic view illustrating the inside of the backlight unit, whereas FIG. 1B is a schematic configuration diagram of the backlight unit taken along cross-section line B-B in FIG. 1A. In FIGS. 1A and 1B, reference numeral 10 denotes a backlight unit, 11 fluorescent lamps, 12 an enclosure, 13 a reflection layer provided at the bottom of the enclosure, 14 a diffusion unit and 15 lamp supporting members. It is to be noted that FIG. 1A illustrates the inside of the unit with the diffusion unit 14 shown in FIG. 1B removed. The backlight unit 10 has a reflection unit adapted to emit the light from the fluorescent lamps 11 in a specific direction. In the present embodiment, the reflection layer 13 is provided as the reflection unit on the inner surface at the bottom of the enclosure 12 of the backlight unit 10. The enclosure 12 may be configured with a shielding plate adapted to shield electromagnetic waves generated from the fluorescent lamps 11. The reflection layer 13 is held above the inner surface at the bottom of the enclosure 12 of the backlight unit 10 with a space therebetween or directly on the inner surface. A foamed PET sheet or a material with an optical reflection surface made of silver or aluminum may be used, for example, for this layer. As a foamed PET sheet, E60L or E60V type of Lumirror (R) from Toray may be preferably used. The diffusion unit 14, provided at the front (surface) of the fluorescent lamps 11, is configured with a material having an optical diffusion characteristic such as acrylic plate to diffuse the incident light directly from the fluorescent lamps 11 or the light that is reflected by the reflection layer 13 and guided again back toward the front. In addition to the above, a functional film or sheet such as a reflective polarizing film, prism sheet or ITO sheet may be included between the diffusion unit 14 and the fluorescent lamps 11 for use in the liquid crystal display device. The transmitted light passing through the diffusion unit 14 is used to illuminate the target (not shown) such as the liquid crystal panel provided further at the front of the diffusion unit. To light the plurality of the fluorescent lamps 11, a high voltage is applied to the lamps 11 from an inverter power circuit (not shown). FIG. 2 is an explanatory view of the layout of the fluorescent lamps 11, schematically illustrating a plan layout of the lamps. Here, the plurality of the fluorescent lamps 11 are laid out so as to be longitudinally parallel to each other. The high- and low-voltage sides H and L of the fluorescent lamps 11 are arranged at the same sides so that the high-voltage side H of each of the lamps 11 is adjacent to that of another lamp and that the low-voltage side L of each of the lamps is adjacent to that of another lamp. The fluorescent lamps 11 have an uneven brightness that causes the brightness of the high-voltage side to be relatively higher in the longitudinal relative brightness distribution as described above. In the present embodiment, the reflection layer 13 is provided with the brightness compensation means tailored for the uneven brightness of the fluorescent lamps 11 to compensate for the uneven brightness in the longitudinal direction inherently present in the lamps 11 and achieve a display screen with an even brightness. As such brightness compensation means, two possible means are available. The first is to reduce the reflectance of the reflection layer 13 at the portion of the fluorescent lamps 11 that is relatively high in brightness (high-voltage side H). The second is to increase the reflectance of the reflection layer 13 at the portion of the fluorescent lamps 11 that is relatively low in brightness (low-voltage side L). These two means may also be used in combination. As an example of the brightness compensation means, a dot pattern is imparted to the reflection layer 13 to control the reflectance. The dot pattern controls the reflectance of the outgoing light from the fluorescent lamps 11, thus compensating for the uneven brightness developed by the fluorescent lamps 11 in the longitudinal direction. FIG. 3 is an explanatory view of an example of the dot pattern imparted to the reflection layer 13. On the other hand, FIGS. 4A and 4B are expanded views of the dot pattern of the reflection layer shown in FIG. 3. FIG. 4A is an expanded view of a region D3 in FIG. 3, whereas FIG. 4B is an expanded view of a region D1 in FIG. 3. In the present embodiment, the dot pattern imparted to the reflection layer 13 reduces the reflectance of the layer 13. The reflectance of the material making up the dot pattern is relatively lower than that of the surface of the reflection layer. In the present embodiment, the reflection layer 13 is provided, as shown in FIG. 3, with regions D1, D2 and D3, i.e., the regions whose reflectance decreases in stages from the low-voltage side L to the high-voltage side H of the fluorescent lamps 11. These regions are formed so as to correspond to the uneven brightness of the fluorescent lamps 11 and compensate for the uneven brightness of the fluorescent lamps 11. In the present embodiment, the dot pattern, equivalent to the brightness distribution compensation in FIG. 18, is imparted to the reflection layer 13. The dot pattern imparted to the reflection layer 13 in the present embodiment has a dot density increasing in stages from the low-voltage side L to the high-voltage side H of the fluorescent lamps 11 in the regions D1, D2 and D3 with the dot pattern so as to reduce the reflectance from the low-voltage side L to the high-voltage side H. As shown in FIGS. 4A and 4B, for example, the dots of the dot pattern are equally sized, and the dot pattern closer to the high-voltage side H has a higher dot density. This changes the reflectance of the reflection layer 13 correspondingly with the uneven brightness in the longitudinal direction of the fluorescent lamps 11, thus achieving an illuminating light with an even brightness distribution. To control the reflectance of the reflection layer with a dot pattern, while the reflectance of the reflection layer 13 can be controlled by imparting to this layer a dot pattern to reduce the reflectance of the reflection surface of the reflection layer 13 as described above, the reflectance of the reflection layer 13 may be controlled by imparting to this layer a dot pattern to increase the reflectance of the reflection surface of the reflection layer 13. In this case, a dot pattern adapted to relatively increase the reflectance is provided in the region of the reflection layer 13 with a relatively low brightness in terms of the brightness distribution of the fluorescent lamps 11. For example, if a foamed PET sheet is used for the reflection layer 13, a dot pattern, made of a high reflectance material such as silver or aluminum, is imparted to the region of the reflection layer 13 corresponding to the low brightness region of the fluorescent lamps 11. This allows to compensate for the uneven brightness in the longitudinal direction of the fluorescent lamps 11. On the other hand, the dot pattern adapted to control the reflectance as described above, may not only vary the equally shaped dot density as shown in the example of FIGS. 3 and 4A and 4B but also the dot shape (size) to control the reflectance. Further, the dot shape and density may be used in combination. Further, taking advantage of the change in the reflectance with change in the dot color, the dot color as well as the dot shape and density may be used in combination to control the reflectance. For example, the dot shape of the dot pattern may be circular, triangular, polygonal, star-shaped or elliptical, whereas the dot color may be gray, dark brown, silver, green, black, white or purple. Further, the dot pattern may impart a gradient that gradually reduces the reflectance from the low-voltage side L to the high-voltage side H (that is, gradually increases the reflectance from the high-voltage side H to the low-voltage side L) correspondingly with the uneven brightness of the fluorescent lamps 11, rather than changes the reflectance in stages as shown in the example of FIG. 3. Such a reflectance gradient can be realized when the dot shape, size, density and color are used alone or in combination with each other. Ink can be imparted to the reflection layer 13, for example, through screen or ink jet printing to form the dot pattern imparted to the reflection layer 13. In addition to printing, the dot pattern may be formed using other means, namely, sputtering, vapor deposition, photolithography, optical machining using a laser beam or lamination of clear dot-patterned films. As another specific example of the brightness compensation means, the reflection layer 13 can be coated with an ink or dye with varying concentration to reduce or increase the reflectance of the reflection unit gradually or in stages. To change the concentration at this time, the concentration of the dye or pigment itself may be varied, or the thickness of the film applied may be varied to change the apparent concentration. Moreover, a plurality of materials with different reflectances may be imparted to the surface of the reflection layer 13 as the brightness compensation means to change the reflectance in stages. Further, the surface roughness of the reflection layer 13 may be varied to control the reflectance based on the difference of the optical diffusion or absorption characteristic of the surface. Further, two different measures, one to relatively reduce the reflectance of the reflection layer 13 and the other to increase it as described above, may be used in combination to control the reflectance of the reflection layer 13. Embodiment 2 FIG. 5 is an explanatory view of still another embodiment of the backlight unit according to the present invention, illustrating a schematic cross-section corresponding to the cross-section along line B-B of the backlight unit in FIG. 1A. The backlight unit of the present embodiment has, as the reflection unit, a reflection surface 12a adapted to reflect the light of the fluorescent lamps 11 toward the diffusion unit 14 in place of the reflection layer 13 in the embodiment 1. The reflection surface 12a is formed with a reflective film made of a high reflectance material such as silver or aluminum and provided on the inner surface at the bottom of the enclosure 12. On the other hand, the high- and low-voltage sides H and L of the fluorescent lamps 11 are arranged at the same sides as shown in FIG. 2. In the present embodiment, the brightness compensation means are provided on the reflection surface 12a to control the optical reflectance as described in the embodiment 1. This compensates for the reflectance of the reflection surface 12a correspondingly with the longitudinal brightness distribution of the fluorescent lamps 11, thus achieving an illumination light with an even brightness distribution. As for a specific configuration of the brightness compensation means, the brightness compensation means in the embodiment 1 can be used. Therefore, duplicated description is omitted. Embodiment 3 FIG. 6 is an explanatory view of still another embodiment of the backlight unit according to the present invention, illustrating a schematic cross-section corresponding to the cross-section along line B-B of the backlight unit in FIG. 1A. The backlight unit of the present embodiment has, as the reflection unit, the reflection layer 13 shown in the configuration of FIGS. 1A and 1B and the reflection surface 12a shown in FIG. 5. On the other hand, the high- and low-voltage sides H and L of the fluorescent lamps 11 are arranged at the same sides as shown in FIG. 2. The enclosure 12 of the backlight unit 10 is provided with the reflection layer 13 as described in embodiment 1. While the reflection layer 13, made, for example, of the foamed PET sheet, is capable of reflecting the light from the fluorescent lamps 11, part of the light passes through the reflection layer 13 to emerge at the rear side. The reflection surface 12a as described in the embodiment 2 is provided on the inner surface at the bottom of the backlight unit 10. This surface reflects the light passing through the reflection layer 13 back toward the reflection layer 13. The light reflected by the reflection surface 12a is separated again into reflected and transmitted lights at the reflection layer 13. The transmitted light travels toward the diffusion unit 14 so that it will be effectively used. The reflection layer 13 is supported using a supporting body in the shape of a frame and a lamp holder or supporting members such as screws or stays. The reflection layer 13 allows an air layer to mediate between this layer 13 and the reflection surface 12a without coming in close contact with the reflection surface 12a. To allow the mediation of the air layer, while a given gap may be provided between the reflection layer 13 and the reflection surface 12a, it suffices to simply place and support the reflection layer 13 on the reflection surface 12a. That is, because of the presence of a thin air layer on the back surface of the reflection layer 13, the difference in refraction index between the reflection layer 13 and air becomes greater on the back surface of the reflection layer 13. This will enhance the reflectance of the reflection layer 13. For example, if a material such as an adhesive having a refraction index close to that of the reflection layer 13 is provided on the back surface of this layer 13, the component of transmitted light increases at the reflection layer 13. This will impair the optical reflection characteristic. While, in the present embodiment, the brightness compensation means described in the aforementioned embodiment may be imparted to the reflection layer 13 to achieve an even illumination light, the above means may be further imparted to both of the reflection layer 13 and the reflection surface 12a or only to the reflection surface 12a. The brightness compensation means imparted to the reflection surface 12a contributes only to transmitted light passing through the reflection layer 13. Therefore, the reflectance distribution must be designed based on the reflectance (that is, transmittance) of the reflection layer 13. Embodiment 4 FIGS. 7A and 7B are explanatory views of still another embodiment of the backlight unit according to the present invention. FIG. 7A is a plan schematic view illustrating the inside of the backlight unit, whereas FIG. 7B illustrates a configuration, including the diffusion unit 14, on the cross-section along the fluorescent lamps 11 in FIG. 7A. In FIGS. 7A and 7B, reference numeral 16 denotes screws used as the holding means of reflection layers 13a and 13b. On the other hand, the high- and low-voltage sides H and L of the fluorescent lamps 11 are arranged at the same sides as shown in FIG. 2. The backlight unit of FIGS. 7A and 7B is provided with the two reflection layers 13a and 13b to emit the light from the fluorescent lamps in a specific direction. The reflection layers 13a and 13b each have a characteristic similar to the aforementioned foamed PET sheet, thus reflecting light at a high reflectance. However, part of the incident light passes through the reflection layers to the rear side. In the present embodiment, two regions are provided, a region W with the reflection layers 13a and 13b stacked one above another vertically (in the direction of incidence of light) and a region S with only the reflection layer 13b. As described above, part of the incident light passes through the reflection layers 13a and 13b to the rear side. In the region W with the reflection layers 13a and 13b stacked one above another, the transmitted light passing through the reflection layer 13a, i.e., the first layer provided on the front side (side of the fluorescent lamps 11), is reflected by the reflection layer 13b, i.e., the second layer provided on the rear side, back to the first reflection layer 13a. The transmitted light passing through the first reflection layer 13a travels toward the diffusion unit 14 so that it will be effectively used. In the region S with only the second reflection layer 13b, on the other hand, although the light reflected by this layer 13b is effectively used, the transmitted light passing through the reflection layer 13b disappears or becomes diffused at the rear side thereof. Even if the transmitted light returns to the reflection layer 13b as a result of reflection, for example, by the inner surface of the enclosure 12, only a small percentage of such a light will be effectively used. Therefore, when the regions W and S are compared, the region W with the two stacked reflection layers 13a and 13b achieves a relatively higher reflectance than the region S with only the reflection layer 13b. It is to be noted that although the second reflection layer 13b on the rear side is larger than the first reflection layer 13a on the front side to form the regions W and S in the configuration of FIGS. 7A and 7B, the first reflection layer 13a may be larger. Using the two reflection layers 13a and 13b, the region W having these layers is provided at the low brightness area of the fluorescent lamps 11. This ensures a relatively higher reflectance, thus achieving an illumination light with an even brightness distribution. A half mirror may be used, for example, for the first reflection layer 13a. Using the half mirror enhances the transmittance of the light reflected by the second reflection layer 13b back to the first reflection layer 13a (half mirror), thus achieving a high reflectance. On the other hand, the brightness compensation means as described in the embodiments 1 to 3 may be used in combination with the configuration having the two reflection layers 13a and 13b. When the two regions, i.e., the region W with the reflection layers 13a and 13b stacked one over another and the region S with only the reflection layer 13b, are formed as in the present embodiment, holding members are preferably provided on each of the reflection layers 13a and 13b, and particularly, on the layer 13a on the front side to impart a holding stability. For example, through-holes are made in all of the members, i.e., the enclosure 12 and the first and second reflection layers 13a and 13b, as shown in FIGS. 7A and 7B. Then, the screws 16 are inserted into the through-holes to hold the reflection layers 13a and 13b with the inner surface of the enclosure 12. This suppresses the bending of the reflection layers 13a and 13b due to the gravity and the like, thus maintaining their shapes. It is to be noted that not only screws but also publicly known means that can hold reflection layers 13a and 13b with the inner surface of the enclosure can be used as the holding means. It is to be noted that, to prevent the holding means such as the screws 16 from showing up on the display screen, the holding means are preferably arranged so as to be hidden behind the fluorescent lamps 11 as shown in FIG. 7B. Further, the holding means may be provided with a capability to hold the reflection layers 13a and 13b and another to hold the fluorescent lamps 11. Embodiment 5 FIG. 8 is an explanatory view of still another embodiment of the backlight unit according to the present invention, illustrating the fluorescent lamp 11 in a plan schematic view. In the present embodiment, the glass tube making up the fluorescent lamp 11 is provided with the brightness compensation means to compensate for the uneven brightness of the lamp 11 and achieve a light with an even brightness distribution. Here, the brightness compensation means provided on the glass tube are used to control the optical transmittance of the glass tube of the fluorescent lamp 11, rather than control the reflectance as described in the aforementioned embodiments. However, both means share the same technical principle of controlling the amount of light emitted to the target to ensure an even brightness. In FIG. 8, a dot pattern is used as the brightness compensation means to reduce the optical transmittance of the glass tube. Here, three dot pattern regions with different densities, namely, regions D11, D12 and D13, are disposed such that the dot density increases in stages from the low-voltage side L to the high-voltage side H of the fluorescent lamp 11. The regions D11, D12 and D13 are formed to correspond to and compensate for the uneven brightness of the fluorescent lamp 11. In the present embodiment, the dot pattern, equivalent to the brightness distribution compensation in FIG. 19, is imparted to the glass tube of the fluorescent lamp 11. With the dot pattern imparted to the reflection layer 13 in the present embodiment, the dot density is increased in stages from the low-voltage side L to the high-voltage side H of the fluorescent lamp 11 in the dot pattern regions D11, D12 and D13 so as to reduce the transmittance from the low-voltage side L to the high-voltage side H of the lamp 11. As shown in FIG. 8, for example, the dots of the dot pattern are equally sized, and the dot density of the dot pattern is higher in the region closer to the high-voltage side H. This changes the transmittance of the glass tube correspondingly with the uneven brightness in the longitudinal direction of the fluorescent lamp 11, thus achieving an illumination light with an even brightness distribution. The dot pattern adapted to control the transmittance as described above may change not only the density of the equally-shaped dots as shown in FIG. 8 but also the dot shape (size). Further, the dot shape and density may be used in combination. Further, the dot color may be changed to change the transmittance. For example, the dot shape of the dot pattern may be circular, triangular, polygonal, star-shaped or elliptical, whereas the dot color may be gray, dark brown, silver, green, black, white or purple. Further, the dot pattern, as described above, may impart a gradient that gradually reduces the transmittance from the low-voltage side L to the high-voltage side H in correspondence with the uneven brightness of the fluorescent lamp 11 without changing the transmittance in stages as shown in the example of FIG. 8. Such a transmittance gradient can be realized when the dot shape, size, density and color are used alone or in combination with each other. Ink is imparted to the glass tube, for example, through screen or ink jet printing to form the dot pattern imparted to the glass tube surface. In addition to printing, the dot pattern may be formed using other means, namely, sputtering, vapor deposition, photolithography, optical machining using a laser beam or lamination of clear films with a dot pattern. As another specific example of the brightness compensation means imparted to the glass tube of the fluorescent lamp 11, the glass tube can be coated with an ink or dye with varying concentration to reduce or increase the transmittance in stages or gradually. To change the concentration at this time, the concentration of the dye or pigment itself may be varied, or the thickness of the film applied may be varied to change the apparent concentration. Moreover, a plurality of materials with different transmittances may be imparted to the glass tube surface as the brightness compensation means. Further, the surface roughness of the glass tube may be varied to control the transmittance based on the difference of the optical diffusion or absorption characteristic of the surface. Embodiment 6 FIGS. 9A to 9D are explanatory views of still another embodiment of the backlight unit according to the present invention. FIG. 9A is a cross-sectional schematic view of the backlight unit, whereas FIGS. 9B to 9D are cross-sectional schematic views of the fluorescent lamp 11 taken respectively along cross-section lines B-B, C-C and D-D in FIG. 9A. In FIGS. 9A to 9D, reference numeral 11a denotes a glass tube making up the fluorescent lamp, 11b a fluorescent substance provided on the inner surface of the glass tube and d a film thickness of the fluorescent substance. In the present embodiment, the brightness compensation means adapted to compensate for the uneven brightness of the fluorescent lamp 11 and achieve a light with an even brightness distribution change the film thickness d of the fluorescent substance 11b formed on the inside of the glass tube 11a of the fluorescent lamp 11 in the longitudinal direction of the fluorescent lamp 11 to compensate for the uneven brightness of the fluorescent lamp 11 during lighting. That is, the present embodiment takes advantage of the change in tube surface brightness with variation in the film thickness d of the fluorescent substance 11b to change the film thickness d of the fluorescent substance 11b correspondingly with the longitudinal position of the fluorescent lamp 11 and achieve an even radiation brightness in the longitudinal direction of the fluorescent lamp 11. In the example of FIGS. 9A to 9D, the film thickness d of the fluorescent substance is optimal for maximum brightness at the low-voltage side L of the fluorescent lamp 11 with relatively low brightness, and the film thickness d is increased toward the high-voltage side H with relatively high brightness. FIG. 10 illustrates an example of the relationship between the film thickness d of the fluorescent substance and the tube surface brightness (radiation brightness) at that time. As shown in FIG. 10, the brightness of the lamp during lighting generally changes correspondingly with the film thickness d of the fluorescent substance, regardless of what the fluorescent substance is made of. The optimal value for the film thickness d exists that allows the fluorescent substance to emit the brightest light. That is, as shown in FIG. 10, if the film thickness d is smaller than the optimal value, the light is darker due to the lack of the fluorescent substance, whereas if the film thickness d is greater than the optimal value, the light is also darker due to the scattering of light in the film. The present embodiment conversely takes advantage of the above-described characteristic to change the film thickness d of the fluorescent substance 11b from the low-voltage side L of the fluorescent lamp 11 with relatively low brightness to the high-voltage side H thereof with higher brightness. At this time, the brightness declines irrespective of whether the film thickness d is smaller or greater than the optimal value as described above. For example, therefore, the fluorescent substance 11b at the low-voltage side L with lower brightness is set to the optimal film thickness, and the film thickness d is reduced or increased toward the high-voltage side H with relatively high brightness. It is to be noted that, as described in embodiments 5 and 6, the method of imparting the brightness compensation means to the glass tube itself of the fluorescent lamp 11 can be applied not only to a straight tube fluorescent lamp but also to U-shaped, block C-shaped and L-shaped fluorescent lamps. Embodiment 7 FIG. 11 is an explanatory view of still another embodiment of the backlight unit according to the present invention. In the present embodiment, the diffusion unit 14 is provided with the brightness compensation means to compensate for the uneven brightness in the longitudinal direction of the lamps and achieve a light with an even brightness distribution. A diffusion plate or sheet capable of diffusing light is used for the diffusion unit 14. The brightness compensation means are provided on the surface of the diffusion unit 14 to control the optical transmittance. For example, a dot pattern is imparted to the surface of the diffusion unit 14 as shown in FIG. 11 to reduce the optical transmittance. Here, three dot pattern regions with different densities, namely, regions D21, D22 and D23, are disposed such that the dot density increases in stages from the low-voltage side L to the high-voltage side H of the fluorescent lamps 11. The regions D21, D22 and D23 are formed to correspond to and compensate for the uneven brightness in the longitudinal direction of the fluorescent lamps 11. Here, the dot pattern is preferably provided on the back side (side of the fluorescent lamps 11) rather than on the front side (side opposite to the fluorescent lamps 11) of the diffusion unit 14 because of a smaller likelihood of the dot pattern to hinder the even diffusion characteristic of the diffusion unit 14 across the surface. In addition to the above, the aforementioned brightness compensation means provided on the fluorescent lamps 11 in the embodiment 5 may be used in the same manner as the brightness compensation means to control the optical transmittance as described above. In the present embodiment, on the other hand, the thickness of the diffusion unit 14 may be changed correspondingly with the uneven brightness in the longitudinal direction of the fluorescent lamps 11 to change the transmittance of the light passing through the diffusion unit 14 and compensate for the uneven brightness of the fluorescent lamps 11. Embodiment 8 While the configuration examples of the direct type backlight unit have been described in the above embodiments, the backlight unit according to the present invention may be applied to the edge light type as well as to the direct type. That is, the brightness compensation means imparted to the reflection layer or surface making up the reflection unit, the fluorescent lamps and the diffusion unit are not specifically applicable to the direct type backlight units. Instead, the brightness compensation means can compensate for the uneven brightness in the longitudinal direction of the fluorescent lamp in the edge light type backlight units to achieve an illumination light with an even brightness. Description will be given of an example of the edge light type backlight unit. FIGS. 12A and 12B are explanatory views of a configuration example of the edge light type backlight unit according to the present invention. FIG. 12A is an explanatory view with some of the components removed in a plan schematic view of the backlight unit, whereas FIG. 12B illustrates a cross-sectional configuration along the longitudinal direction of the fluorescent lamps. With the edge light type backlight unit 10 shown in FIGS. 12A and 12B, the fluorescent lamp 11 is arranged at the side of a light guide plate 17 as an edge light. The reflection layer 13 is provided at the back of the light guide plate 17. The light of the fluorescent lamp 11 is guided to the front by the light guide plate 17 and the reflection layer 13 and then emitted from the surface of the diffusion unit 14 as an illumination light. The reflection layer 13, i.e., the layer equivalent to the reflection layer 13 in the first embodiment, can be formed with a foamed PET sheet or a material having a high reflectance reflection surface made, for example, of silver or aluminum. Thus, the brightness compensation means described in the above embodiments are imparted to one or a plurality of the reflection layer 13, the fluorescent lamp 11 and the diffusion unit 14 correspondingly with the uneven brightness of the fluorescent lamp 11. This compensates for the uneven brightness in the longitudinal direction of the fluorescent lamp 11 in the edge light type backlight unit as well, thus achieving an illumination light with an even brightness. That is, as for the fluorescent lamp 11, it suffices to provide the brightness compensation means to compensate for the uneven brightness from the high-voltage side H to the low-voltage side L of the lamp 11. As for the reflection layer 13 and the diffusion unit 14, on the other hand, it suffices to impart the brightness compensation means as described above correspondingly with the uneven brightness of the light emitting surface of the light guide plate 17 resulting from the uneven brightness from the high-voltage side H to the low-voltage side L of the fluorescent lamp 11. Embodiment 9 When configured with a backlight unit having the brightness compensation means as shown in the above embodiments, the liquid crystal display device offers a high-quality display image free of uneven brightness on the display screen. FIG. 13 is an explanatory view of an embodiment of the liquid crystal display device according to the present invention, illustrating a cross-sectional schematic configuration of the liquid crystal display device having a backlight unit. In FIG. 13, reference numeral 20 denotes a liquid crystal display device and 21 a liquid crystal panel. The liquid crystal display device 20 has the ordinary liquid crystal panel 21, mainly configured by a liquid crystal material sealed between two clear insulating substrates, and the backlight unit 10 operable to apply light to the liquid crystal panel 21. The backlight unit according to one of the first to eighth embodiments can be used for the backlight unit 10 in the liquid crystal display device 20 according to the present embodiment. When the liquid crystal panel 21 is illuminated with the backlight unit 10 provided with the brightness compensation means according to the present invention, the uneven brightness is compensated for in the longitudinal direction of the fluorescent lamps 11. This achieves an illumination light with even brightness, thus achieving a high-quality display screen free of uneven brightness on the liquid crystal panel 21. As described above, the liquid crystal display device 20 ensures a high light utilization efficiency when a polarizing reflective film, that is not shown, is provided between the liquid crystal panel 21 and the diffusion unit 14 of the backlight unit 10. Here, the polarization transmission axis of the polarizing reflective film is aligned with that of the polarizer at the incident side of the liquid crystal panel 21. Then, if, as a result of the diffusion or reflection of the polarization fraction reflected by the polarizing reflective film, for example, by the diffusion unit 14 or the reflection layer 13, the polarization fraction thereof in the orthogonal direction (fraction coinciding with the polarization transmission axis) occurs, this fraction passes through the polarizing reflective film and therefore can be used as the effective light to the liquid crystal panel 21. Thus, the polarizing reflective film can efficiently produce a uniformly polarized illumination light. A liquid crystal display device with high light utilization efficiency can be obtained when the polarization direction of this light coincides with the polarization axis of the polarizer at the incident side of the liquid crystal panel. Further, a functional film or sheet such as an ITO sheet, diffusion film or prism sheet may be provided between the polarizing reflective film and the diffusion unit 14. Embodiment 10 The present embodiment controls the display image data supplied to the liquid crystal panel in the liquid crystal display device to compensate for the uneven brightness in the longitudinal direction of the fluorescent lamp and achieve a display screen with an even brightness. The present embodiment will be described below with reference to FIGS. 14 to 16. Here, FIG. 14 is a block diagram of the major components illustrating a schematic configuration of the liquid crystal display device according to the present embodiment. FIG. 15 is an explanatory view illustrating the display screen region in the liquid crystal display device according to the present embodiment. FIG. 16 is an explanatory view illustrating gradation conversion characteristics (input/output characteristics) of a gradation conversion unit in the liquid crystal display device according to the present embodiment. As shown in FIG. 14, the liquid crystal display device according to the present embodiment is provided with a gradation conversion unit 31 operable to carry out a given gradation conversion process of input image data and an LCD control portion 32 operable to output an LCD drive signal to a gate driver 34 and a source driver 35 of a liquid crystal panel 33 based on the image data whose gradation has been converted by the gradation conversion unit 31. The liquid crystal display device is also provided with a microcomputer 36 that not only switches between the gradation conversion characteristics of the gradation conversion unit 31 based on a synchronizing signal of the input image data but also controls a light source drive unit 38 to drive a backlight source (linear fluorescent lamps) 37. That is, the microcomputer 36 determines, based on the synchronizing signal of the input image data, the screen position to display the image data, and instructs the gradation conversion unit 31 to switch between the gradation conversion characteristics of the gradation conversion unit 31 based on the screen position. Here, we assume that the display screen is divided into three regions, as shown in FIG. 15, a region D31 of the screen corresponding to the low-voltage side of the linear fluorescent lamps 37, a region D32 of the screen corresponding to the slightly higher voltage side of the lamps 37 and a region D33 of the screen corresponding to the highest voltage side of the lamps 37, and that the gradation conversion characteristic for the data is switched depending on which of the regions D31 to D33 is used to display the data. The gradation conversion unit 31 has three gradation conversion characteristics as shown in FIG. 16 that can be switched from one to another, i.e., a gradation conversion characteristic a adapted to output the input gradation level as is (without converting it), a gradation conversion characteristic b adapted to output the gradation level after slightly suppressing the input level and a gradation conversion characteristic c adapted to output the gradation level after further suppressing the input level. The gradation conversion unit 31 may be configured, for example, with a lookup table (LUT) or a multiplication circuit adapted to multiply the input image data by a given coefficient. If the latter is used, the multiplication coefficient is switched to one of ka=1.0, ka=0.9 and ka=0.8 correspondingly with the control signal from the microcomputer 36. This causes the input image data to be multiplied by the multiplication coefficient, thus realizing three gradation conversion characteristics shown in FIG. 16, namely, the characteristics a to c. When judging that the screen position to display the image data belongs to the region D31 of the display screen, the microcomputer 36 outputs a control signal to the gradation conversion unit 31 to select the gradation conversion characteristic a. That is, the gradation conversion characteristic a is selected for the image data to be displayed in the region D31 of the display screen. Therefore, the image data is output as is (without any conversion) to the LCD control portion 32. On the other hand, when judging that the screen position to display the image data belongs to the region D32 of the display screen, the microcomputer 36 outputs a control signal to the gradation conversion unit 31 to select the gradation conversion characteristic b. That is, the gradation conversion characteristic b is selected for the image data to be displayed in the region D32 of the display screen. Therefore, the image data is subjected to a gradation conversion process. As a result, the display brightness is slightly reduced in the region D32 of the display screen. Further, when judging that the screen position to display the image data belongs to the region D33 of the display screen, the microcomputer 36 outputs a control signal to the gradation conversion unit 31 to select the gradation conversion characteristic c. That is, the gradation conversion characteristic c is selected for the image data to be displayed in the region D33 of the display screen. Therefore, the image data is subjected to a gradation conversion process. As a result, the display brightness is further reduced in the region D33 of the display screen. This leads to a reduced amount of transmitted light passing through the liquid crystal panel 33 located at the high-voltage side of the linear fluorescent lamps 37 (reduced display brightness), thus realizing an even brightness distribution over the entire display screen. As described above, the present embodiment controls the gradation level of the image data correspondingly with the screen position to display the image data, thus reducing the uneven brightness in the longitudinal direction of the linear fluorescent lamps 37 and ensuring an even brightness distribution. It is to be noted that while the display screen is divided into the three regions D31 to D33 correspondingly with the longitudinal position of the linear fluorescent lamps 37 in the above embodiment so that the gradation conversion characteristics a to c are selected for the image data displayed respectively in the regions D31 to D33, it is needless to say that the number of divisions of the display screen and the positions at which to divide the screen can be changed as appropriate correspondingly with the brightness distribution (uneven brightness) in the longitudinal direction of the linear fluorescent lamps 37. On the other hand, the reference gradation voltage to drive the liquid crystal panel may be varied correspondingly with the display screen position of the liquid crystal panel to compensate for the uneven brightness in the longitudinal direction of the linear fluorescent lamps. Embodiment 11 In the liquid crystal display device, the aperture ratio can be alternatively changed correspondingly with the display screen position of the liquid crystal panel to compensate for the uneven brightness in the longitudinal direction of the fluorescent lamps and provide a display screen with an even brightness. That is, the aperture ratio of the liquid crystal panel can be changed correspondingly with the longitudinal position of the linear fluorescent lamps to reduce the uneven brightness between the two ends of the light source of the linear fluorescent lamps. In the case of the direct type, for example, the portion of the liquid crystal panel facing the high-voltage side of the linear fluorescent lamps is formed to have a small aperture ratio so as to reduce the amount of transmitted light passing through the panel, whereas the portion of the liquid crystal panel facing the low-voltage side of the linear fluorescent lamps is formed to have a large aperture ratio so as to increase the amount of transmitted light passing through the panel. This allows reduction of the uneven brightness in the longitudinal direction of the linear fluorescent lamps, thus ensuring an even brightness distribution. In the case of the edge light type, on the other hand, the aperture ratio of the liquid crystal panel is controlled correspondingly with the uneven brightness of the illumination light across the surface resulting from the uneven brightness in the longitudinal direction of the fluorescent lamp. This ensures an even brightness distribution. FIG. 17 illustrates an example of a configuration adapted to control the aperture ratio. In the figure, reference numeral 21 denotes a liquid crystal panel, 41 a screening film, 42 clear electrodes, 43 TFT drive elements, ian incident light on the liquid crystal panel and o an outgoing light from the liquid crystal panel. In the liquid crystal panel 21, the screening film 41 is generally provided that is made of a grid-patterned metal film. In an example of the present embodiment, the aperture ratio of each of the pixels is controlled by the screening film 41 correspondingly with the uneven brightness of the fluorescent lamps during the formation of this film 41. This compensates for the uneven brightness in the longitudinal direction of the fluorescent lamps with the pixel-by-pixel optical transmittance, thus achieving a display screen with an even brightness. As is apparent from the above description, the present invention imparts to the backlight unit the brightness compensation means adapted to compensate for the uneven brightness of the fluorescent lamps so as to compensate for the uneven brightness in the longitudinal direction inherently present in the linear fluorescent lamps and achieve a display screen with an even brightness. This compensates for the difference in brightness between the high- and low-voltage sides of the fluorescent lamps provided as the light source, thus achieving a backlight unit whose outgoing light delivers an even brightness. On the other hand, this backlight unit can be used to obtain a liquid crystal display device that delivers an even brightness over the entire display screen. Further, a liquid crystal display device can be obtained that delivers an even brightness over the entire display screen when the image data supplied to the liquid crystal panel or the aperture ratio of this panel is controlled to compensate for the brightness in the longitudinal direction of the fluorescent lamps.
<SOH> BACKGROUND OF THE INVENTION <EOH>A backlight unit is used to illuminate the target such as an LCD display panel. An LCD display device employs either one of two types of backlight configurations as a backlight unit; the direct type and the edge light type (light guide plate type). With the direct type, fluorescent tubes, i.e., a light source, are arranged directly below the liquid crystal panel to be illuminated. This allows fluorescent tubes to be increased with the change in the display screen size, thus achieving a sufficient brightness. In this case, however, the backlight unit is prone to an uneven brightness between areas having a fluorescent lamp and others not. Moreover, the direct type backlight unit must be built with sufficient strength. For example, the backlight case is fabricated with a metal plate. Then, a reflective sheet is affixed to the inner surface of the backlight, with a plurality of straight tube lamps arranged thereabove. With the edge light type, on the other hand, a fluorescent lamp is arranged at the edge of a light guiding body made, for example, of a clear acrylic plate. This type of backlight unit takes advantage of multireflection in the light guiding body to use one surface thereof as an area light source. The edge light type has a reflector at the back of the straight tube lamp and L-shaped lamp. Although the display device using the edge light type backlight unit can be reduced in thickness, the light guiding body of the large-size model becomes excessively heavy. Besides, upsizing of the device makes it difficult to secure sufficient screen brightness. The aforementioned features are the reasons why, in general, the direct type backlight unit is used for a large-screen liquid crystal display device, whereas the edge light type backlight unit is used for those with a small screen. The fluorescent lamps used for the backlight unit as described above are driven by a high voltage of 1 KV at a high frequency of 50 to 70 KHz to achieve even and high brightness. At this time, the fluorescent lamps develop uneven brightness, i.e., uneven brightness, in the form of a brightness gradient between the high- and low-voltage sides as a result of a leak current. This problem is caused by the following reason. The fluorescent lamps are driven by a high voltage at a high frequency. This causes the air layer to act as a stray capacitance and leads to a leak current flowing from the fluorescent lamps to the lamp reflector and the surrounding metal objects. As a result, the current flowing into the low-voltage side of the fluorescent lamps diminishes. This causes the low-voltage side to illuminate relatively less brighter than the high-voltage side. Therefore, if the fluorescent lamps are long, the leak current rises proportionally to the length thereof. In the presence of a large leak current, the farther the fluorescent lamps are from the drive circuit, the darker they become. This constitutes the cause of uneven brightness. That is, the larger the liquid crystal display device, the more likely the difference in brightness occurs between the high- and low-voltage sides of the lamps. It can be said that the technique allowing the realization of a backlight unit with minimal uneven brightness is essential. FIG. 18 is an explanatory view of the brightness characteristic of fluorescent lamps, illustrating an example of the brightness distribution in the longitudinal direction (i.e., in the direction of voltage application) of the fluorescent lamps generally used for a backlight type liquid crystal display device. As shown in FIG. 18 , the fluorescent lamps have a brightness gradient whose relative brightness diminishes from a high-voltage side H to a low-voltage side L. The brightness drop is particularly noticeable near the edge of the low-voltage side L. The brightness distribution curve itself also varies depending on the shape of the fluorescent lamps, the length of the fluorescent tube, the drive voltage or the drive frequency. Basically, however, the fluorescent lamps develop uneven brightness in the form of relatively low brightness at the low-voltage side L as compared with the high-voltage side H. FIG. 19 is a graph showing the brightness distribution characteristic in the longitudinal direction (in the direction of voltage application) of the fluorescent lamps having the brightness gradient shown in FIG. 18 when the drive voltage is further raised. In the example of FIG. 19 , the brightness of the fluorescent lamps at the center and low-voltage side L is roughly equal. However, the brightness is relatively higher near the edge at the high voltage side H. For example, assuming that the brightness is 100 at the center and the low-voltage side, the brightness is relatively higher or 115 to 125 at the high-voltage side H. The brightness, highest at the edge of the high-voltage side H, gradually declines toward the center of the fluorescent lamps. The display screen also develops uneven brightness due to uneven brightness developed by the fluorescent lamps in the longitudinal direction as described above. As a technique to reduce such uneven brightness in the display screen, the liquid crystal display device using a backlight is known as shown below. FIGS. 20A and 20B are explanatory views of an example of the liquid crystal display device having a conventional direct type backlight unit. FIG. 20A illustrates a side cross-sectional schematic configuration of the LCD device, whereas FIG. 20B illustrates a plan schematic configuration of the fluorescent lamps, i.e., the light source of the backlight unit. As shown in FIGS. 20A and 20B , the backlight unit has a plurality of fluorescent lamps 101 , reflectors 102 adapted to reflect the light from the fluorescent lamps 101 and an optical diffusion unit 103 provided at the front of the fluorescent lamps 101 and adapted to diffuse the light directly incident from the fluorescent lamps 101 or that reflected by the reflectors 102 . The backlight unit is used to illuminate a liquid crystal panel 104 provided at the front (surface side) thereof through the optical diffusion unit 103 . With the aforementioned backlight unit, the fluorescent lamps 101 are arranged in sets of two such that the high-voltage side of one lamp is adjacent to the low-voltage side of the other to compensate for uneven brightness in the lamps 101 and achieve a display screen with even brightness. That is, as shown in FIGS. 20A and 20B , the backlight unit is provided with a plurality of sets (S 1 , S 2 , S 3 and beyond) of the two fluorescent lamps 101 , with the high-voltage side H of one lamp adjacent to the low-voltage side L of the other lamp. Such a configuration cancels out uneven brightness resulting from each fluorescent lamp, thus eliminating uneven brightness on the display screen and achieving an even display. A liquid crystal display device in Patent Document 1 is disclosed as an example with the high- and low-voltage sides H and L arranged adjacent to each other. Further, the technique as shown in FIGS. 21A and 21B is available that is associated with the liquid crystal display device operable to improve the reflectance of the light from the backlight. FIGS. 21A and 21B illustrate another example of the backlight unit in a conventional liquid crystal display device. FIG. 21A illustrates a side cross-sectional schematic configuration of the backlight unit, whereas FIG. 21B illustrates a plan schematic configuration of the inside of the unit, with the optical diffusion sheet, provided on the backlight unit surface, removed. In FIGS. 21A and 21B , reference numeral 201 denotes linear fluorescent lamps, 202 optical diffusion sheets, 203 a reflection sheet and 204 a reflection layer and 205 an enclosure. The backlight unit shown in FIGS. 21A and 21B has the reflection layer 204 , made of a high reflectance material such as aluminum, on the inner surface at the bottom of the enclosure 205 further at the back of the reflection sheet 203 provided at the back of the linear fluorescent lamps 201 to efficiently enhance the brightness. Here, of the light incident on the reflection sheet 203 , the fraction that passes through the sheet 203 without being reflected is reflected again by the reflection layer 204 back toward the reflection sheet 203 , rather than disappears or becomes diffused at the back of the reflection sheet 203 . This ensures efficient use of the light passing through the sheet 203 from the back, thus enhancing the brightness. In general, a foamed PET (Poly Ethylene Terephthalate) sheet is often used for the direct type reflection unit (equivalent to the reflection sheet 203 described above). The foamed PET reflection sheet is manufactured by foaming PET to produce fine air bubbles within the sheet. The light incident on the foamed PET sheet is refracted by the air bubbles to regress and emerge again from the incident side. Such a light reflection takes advantage of the refraction characteristic between the PET material and the air in the air bubbles, thus minimizing light loss and achieving a high reflectance reflection unit, despite the use of an inexpensive member. In addition to the above, other materials may be alternatively used including those coated on the surface with a high reflectance material such as silver or aluminum. For example, while the reflection sheet 203 , formed with a foamed PET sheet as described above, achieves a high reflectance, part of the incident light from the light source passes through the foamed PET sheet to the rear side (back side opposite to the light source). This leads to reduced light utilization efficiency. To improve these points for enhanced light utilization efficiency, the reflection layer 204 made of a high reflectance material such as aluminum is provided on the inner surface of the enclosure 205 at the back of the reflection sheet 203 to reflect the light passing through the reflection sheet 203 with the reflection layer 204 . Part of the reflected light from the reflection layer 204 passes again through the reflection sheet 203 and emerges on the front side (light source side). This ensures improved light utilization efficiency. An edge light type backlight device using a light guide plate is disclosed, for example, in Patent Document 2 as the backlight device having another reflection layer stacked at the back of the reflection sheet as described above. Further, Patent Document 3 discloses a technique that changes the leak current flowing between the high- and low-voltage sides of the fluorescent tube in an edge light type backlight unit to suppress the uneven brightness of the screen. With this backlight unit, the fluorescent lamp is shaped to have straight tube portions in one piece; the one portion running along one of the longer sides of the light guide plate and the other portions each running along one of the shorter sides of the plate. The reflector, provided on the straight tube portion at the high-voltage side of the fluorescent lamp, i.e., one of the tube portions running along the shorter sides of the light guide plate, is formed with a white reflecting member, whereas the reflector at the low-voltage side is deposited on the inside with silver. Such a configuration changes the leak current flowing between the high- and low-voltage sides, thus securing a proper fluorescent lamp length to generate necessary brightness over the rectangular screen and minimizing the difference in brightness between the left and right sides of the screen. Further, the problem here derives from the driving at a high frequency. Therefore, the method is under consideration to drive the fluorescent lamp at the lowest possible frequency for increased the impedance of the stray capacitance and reduced leak current, thus eliminating uneven brightness. Description will be given next of the problems associated with the conventional techniques described above. With the liquid crystal display device described in Patent Document 1, the fluorescent lamps are arranged parallel with each other in sets of two such that the high-voltage side H of one lamp is adjacent to the low-voltage side L of the other. At this time, because of the proximity between the high-voltage side terminal of one fluorescent lamp and the low-voltage side terminal of the other lamp adjacent thereto, discharge may occur between the two electrodes. This renders the stable discharge of the fluorescent lamps itself extremely difficult and possibly deteriorates the reliability of the device. Moreover, the high- and low-voltage terminals of the fluorescent lamps are disposed separately on both sides of the display screen. This requires two inverter power circuits, resulting in higher cost. Further, the thinner and larger the display device, the more difficult it is to make wiring connections to the fluorescent lamps. As a result, additional measures are required to ensure wiring safety and prevent the current leak. With the backlight device of Patent Document 2, on the other hand, if the brightness distribution of the fluorescent lamp is not uniform in the longitudinal direction, the entire display screen may develop uneven brightness as a result of the uneven brightness of the fluorescent lamp. This makes it difficult to control the brightness distribution. In particular, the GND side (low-voltage side) is prone to current leak from the fluorescent lamp. This results in high brightness only at the high-voltage side of the fluorescent lamp and low brightness at the GND side. In the case of Patent Document 3, provision of the white reflector only on one of the shorter sides of the fluorescent lamp alone cannot compensate for the brightness gradient inherently present in the fluorescent lamps. The fluorescent lamp invariably develops a brightness gradient at least along its longer sides. This results in uneven brightness in the liquid crystal display device. If the fluorescent lamp is longer as a result of the upsizing of the liquid crystal display device, the aforementioned problem becomes more noticeable. Further, while the method of lighting the lamps at a lower drive frequency could be possible to the extent that thermal runaway does not occur in the transformer, an excessively low frequency design could degrade the reliability. Besides, lowering the drive frequency will result in larger components such as the transformer. In light of the foregoing, the present invention was conceived and the object thereof is to provide a backlight unit operable to compensate for the brightness difference between the high- and low-voltage sides of the fluorescent lamps, provided as a light source, and to ensure an even brightness of the outgoing light, and a liquid crystal display device operable to ensure an even brightness over the entire display screen. Patent Document 1: Japanese Laid-Open Patent Publication No. H11-295731 Patent Document 2: Japanese Laid-Open Patent Publication No. H08-335048 Patent Document 3: Japanese Laid-Open Patent Publication No. H10-112213
<SOH> BRIEF DESCRIPTION OF THE DRAWINGS <EOH>FIGS. 1A and 1B are explanatory views of an embodiment of a backlight unit according to the present invention; FIG. 2 is an explanatory view of a layout example of fluorescent lamps in a backlight unit applied to the present invention; FIG. 3 is an explanatory view of an example of a dot pattern imparted to a reflection layer; FIGS. 4A and 4B are expanded views of the dot pattern of the reflection layer shown in FIG. 3 ; FIG. 5 is an explanatory view of another embodiment of the backlight unit according to the present invention; FIG. 6 is an explanatory view of still another embodiment of the backlight unit according to the present invention; FIGS. 7A and 7B are explanatory views of still another embodiment of the backlight unit according to the present invention; FIG. 8 is an explanatory view of still another embodiment of the backlight unit according to the present invention; FIGS. 9A to 9 D are explanatory views of still another embodiment of the backlight unit according to the present invention; FIG. 10 illustrates an example of the relationship between the film thickness of a fluorescent substance and the tube surface brightness at that time; FIG. 11 is an explanatory view of still another embodiment of the backlight unit according to the present invention; FIGS. 12A and 12B illustrate a configuration example of the edge light type backlight unit according to the present invention; FIG. 13 is an explanatory view of an embodiment of a liquid crystal display device according to the present invention; FIG. 14 is a block diagram of the major components illustrating a schematic configuration of another embodiment of the liquid crystal display device according to the present invention; FIG. 15 is an explanatory view of the display screen region of the liquid crystal display device of FIG. 14 ; FIG. 16 illustrates gradation conversion characteristics (input/output characteristics) of a gradation conversion unit in the liquid crystal display device of FIG. 14 ; FIG. 17 is an explanatory view of the aperture ratio control in a liquid crystal panel; FIG. 18 is an explanatory view of an example of the relative brightness distribution characteristic in the longitudinal direction (in the direction of voltage application) of the fluorescent lamps; FIG. 19 is a graph illustrating the relative brightness characteristic in the longitudinal direction (in the direction of voltage application) of the fluorescent lamps when a drive voltage, applied to the fluorescent lamps having the brightness gradient shown in FIG. 18 , is further raised; FIGS. 20A and 20B are explanatory views of an example of the liquid crystal display device having a conventional direct type backlight unit; and FIGS. 21A and 21B illustrate another example of the backlight unit in the conventional liquid crystal display device. detailed-description description="Detailed Description" end="lead"?
20050329
20081104
20060302
72518.0
F21V704
0
MACCHIAROLO, LEAH SIMONE
BACKLIGHT UNIT AND LIQUID CRYSTAL DISPLAY UNIT USING BACKLIGHT UNIT
UNDISCOUNTED
0
ACCEPTED
F21V
2,005
10,529,717
ACCEPTED
Power consumption protocol
Low power consumption protocol A telemetry unit (100) is provided for mounting inside a pneumatic tyre, which includes a piezoelectric element (114) supported in a housing (112), with an actuator (136) arranged for contact with the element (114), to deflect the element (114) in response to external forces acting on the actuator (136) during rotation of the tyre. For every rotation of the tyre, cyclic pulses of electrical charge are generated by the deflection of the element (114). The charge is stored and utilised under a power consumption protocol including the steps of: initiating power to a data measurement circuit for measuring data from the environment local to the unit (100); disabling power to the data measurement circuit; initiating power to a data transmission circuit; transmitting data from the measurement circuit; and disabling power to the transmission circuit. The power consumption protocol therefore minimises consumption of the generated power, during measurement and transmission of data by the unit (100).
1. A method for selectively controlling the power consumption of a piezoelectrically powered telemetry unit, the telemetry unit forming part of a tyre monitoring system and having a piezoelectric power generator including a storage device for storing charge generated by the piezoelectric power generator, the unit further including a microprocessor, a data measurement circuit, and a data transmission circuit, in which the method incorporates a power consumption protocol for regulating the consumption of power from the piezoelectric power generator, including the successive steps of: initiating power from the piezoelectric generator to the data measurement circuit for measuring data from the environment local to the unit; disabling said power to the data measurement circuit; initiating power from the piezoelectric power generator to the data transmission circuit; transmitting the measured data; and disabling said power to the transmission circuit; wherein the protocol further includes a sleep mode, the length of which is varied in dependence on the amount of charge stored in the storage device, or upon the rate at which electric charge is generated by the generator. 2. A method as claimed in claim 1, in which the protocol is cyclic, so that the first protocol step of power being initiated from the piezoelectric power generator to the data measurement circuit is carried out after each transmission of measured data. 3. A method as claimed in claim 1, in which the measured data is stored in the microprocessor before disabling power to the data measurement circuit. 4. A method as claimed in claim 1, in which the protocol initializes power to the data measurement circuit after a predetermined time from the disabling of power to the transmission circuit. 5. A method as claimed in claim 4, in which the microprocessor monitors the time from the disabling of power to the transmission circuit. 6. A method as claimed in claim 5, in which the microprocessor monitors the time from the disabling of power to the transmission circuit via an externally referenced clock. 7. A method as claimed in claim 6, in which the microprocessor switches from the externally referenced clock to an internal clock, after the predetermined time. 8. A method as claimed in claim 7, in which the microprocessor switches to the externally referenced clock after the measured data has been stored. 9. A method as claimed in claim 1, in which a predetermined time is allowed to elapse between initializing power to the data measurement circuit and the measurement of data. 10. A method as claimed in claim 1, in which a predetermined time is allowed to elapse between initializing power to the data transmission circuit and transmission of the measured data.
The present invention relates to a power consumption protocol or method for selectively controlling the power consumption of a telemetry unit having a power source. The invention is of particular advantage in controlling the consumption of power from a piezoelectric power generator, for supplying power to a remote telemetry apparatus for transmitting data from a rotatable body, for example from within a pneumatic tyre. It is known to provide a tyre monitoring apparatus for measuring the pressure within vehicle tyres. The tyre monitoring apparatus may also measure other parameters within a tyre environment, such as the local temperature of a tyre. The measured data is transmitted, for example via a radio wave link, to the cabin of the vehicle where it is electronically processed before being displayed to the vehicle driver. This enables the recipient of the transmitted data to monitor changes in the condition of the tyre, for example to reduce damage to the tyre(s) of a vehicle, or to predict tyre failure. This is of particular advantage at high vehicle speeds, when the environment within a tyre is at its most hostile and the likelihood of damage to a tyre and, indeed, injury to the occupants of the vehicle, is at its greatest. The majority of existing tyre monitoring apparatus use a battery as the power source, which is located on or within a wheel or tyre. Such arrangements have several undesirable limitations, for example limited battery life and size or weight which can be accommodated within a tyre. This can have a further undesirable knock on effect, in that if there is a limited power source available, for example as a result of weight implications, the number and frequency of data transmissions that can be relayed for processing is compromised. It is an object of the invention to reduce or substantially obviate the disadvantages referred to above. According to the present invention, there is provided a method for selectively controlling the power consumption of a telemetry unit having a power source, the unit including a micro processor, a data measurement circuit, and a data transmission circuit, in which the method incorporates a power consumption protocol including the successive steps of: initiating power to the data measurement circuit for measuring data from the environment local to the unit; disabling power to the data measurement circuit; initiating power to the data transmission circuit; transmitting the measured data; and disabling power to the transmission circuit. Preferably, the measured data is stored in the microprocessor before disabling power to the data measurement circuit. Conveniently, the protocol is cyclic, and may include a sleep mode between the transmission of data and the initialising of power to the measurement circuit. Preferably, the protocol initialises power to the data measurement circuit after a predetermined time from the disabling of power to the transmission circuit. In a preferred embodiment, the microprocessor monitors the time from the disabling of power to the transmission circuit. Preferably, the microprocessor monitors the time from the disabling of power to the transmission circuit via an externally referenced clock. Preferably, the microprocessor switches from the externally referenced clock to an internal clock, after the predetermined time, and may switch to the externally referenced clock after the measured data has been stored. In a preferred embodiment, a predetermined time is allowed to elapse between initialising power to the data measurement circuit and the measurement of data. A predetermined time may be allowed to elapse between initialising power to the data transmission circuit and transmission of the measured data. Preferably, the power source comprises an electrical generator and a storage device for storing electrical charge. The generator may be a piezoelectric generator. In such an arrangement, the length of the sleep mode can be varied in dependance on the amount of charge stored in the storage device or upon the rate at which electric charge is generated by the generator. Preferably, the telemetry unit forms part of a tyre monitoring system. The invention is of primary advantage when used with a telemetry unit in which the power source is a piezoelectric element, for selectively controlling the consumption of the small amounts of charge generated by the piezoelectric element, in particular for a tyre monitoring apparatus. The invention will now be described, by way of example, with reference to the accompanying drawings, in which: FIG. 1 is an exploded perspective view of an in-tyre power/sensor or telemetry unit having a power generator; FIG. 2 is a partial cross-sectional view of the unit shown in FIG. 1 in an assembled, rest position; FIG. 3 is a perspective view the unit shown in FIG. 2; FIG. 4 is a schematic plan view of the piezoelectric disc and brass mounting which forms part of the unit shown in FIGS. 1 to 3; FIG. 5a is a block diagram showing the interrelationship between components of the power generator; FIG. 5 is a flow diagram showing the stages involved in a low power consumption protocol according to a preferred embodiment of the invention, for controlling the measurement and transmission of data from the unit shown in FIGS. 1 to 3; FIG. 6 is a perspective view of a further embodiment of an in-tyre power/sensor or telemetry unit having a power generator; FIG. 7 is perspective exploded view of the unit of FIG. 6, from above; FIG. 8 is a perspective exploded view of the unit of FIGS. 6 and 7, from below; FIG. 9 is a cross-sectional view through the unit of FIGS. 6 to 8; FIG. 10 shows an end view of the unit of FIGS. 6 to 9 in use in a pneumatic tyre; and FIG. 11 is a side view of the unit as shown in FIG. 10. Referring to FIGS. 1 to 4, a power generator/sensor unit is indicated generally at 10, for use in a tyre monitoring apparatus. The unit 10 includes a housing 12 made as a reinforced injection moulding composite for mounting in and adapted to withstand the harsh environment of pneumatic vehicle tyre. Although the housing 102 is described as being made as a composite moulding, any suitable material can be used. The housing 12 has a base or footing 16 having a shallow convex outer profile, indicated at C in FIG. 2, for bonding to a correspondingly arcuate interior surface of a vehicle tyre. The base 16 defines a chamber, indicated at 18 in FIG. 1, having an internal base wall 20. The unit 10 includes a piezoelectric element 11 in the form of a piezoceramic disc 14 having a radius R, which is mounted centrally on a brass supporting disc 15 having a radius greater than R. The element 11 is mounted in the housing 12 for generating electrical power to operate circuitry within the unit 10. The base 16 of the housing 12 includes two opposed recesses 22, one of which can be seen clearly in FIG. 1, for supporting part of the periphery of the brass disc 15. When supported on the base 16, the central portion of the brass disc 15 is spaced apart from the base wall 20 by a small distance. A cover 26 is received on the base 16, which overlays the part of the periphery of the brass disc 15 supported on the recesses 22, such that the disc is clamped between the cover 26 and the recesses 22 along two edge portions 47. A cap 28 is provided over the cover 26, the cap including a central formation 30 which extends through a central aperture 27 in the cover 26. A printed circuit board (PCB) 32 is mounted in the housing 12 on the cap 28. As shown in FIG. 5a, the PCB 32 includes a micro processor, a radio frequency (RF) transmitter, pressure and temperature sensor circuitry, including pressure and temperature sensors, and supervision and control circuitry, which form part of a tyre monitoring apparatus. The PCB 32 also includes a rectifier for converting an alternating current output from the piezoceramic disc 14 into a direct current output; an energy storage element in the form of a series of a capacitors, which store the direct current output from the rectifier until required, and a DC-DC controller which is provided for regulating voltage output from the capacitors. The unit 10 uses ultra low leakage type capacitors, to ensure that as high a percentage of the generated charge is retained as possible and that internal leakage is kept to a minimum. The PCB 32 is in electrical communication with the piezoceramic disc 14 via two wires, not shown, and is securably located on the cap 28 by a potting compound 34, to protect the PCB 32 during installation or transit, and from the harsh environment within a rotating pneumatic tyre. The potting compound 34 can be any suitable type but in this embodiment is a two-part epoxy adhesive. An actuator 36 is disposed between the piezoceramic disc 14, the cover 26 and the cap 28, the actuator consisting of an integrally formed foot 38 and a stem 40. The stem 40 extends into the central formation of the cap 28 and includes a central bore 42. As can be seen clearly in FIG. 2, the foot 38 includes an integrally formed elongate projection or nose 44, which is in contact with the piezoceramic element. The nose 44 extends diametrically across the piezoelectric element 11, as indicated in FIG. 4, which shows the contact area 45 of the nose 44 on the piezoelectric element 11 and the areas of support 47 for the disc 15 on the base 16. It will be appreciated that the piezoelectric element 11 is configured substantially as a simply supported beam, supported on one side by the recesses 22 in the base 16 and contactable on its opposite side by the nose 44 of the actuator 36. The actuator 36 is connected to the cap 28 by a screw 46 which passes through the cap 28 and is securably received in the bore 42 of the stem 40. The base 16 is connected to the cover 26 by four screws 48, which pass through the corners of the base 16 and which are securably received in the cover 26. The arrangement is such that the piezoelectric element 11 can be deflected downwardly (as viewed in FIG. 2) under the influence of the actuator 36, as will be described in more detail below. However, the maximum deflection of the piezoelectric element 11 is limited by the distance between the underside of the brass disc 15 and the internal base wall 20, set at 0.4 mm in the embodiment of FIGS. 1 to 4. Thus, the element 11 is protected against excess deflexion, which might otherwise damage the structure and generating capacity of the element 11. The movement of the actuator 36 within the housing 12 in the opposite direction, i.e. perpendicularly away from the piezoceramic disc 14, upwards as viewed in FIG. 2, is restricted by walls 27 of the cover 26. In the embodiment of FIGS. 1 to 4, the maximum distance between the upper side of the foot 38 of the actuator 36 and the walls 27 of the cover 26 is 0.6 mm when the power generator 10 is in the rest position shown in FIG. 2. Hence, the maximum travel of the actuator 36 within the housing 12 is 1 mm in the embodiment of FIGS. 1 to 4. This maximum distance of travel of the actuator 36 within the housing 12 is set at a predetermined low value to protect the piezoceramic disc 14 from damage due to deflection and/or impact of the actuator 36 on the upper surface of the piezoceramic disc 14 in use. It will be understood that the maximum travel of the actuator and deflection of the piezoelectric element can be limited to any distance suitable for protecting the integrity of the structure and charge generating capacity of the piezoelectric element. The arrangement of the piezoceramic disc 14, in combination with the components of the PCB 32 which are associated with the piezoceramic disc 14, as described above, form part of a power generator, for supplying power for the circuitry of the unit 10. Operation of the power generator will now be described, by way of example, in which the unit 10 is mounted in a pneumatic tyre on the wheel of a vehicle, with the outer surface of the base 16 of the housing 12 bonded to a correspondingly arcuate profile of an interior surface of the tyre, and in which the unit 10 includes a piezoceramic disc 14 of any suitable known construction. It will be appreciated that mechanical excitation of the disc 14 generates a voltage. The effect is substantially linear, i.e. the electric field generated varies directly with the applied mechanical stress, and is direction dependent, so that compressive and tensile stresses generate voltages of opposite polarity. The cap 28, PCB 32, potting compound 34 and the actuator 36 act on the disc 14 as a single unit mass, in use, i.e. with the cap, actuator, circuitry and potting compound acting as a composite actuating mass. When the wheel is in rotation, centrifugal forces act on the cap 28, PCB 32 and the potting compound 34, which urge the actuator 36 radially outwards in the direction of the piezoelectric element 11. This centrifugal action on the actuator 36 causes the piezoelectric element 11 to deflect, typically between 0.2 to 0.4 mm at its central region 45 from a rest position when the wheel is not in rotation. Since the piezoelectric element 11 acts as a simply supported beam and the nose 44 of the actuator 36 is in contact with the disc 14 at the central position 45 between the area of support for the brass disc 15, the deflection is in the form of a uniform bending of the discs 14 and 15 between the two areas of support 47 of the brass disc 15. It will be understood that, as the vehicle is in motion, the external area of the tyre adjacent the unit 10 comes in to contact with the surface along which the vehicle is travelling, once with every revolution of the wheel. This contact deforms the area of the tyre adjacent the unit, which deformation is transmitted to the power generator, ultimately in the form of a deformation of the piezoelectric element 11 by the actuator 36. Hence, the piezoceramic disc 14 is subjected to variations in mechanical excitation during rotation of the wheel on the road surface, whereby each excitation results in a potential difference being generated by the piezoceramic disc 14. This process is set out below, with reference to a rotating wheel, starting from a position where the area of the tyre adjacent the unit 10 is moving towards contact with a road surface. With the wheel in rotation, the actuator 36 is in contact with the piezoceramic disc 14, under centrifugal action from the cap 28, PCB 32 and potting compound 34, as described above. The piezoceramic disc 14 therefore experiences a substantially constant deflection under the centrifugal forces which are transmitted through the actuator 36. As the wheel rotates further, the area of the tyre adjacent the unit 10 comes into contact with the road surface and deforms. The deformation results in a deceleration of the tyre in the region of the point of contact with the road surface, causing a sudden reduction in the centrifugal forces experienced by the actuator 36, almost instantaneously, substantially to zero. This change in centrifugal acceleration causes a reduction in the deflection experienced by the piezoceramic disc 14 under action of the actuator 36 and generates a first pulse of electrical charge, which is communicated to the PCB 32. As the wheel rotates further, at the instant where the area of the tyre adjacent the unit 10 moves away from contact with the road surface, the acceleration of the tyre adjacent the unit 10 increases suddenly, which results in an instantaneous increase in the centrifugal forces experienced by the actuator 36. Hence, piezoceramic disc 14 is again caused to deflect under centrifugal action of the actuator 36, cap 28, PCB 32 and potting compound 34, as described above, which generates a second pulse of electrical charge of opposite polarity to the first pulse described above, which is communicated to the PCB 32. Hence, during a single revolution of the wheel two pulses of electrical charge, of opposite polarity, are generated in quick succession, constituting a single alternating current output. The rectifier rectifies the alternating current output into a direct current output, which is stored in the capacitors for use to power the tyre monitoring apparatus. For each revolution of the wheel, a small storable electrical charge is generated, typically of 5-10 nano coulombs. In addition to the storable charge generated with each revolution of the wheel due to contact with the road surface, the unit 10 may also transmit other excitation forces to the piezoelectric element 14, for example accelerations/deflections which are caused by vibrations due to imperfections in the road surface, or out of balance forces on the wheel itself. If the excitation is sufficient to cause deflection of the piezoelectric disc 14, an additional storable charge will be generated and stored in the capacitors, as described above. In some circumstances, the forces acting on the unit 10 inside a vehicle tyre will not be sufficient to cause uniform bending of the piezoceramic disc 14, as described above. Instead, the deformation will be in the form of a localised ‘squashing’ of the structure of the disc 14 at the point of contact with, and in the region immediately adjacent to, the actuator. In operation, the localised ‘squashing’ of the disc structure also generates a potential difference across the element 11, for generating charge substantially as described above. The unit 10 is particularly advantageous in that the control circuitry is used as an actuating mass for the piezoelectric element 11. In the described embodiment, the weight of the cap 28, the PCB 32 and the potting compound 34 operate as a single unit to act as an actuating mass/exciter for the piezoceramic disc 14, without the need for any additional mass. Hence there is an overall saving in weight in the power generator, to minimise localised wear caused by the unit 10 adjacent the area of mounting in the vehicle tyre, and thus reduce the likelihood of a localised bald spot occurring in the tread of the tyre. The outer surface C of the base 16 may include an external profile for complimentary engagement with the internal pattern of a vehicle tyre, to limit further the effects of localised wear on the tyre, in use. In order to utilise the small amounts of power generated by the power generator and to remove the need for a battery backup to power the tyre monitoring apparatus, the invention provides an ultra low power consumption protocol, for controlling the consumption of power stored by the capacitors. Operation of a tyre monitoring apparatus will now be described by way of example, illustrating the stages which are implemented to ensure that the optimum low power protocol is realised, starting with the monitoring apparatus in a ‘sleep’ mode, with reference to FIG. 5. As referred to above, the tyre monitoring apparatus includes a unit 10 having a piezoelectric power generator, a micro processor, a radio frequency (RF) transmitter, pressure and temperature sensor circuitry and supervision and control circuitry. EXAMPLE 1 Stage 1 The micro processor is in ‘sleep’ mode, in which all internal processing is suspended, apart from a monitor circuit, for monitoring the ‘wake up’ requirements of the micro processor. In this embodiment, the monitor circuit monitors an externally referenced clock in the form of a crystal oscillator, located outside the micro processor in the unit. Hence, in sleep mode, the majority of the micro processor circuitry is disabled and the power consumption of the tyre monitoring apparatus is at a minimum level, for example approximately 24 micro ampere of supply current. Stage 2 After a predetermined time, in this embodiment 60 seconds, the monitor circuit ‘wakes up’ the micro processor. Upon ‘wake up’, the micro processor switches from the external clock to an internal clock, in the form of an internal resistor capacitor oscillator. This switch is implemented to facilitate a higher speed operation of the analogue to digital conversions and subsequent calculations which are utilised by the tyre monitoring apparatus. The switch also initiates power to the internal circuitry of the micro processor, which allows the main program of the micro processor to be used and to enable the micro processor to enter a measure and control phase. Stage 3 Once the micro processor has ‘woken up’, power is provided to the temperature and pressure sensor circuitry. A prescribed time is then allowed to elapse, in this embodiment 0.5 milli seconds, to facilitate settling of the sensor circuitry, after which time the micro processor measures the local pressure and temperature within the tyre. The values are then stored within the micro processor and the power to the sensor circuitry is removed instantaneously. Stage 4 The stored pressure and temperature values are concatenated with a sensor identification and cyclic redundancy check to form a data packet for transmitting to a receiver unit/display unit in the vehicle. Stage 5 The micro processor then switches from the internal clock back to the external clock. This change is employed to ensure accurate time signals for the transmission of the data via the radio frequency (RF) link, since the external clock is a quartz crystal time reference unit, which ensures that a higher absolute frequency accuracy is attainable than with the internal clock. Stage 6 The micro processor sets a control line to a logic high of 3 v, which enables the RF transmitter, thus causing it to emit a radio frequency carrier. A settling time of approximately 1 milli second then elapses to facilitate settling of the RF transmitter components prior to the transmission of data from the PCB 32. A pseudo bit pattern, used to bias a radio frequency data slicer, is then concatenated with the sensor identification and cyclic redundancy check for transmitting. The data to be transmitted is then frequency modulated onto a 433 MHz radio wave for propagation to the receiver unit. Stage 7 The data is transmitted and power to the RF transmitter is then inhibited instantaneously, at which point the micro processor then re-enters ‘sleep mode’. Hence, by utilising the low power protocol described in stages 1-7 of the above example, the tyre monitoring apparatus utilises only a minimum amount of power from the power generator, to transmit a reading of the local pressure and temperature within the tyre. After use, the micro processor remains in sleep mode for a predetermined period, as referred to in Stage 2 above, while the energy stored in the capacitors is recharged by excitation of the piezoceramic disc 14, as described with reference to FIGS. 1 to 4. Hence, using a continuous cycle of stages 1-7, the tyre monitoring apparatus is able to monitor the local condition of the tyre utilising the small electrical charges generated by the piezoceramic disc 14, without the need for a back-up battery supply. The continuous cycles are of advantage during normal operating conditions of the tyre, whereby any changes in tyre pressure or temperature, which might indicate a potential problem or failure of the tyre, can be monitored, to a void a blow out, for example. This has particular advantage at high vehicle speeds. Principally, there is a tri-way interdependency of critical factors in the protocol for the telemetry unit, between the charge generation capability of the piezoelectric element, the charge storage size and efficiency, and the RF transmitter reliability governed by the transmitter ‘on’ time. For a given type of piezoelectric element, there is an optimum charge capacitance for the power generator and optimum transmission time for the RF transmitter. The piezoelectric element must have sufficient charge generation overcome the impedance of the storage capacitors, and the capacitors must have sufficient capacitance to hold the charge required to perform the measurement/transmission cycle. The RF transmitter ‘on’ time, i.e. when the transmitter is active and transmitting, must be optimised between a maximum period in which there is sufficient charge to transmit the data prior to the energy storage being exhausted, and a minimum period below which the reliability of the RF link is adversely effected. If transmission time is extended beyond the optimum period, the effective frequency of data transmissions is reduced for a given capacitance. The data transmitted to the in-car receiver unit is shown to the driver of the vehicle on the display unit for the or each of the sensor circuits in the tyre monitoring apparatus, with respect to each tyre of the vehicle. The display unit informs the driver of the data visually and/or by audible means, for example a link to the audio system in the vehicle. Each tyre/wheel of the vehicle is marked by an individual identifying feature that relates to a specific sensor located within that tyre. This identifying feature is also represented on the display unit, in combination with the data from the sensor within the tyre. In the event that the wheel is moved to another position on the vehicle it can always be related to the relevant information on the display unit. Suitable identifying features include colour-coded symbols and alpha numeric symbols. Each sensor has a unique electronic serial number, which can be used to aid the security of the radio transmission data. The unique electronic serial number can also act as an electronic tagging feature for security and anti counterfeiting purposes. With reference to the preferred embodiment of the power generator, it has been described that a storable electrical charge is generated by the piezoelectric element with each revolution of the vehicle wheel. Therefore, it will be appreciated that the generation of charge is proportional to the speed at which the vehicle is travelling. In the above example of the power consumption protocol, the time delay between transmission of data from the tyre monitoring apparatus and the “wake up” of the micro processor for measuring and transmitting a further reading is set to a predetermined value. In a slow moving vehicle, the electrical charge which is generated and stored within a predetermined time period is less than would be generated and stored in a vehicle travelling at a faster speed in the same time period. Therefore, the time interval between “wake up” of the microprocessor is set at a predetermined value, selected to allow a sufficient electrical charge to be generated and stored for measurement and transmission of the parameters of a tyre on a slow moving vehicle, for example 25 kmh. However, as the speed of the vehicle increases, the rate of electrical charge generation also increases. Thus, the time period required to generate sufficient electrical charge to enable the tyre monitoring system to measure and transmit the tyre parameters is reduced. To take advantage of this, the low power protocol described above can be modified so that the micro processor is “awoken” from its sleep mode at intervals relative to a function of the speed of the vehicle or the state of the electrical charge stored in the capacitors, which enables the transmission of data to be varied in proportion to the speed of the vehicle. The following example shows a preferred mode of operation, in which the rate of transmission of data from the tyre monitoring apparatus is proportional to the speed of the vehicle, starting with the monitoring system in a “sleep” mode, substantially as described in example 1. EXAMPLE 2 Stage 1 As the wheel rotates, storable power outputs are produced by the power generator, one per revolution, as described above. In this example, this characteristic of the power generator is used to monitor the speed of the vehicle and/or the state of charge of the capacitors. A small portion of each storable power output is signal conditioned to take in to consideration false triggers of power which may be experienced by the piezoelectric disc 14 during rotation of the wheel, for example accelerations/deflections which are caused by vibrations due to imperfections in the road surface. The conditioned signal is then supplied to an interrupt circuit in the micro processor, which momentarily wakes the micro processor from its sleep mode and increments a counter in the micro processor. The micro processor then returns instantly to the sleep mode. Stage 2 Both the average charge generated per revolution of the wheel and the value of stored charge sufficient to measure and transmit data from the unit 10 are known. Hence, the number of “interrupts” or increments of the counter required for the capacitors to store a charge sufficient for measurement and transmission of data from the apparatus can be calculated. Therefore, the micro processor can be set to “wake up”, substantially as described in stage 2 of example 1, after a predetermined number of revolutions of the wheel, for example 50 revolutions. At this point, power is initiated to the internal circuitry of the micro processor, which allows the main program of the micro processor to be used and to enable the micro processor to enter a measure and control phase. The internal clock of the micro processor monitors the time taken for the predetermined number of revolutions to be completed. Hence, a value of average speed of the vehicle during the time period can be calculated from the elapsed time and the distance travelled which is cross-referenced from a table of data relating to the diameter of the wheel. Stage 3 As described in example 1, once the micro processor has ‘woken up’, power is provided to the temperature and pressure sensor circuitry. A prescribed time is then allowed to elapse, for example 500 micro seconds, to facilitate settling of the sensor circuitry, after which time the micro processor measures the local pressure and temperature within the tyre. The values are then stored within the micro processor and the power to the sensor circuitry is removed instantaneously. Stage 4 The stored pressure and temperature values are concatenated with a sensor identification and cyclic redundancy check, as described in stage 4 of example 1, and the value of speed calculated during stage 2. Further stages 5 to 7 are then carried out substantially as described with reference to stages 5 to 7 in the above example. Since the speed of the data transmissions is proportional to the speed of the vehicle, this mode of operation provides a major safety improvement over known tyre monitoring apparatus, in that the information is transmitted and updated regularly, depending on the speed of the vehicle. This has particular advantage in that a catastrophic failure of a tyre is more likely to occur, possibly with greater consequences, at high vehicle speed. The unit 10 is more regularly updated at high vehicle speeds than at lower speeds, thereby improving vehicle safety by warning the driver of any deflation of the vehicle tyres, for example. A further embodiment of power/sensor or telemetry unit is indicated at 100 in FIGS. 6 to 11, which corresponds substantially to the unit 10 described above. As shown in FIG. 6, the unit 100 includes a housing 112, which consists of a base portion 116 and a cap 128 mounted on the base portion 116. The housing 112 is removably mounted on a resilient base or footing 151 made of a rubber or any other suitable material. A pair of resilient clip arms 153 are pivotably provided on the footing 151, for snap-fitting engagement with formations 117 on the base portion 116 of the housing 112. The unit 100 can be simply removed from the footing 151 by unclipping the arms 153 from their engagement with the formations 117, for repair or installation in another tyre using a new footing 151, for example. The footing 151 is adapted to be permanently secured to an internal surface 159 of a tyre, as shown in FIGS. 10 and 11, and can be disposed of with the tyre after use. Two air channels 155 are provided in the footing 151, which have the dual function of allowing air movement about the unit 100, in use, and providing a footing of sufficient flexibility to aid protection and shock absorption for the internal components of the unit 100, whilst propagating the flexure of the tyre during rotation to the internal components of the unit 100. The footing 151 is generally elliptical and has a greater surface area than the base portion 116 of the housing 112. The shape and size of the footing 151 is designed to spread the load of the unit 100 on a tyre, to reduce adverse tyre wear in the region of the unit 100, that may otherwise be expected when providing a localised mass on the inside of a tyre, the mass of the unit 100 being in the region of between 30-50 grams. Referring specifically to FIGS. 7 to 9, the internal configuration of the housing 112 and the internal components of the unit 100 will now be described. The unit 100 includes a piezoelectric element 114 mounted on a brass supporting disc 115, substantially as described with reference to FIGS. 1 to 4. The base portion 116 of the housing 112 defines a compartment 118 formed by a base wall 120 and a peripheral wall 121. Recesses 122 are formed in the peripheral wall 121, for supporting a part of the periphery of the brass disc 115. When supported on the base portion 116, the central portion of the brass disc 115 is spaced apart from the base wall 120. In this embodiment, tabs 123 are provided which extend over a portion of the recesses 122, for engagement with the periphery of the brass disc 115, for retaining the brass disc 115, and thereby the piezoelectric element 114, on the base portion 116. The unit 100 includes a one-piece moulded actuator 136 defining a chamber 137, which is movably mounted in the housing 112. A printed circuit board or PCB (not shown), corresponding to the PCB 32 described with reference to the embodiment of FIGS. 1 to 4 is mounted in the chamber 137. The PCB is in electrical communication with the piezoceramic disc 114 via wires (not shown), which pass through an aperture 139 in the floor of the chamber 137. The PCB is securely located on the actuator 136 by a potting compound (not shown), which protects the PCB during installation or transit of the unit 100, as well as from the harsh environment within a rotating pneumatic tyre in use. An elongate projection or nose 144 is formed on the underside of the actuator 136, as can be seen in FIG. 8. In a normal rest position in the housing 112, the nose 144 is in contact with the piezoceramic disc 114, as can be seen in FIG. 9. In the rest position, the underside of the actuator 136 is spaced from an internal surface 141 of the base portion 116 by a distance of approximately 0.3 mm. In use, the piezoelectric element 114 is deflected in the direction of the base wall 120 under action of the actuating mass, and it will be appreciated, therefore, that the maximum deflection is limited to approximately 0.3 mm, as the periphery of the actuator 136 comes into contact with the internal surface 141. This maximum deflection is limited to protect the piezoelectric element 114 from excessive bending, and may be any suitable distance, for example between 0.2 and 0.5 mm. It will be appreciated that the components of the PCB and potting compound form part of an actuating mass for excitation of the piezoelectric element, with the actuator 136. The housing 112 is injection moulded from plastics and is adapted to withstand the harsh environment within a pneumatic vehicle tyre. The piezoceramic disc 114, and actuator 136 and control circuitry form are thus part of a power generator. The unit 100 operates substantially in the same way as the unit 10, as described above therefore operation of the unit 100 is not described in significant detail. In summary, it will be appreciated that the units 10, 100 each serve as a telemetry unit, which is capable of measuring and transmitting data relevant to tyre conditions local to the unit. The concept of mounting an in-tyre telemetry unit to the inner surface of a tyre by means of a sacrificial footing 151 which can be permanently bonded to the tyre is not limited to the application with units having a piezoelectric power generator as described above. The footing can be used with any suitable telemetry unit. Accordingly, the applicant may claim independent patent protection to this concept.
20050330
20070501
20051229
99512.0
0
WALK, SAMUEL J
POWER CONSUMPTION PROTOCOL
SMALL
0
ACCEPTED
2,005
10,529,805
ACCEPTED
Portable X-Ray Device
Portable x-ray devices and methods for using such devices are described. The devices have an x-ray tube powered by an integrated power system. The x-ray tube is shielded with a low-density insulating material containing a high-Z substance. The devices can also have an integrated display component. With these components, the size and weight of the x-ray devices can be reduced, and the portability of the devices enhanced. Thus, the portable x-ray devices are especially useful for applications where portability is an important feature such as in field work, remote operations, and mobile operations such nursing homes, home healthcare, teaching classrooms. This portability feature can be particularly useful in multi-suite medical and dental offices where a single x-ray device can be used in multiple offices instead of single using an x-ray device in each office.
1. A portable x-ray device, comprising: an x-ray source; and an integrated power system; wherein the x-ray device has a high current load. 2. The device of claim 1, wherein power system comprises a plurality of low voltage power supplies. 3. The device of claim 1, wherein each power supply provides a power ranging from about 20 to about 50 kV. 4. The device of claim 2, wherein the power system provides a continuous high voltage DC power. 5. The device of claim 1, further comprises an integrated display means. 6. The device of claim 1, wherein the x-ray source is shielded with a low-density insulating material. 7. The device of claim 6, wherein the low-density insulating material comprises silicone or epoxy. 8. The device in claim 6, wherein the shielding further comprises a high-Z substance. 9. The device in claim 8, wherein the high-Z substance is compounds of Pb, W, Ta, Bi, Ba, or combinations thereof. 10. A handheld x-ray device, comprising: an x-ray source shielded with a low-density insulating material; and an integrated power system; wherein the x-ray device has a high current load for radiographic imaging. 11. The device of claim 10, wherein the power system comprises a plurality of low voltage power supplies with each power supply providing a power ranging from about 20 to about 50 kV 12. The device of claim 10, wherein the low-density insulating material comprises silicone or epoxy. 13. The device in claim 12, wherein the shielding further comprises a high-Z substance like compounds of Pb, W, Ta, Bi, Ba, or combinations thereof. 14. A system for x-ray analysis, the system containing a portable x-ray device with a high current load and containing an x-ray source and an integrated power system. 15. The system of claim 14, wherein the power system comprises a plurality of low voltage power supplies with each power supply providing a power ranging from about 20 to about 50 kV. 16. The system of claim 14, wherein x-ray source is shielded with a low-density insulating material containing a high-Z substance. 17. A method for making a portable x-ray device with a high current load, the method comprising: providing an x-ray source; and providing an integrated power system. 18. The method of claim 17, including: providing the power system with a plurality of low voltage power supplies with each power supply providing a power ranging from about 20 to about 50 kV; and providing the x-ray source with a shielding comprising a low-density insulating material containing a high-Z substance. 19. A method for analysis, comprising: providing a portable x-ray device with a high current load and containing an x-ray source and an integrated power system: and actuating the x-ray source using the integrated power system. 20. The method of claim 19, including: providing the power system with a plurality of low voltage power supplies with each power supply providing a power ranging from about 20 to about 50 kV; and providing the x-ray source with a shielding comprising a low-density insulating material containing a high-Z substance. 21. A method for dental imaging, comprising: providing a portable x-ray device with a high current load for radiographic imaging, the device containing an x-ray source and an integrated power system; and actuating the x-ray source using the integrated power system so that x-rays impinge in the teeth of a patient. 22. The method of claim 21, including: providing the power system with a plurality of low voltage power supplies with each power supply providing a power ranging from about 20 to about 50 kV; and providing the x-ray source with a shielding comprising a low-density insulating material containing a high-Z substance. 23. A portable x-ray camera, comprising: an x-ray source; and an integrated power system; wherein the x-ray device has a high current load for radiographic imaging. 24. The device of claim 23, wherein the power system contains a plurality of low voltage power supplies with each power supply providing a power ranging from about 20 to about 50 kV, and the x-ray source contains a shielding comprising a low-density insulating material containing a high-Z substance.
CROSS-REFERENCE TO RELATED APPLICATION This application claims priority of U.S. Patent Application Ser. No. 60/546,575, filed on Feb. 20, 2004, the entire disclosure of which is incorporated herein by reference. FIELD OF THE INVENTION The invention generally relates to x-ray devices and methods for using the same. More particularly, the invention relates to x-ray tubes used in x-rays devices. Even more particularly, the invention relates to portable x-ray devices that contain an integrated power system, methods for using such portable x-ray devices, and systems containing such portable x-ray devices. BACKGROUND OF THE INVENTION Typical x-ray tubes and x-ray devices (device containing x-ray tubes) have been known and used for some time. Unfortunately, they are usually bulky and are powered by heavy, high-voltage power supplies that restrict mobility. As well, they are often difficult and time-consuming to use. In many instances, a sample for analysis must be sent to an off-site laboratory for analysis by the x-ray device. These limitations can be very inconvenient for many popular uses of x-ray devices containing them. Such uses include x-ray fluorescence (XRF) of soil, water, metals, ores, well bores, etc., as well as diffraction and plating thickness measurements. Typical x-ray imaging applications require the sample to be imaged to be brought to the x-ray device. These limitations have led to an increased interest in making x-ray devices portable. See, for example, U.S. Pat. Nos. 6,661,876, 6,459,767, 6,038,287, and 6,205,200; U.S. Published Patent Applications 2003/0048877, 2003/0002627, and 2003/0142788; and European Patent Nos. EP0946082, EP0524064, EP0247758, EP0784965, and EP0488991; the entire disclosures of which are incorporated herein by reference. Many of these existing designs increase the portability of x-ray devices. At the same time, however, these designs are limited for several reasons. First, most of the designs are not truly portable since they have an external power source (i.e., require utility-supplied line voltage). Second, while some of the portable designs, especially the XRF systems, have internal or “integrated” power supplies, they don't have the high x-ray tube current load that is often necessary for x-ray imaging. For example, energy-dispersive XRF typically requires x-ray beam currents of less than 1 milliampere while x-ray imaging typically requires greater than about 2 milliamperes. Third, high-quality imaging displays for displaying the results of the x-ray analysis are not present. Finally, the radiation shielding for the x-ray tubes usually comprises lead, which is quite heavy and limits the portability of the device. A further limitation on design of the increased portability is the image collection and display components. Many of the portable designs have the image collection component and the image display component external to the chassis or housing containing the x-ray tube. Such a configuration, however, increases the size of the device and the number of system components, and consequently decreases the portability of the device. SUMMARY OF THE INVENTION The invention relates to portable x-ray devices and methods for using such devices. The devices have an x-ray tube powered by an integrated power system. The x-ray tube is shielded with a low-density insulating material containing a high-Z substance. The devices can also have an integrated display component. With these components, the size and weight of the x-ray devices can be reduced, and the portability of the devices enhanced. Thus, the portable x-ray devices are especially useful for applications where portability is an important feature such as in field work, remote operations, and mobile operations such nursing homes, home healthcare, teaching classrooms. This portability feature can be particularly useful in multi-suite medical and dental offices where a single x-ray device can be used in multiple offices instead of single using an x-ray device in each office. BRIEF DESCRIPTION OF THE DRAWINGS The following description of the invention can be understood in light of the Figures, in which: FIGS. 1-2 depict the x-ray device in one aspect of the invention; FIG. 3 depicts the x-ray device in another aspect of the invention; FIG. 4 depicts the x-ray device in another aspect of the invention; FIG. 5 depicts the x-ray tube and power supply of the x-ray device in one aspect of the invention; FIGS. 6-7 depict the power source of the x-ray device and method for connecting the power source to the x-ray device in one aspect of the invention; FIG. 8 depicts the x-ray tube of the x-ray device in one aspect of the invention; and FIG. 9 depicts a conventional x-ray tube in a conventional configuration. FIGS. 1-9 illustrate specific aspects of the invention and are a part of the specification. In the Figures, the thickness and configuration of components may be exaggerated for clarity. The same reference numerals in different drawings represent the same component. Together with the following description, the Figures demonstrate and explain the principles of the invention. DETAILED DESCRIPTION OF THE INVENTION The following description provides specific details in order to provide a thorough understanding of the invention. The skilled artisan, however, would understand that the invention can be practiced without employing these specific details. Indeed, the invention can be practiced by modifying the illustrated method and resulting product and can be used in conjunction with apparatus and techniques conventionally used in the industry. While the invention is described for use in x-ray imaging for dental purposes, it could be used in other medical applications such as medical imaging, veterinary, and bone densitometry. As well, it could be used for non-dental and non-medical applications such as industrial imaging, metal fatigue inspections, weld-inspection for cracks/voids and pipes, for security inspections allowing random inspection of parcels and carry-on baggage, and the like. As described above, the invention includes a portable x-ray device that is used primarily for remote and/or applications, including in multi-suite locations. The x-ray device can be designed to be either handheld or temporarily fixed to a given location, such as a tripod-mount operation. As well, the invention could be mounted on any other semi-stable apparatus, such as an articulating arm or C-arm as commonly used in radiology applications and described in the publications mentioned above. The x-ray device is portable in that it can be transported by hand carrying it from one location to a second location without support by any mechanical apparatus. Most importantly, because of its integrated power system, the location of use can be independent of any external fixed power source, such as utility-supplied AC voltage commonly available in the home or office. This independence from external power source is a defining feature of the portable x-ray device described above. As shown in FIGS. 1-2, the x-ray device 10 of the invention contains a housing or chassis 20 to contain all the internal components of the device. The housing 20 encloses an x-ray tube 30 for producing the x-rays. The x-ray device 10 contains a power system (including power source 40) to provide power for the device 10 and means for sensing the x-rays, such as film, CCD sensors, or imaging plates (not shown). The x-ray device 10 also contains means for displaying the results of the analysis such as an integrated image display screen 60 (shown in FIG. 4); control means such as controller 70; and radiation shielding 80 to shield the operator of the device from backscattered radiation from the sample. The x-ray device 10 also contains any other components known in the art for efficient operation (such as x-ray collimator 32), including those components described in the documents mentioned above. The x-ray device 10 contains a unique system for providing power to the x-ray device. The power system of the x-ray device comprises a power source 40, power supply 34, and conversion means. The power source 40 used in the x-ray device of the invention can be any known in the art that can supply the desired amount of power, yet fit within the space limitations of the x-ray device. In one aspect of the invention, the power source comprises a battery, such as a 14.4V NiCd battery pack. The power source can be recharged by any suitable means, such as by connection to an appropriate voltage when using batteries that are re-chargeable. In one aspect of the invention, the power source 40 is removable from the remainder of the x-ray device 10. In this aspect of the invention, the power source 40 comprises mechanical and electrical means for connecting the power source 40 to the x-ray device 10. The electrical and mechanical connection means can be any of those known in the art. As depicted in FIG. 6, the electrical connection means can comprise an extension member 41 with an electrical connector 42 contained in an upper portion thereof. The mechanical connection means comprises a release mechanism 43a. As shown in FIG. 7, the x-ray device 10 contains a locking mechanism 43b. To connect the power source 40 to the x-ray device 10, the power source 40 is gently pushed into the bottom of the handle 15 of the x-ray device 10. When completely connected, the electrical connector 42 connects with the internal electronics of the x-ray device 10. The locking mechanism 43b is automatically engaged to retain the power source 40 connected to the x-ray device 10 in this position. To remove the power source 40, the release mechanism 43a is actuated to unlock the locking mechanism 43b, and the power source 40 can be gently slid out from the handle 15. The power source 40 is electrically connected to the conversion means using any connection means known in the art, including those described in the publications above. The conversion means converts the initial voltage supplied by the power source 40 to a converted voltage that is provided to the power supply 34. The conversion means generally converts the 14.4V (or similar voltage) provided by the power source 40 to a voltage ranging from about 80 to about 200V. In one aspect of the invention, the initial voltage is converted to a converted voltage of about 100V. Any conversion means known in the art that operates in this manner can be used in the invention, including the power management boards 36. The conversion means is electrically connected to the power supply 34. The power supply 34 steps up the converted voltage (i.e., the 100V) provided by the conversion means to a voltage that can be used by the x-ray tube 30. The power produced by the power supply 34 and input into the x-ray tube 30 via connection 35 (shown in FIG. 8) depends on the power needed to operate the x-ray tube, and the maximum power available from the power source. Generally, the power provided by the power supply 34 to the x-ray tube 30 can range from about 20 to about 150 kV. Typically, this power provided by the power supply can range from about 40 kV to about 100 kV. In one aspect of the invention, the power provided by the power supply is provided by a plurality of individual power supplies. The number of individual power supplies used depends on the voltage needed for the x-ray tube, the space needed for the power supply 34, the total power available from the power source, and the number of electron-accelerating grids in the x-ray tube. In one aspect of the invention, the plurality of individual power supplies is two (as represented in FIG. 5 by 45, 46) where 45 supplies positive voltage to the anode and 46 supplies negative voltage to the cathode. The power provided by each individual power supply depends on the number of individual power supplies used, the maximum power available from the power source, and the heat-dissipating capability of the x-ray tube. Generally, the power supplied by each individual power supply is the total power needed to operate the x-ray tube divided by the number of individual power supplies. For example, the power provided by each individual power supply (when there are 2) can range from about 20 kV to about 50 kV. In one aspect of the invention, the power provided by each individual power supply (when there are 2) is about +35 kV and −35 kV. In this embodiment, the +35 kV is attached to the anode of the x-ray tube and the −35 kV is attached to the cathode of the x-ray tube. A filament transformer is included in the cathode power supply to provide current to the x-ray tube filament and generate an electron beam at the cathode of the tube. The total power produced by the power supply is the therefore sum of the individual anode power supply and the individual cathode power supply. When such individual low voltage power supplies are used, the x-ray tube 30 of the invention becomes more portable. Conventional x-ray tubes operate at much higher voltages in the range of 70 kV and higher. Because of these high voltages, and the need for the high voltage standoff, the conventional x-ray tube 300 is often encased in insulating oil 302 (or a similar material) within a liquid-tight case 306 as shown in FIG. 9. The oil 302 also has the advantage of dissipating the high temperatures that existed during operation. By splitting the needed operation voltage into 2 (or more) individual power supplies, the individual power supplies only need to provide (and also stand off) half of the higher voltage. With these lower voltages, the x-ray tube 30 of the invention can be encapsulated in materials other than high-density oil. These other materials need only insulate proportionately to the reduced voltage, i.e., these other materials need only insulate half as much as oil since the voltage produced is about half of that conventionally used. Any known material that can insulate in this manner can be used in the invention, including low-density materials like insulating gel, silicone rubber, epoxy, or combinations thereof. The insulating material is provided in a layer 33 that substantially encapsulates the x-ray tube 30 except for that portion of the tube where x-rays are actually emitted by the tube (i.e., into the x-ray collimator 32). The thickness of the layer of insulating material 33 need only be sufficient for the purpose indicated above. Generally, the thickness of the insulating material can range from about ¼ inch to about 1 inch. In one aspect of the invention, such as where silicone rubber is used, the thickness of the insulating material can range from about ⅓ inch to about ½ inch. In another aspect of the invention, the insulating material comprises a dual-layer around the x-ray tube with the first layer comprising one of the insulating materials and the second layer comprising another of the insulating materials. Eliminating the need to use the high-density oil provides a significant reduction in the weight of the unit. An added advantage is that there is no need for a liquid-tight case 306 to hold the liquid oil 302. Indeed, when a solid material is used such as silicone rubber, there is no need for any case, even though one can optionally be used. In one aspect of the invention by removing the case, and instead using silicon rubber that is conformal with the x-ray tube, the total volume of the insulating material is reduced significantly. As shown in FIG. 9, conventional x-ray tubes 300 also contain a shielding to absorb stray x-rays that are emitted from the x-ray tube. The shielding usually was made of lead and incorporated into the liquid-tight case. Lead was used because of its excellent x-ray absorption properties. But lead shielding is quite heavy and consequently limits the portability of the x-ray device. With the x-ray device of the invention, this lead shielding has been eliminated, thereby increasing the portability by reducing the need for an additional component in the x-ray device. Instead, the insulating material (i.e., silicone rubber) has dispersed within it a high-Z material. The high-Z material absorbs any stray x-rays that are emitted. Any high-Z material known in the art can be used, including compounds of Pb, W, Ta, Bi, Ba, or combinations thereof. The concentration of the high-Z material in the insulating material need only be sufficient to absorb the expected amount of stray x-rays. Typically, the concentration of the high-Z material can range from about 30 wt % to about 60 wt %. In one aspect of the invention, the concentration of the high-Z material can range from about 45 wt % to about 50 wt %. In one aspect of the invention, the insulating material also contains substances that are known to optimize the thermal conductivity, such as metallic particles, or inclusions of high-thermal-conductivity materials. The x-ray device of the invention optionally contains shielding 80 for the operator. When in operation, x-rays can often backscatter from the object being analyzed, such as the teeth of a patient, and strike the operator. The shielding 80 is used to protect the operator from such aberrant radiation. In one aspect of the invention, the shielding used is a Pb-filled acrylic radiation scatter shield. The x-ray device of the invention also contains control means for operating the x-ray device. Any controls known in the art can be used in the control means of the invention. Examples of such controls include up and down arrow membrane switches with an LED readout to adjust exposure time. Indicators can include “power on,” “start,” and “x-rays on” LEDs. In the aspect of the invention illustrated in FIG. 1, the control means (controller 70) is integrated into the housing 20 of the device. In another aspect of the invention, the control means (such as controller 76) is external to the device and is connected to remainder of the device using any known electronic connection, such as cable 72 (See FIG. 3). In either instance, the control means also contains a trigger 74 that is incorporated into the handle 15 and used by the operator to begin (and conclude) the x-ray exposure. The invention also contains means for sensing the x-rays. Any sensing means known in the art that is sensitive to x-ray radiation can be used in the invention. Examples of such sensing means include x-rays receptors, x-ray film, CCD sensors, CMOS sensors, TFT sensors, imaging plates, and image intensifiers. In one aspect of the invention, a CCD sensor is used as the sensing means in the x-ray devices of the invention. The x-ray device may also contain means for displaying the x-rays detected by the detecting means. Any display means that displays the detected x-rays in a manner that can be understood by the operator of the device can be used for the invention. Examples of displaying means that can be used include film, imaging plates, and digital image displays such as cathode ray tubes (CRT) or liquid crystal display (LCD) screens. In one aspect of the invention, the display means can be used as a densitometer for the x-ray absorption. In one aspect of the invention, the display means is integrated into the housing of the x-ray device. Such integration, however, will limit the size of the display means since too large a display means will detract from the portability of the device. In this aspect of the invention, any small display means with sufficient resolution can be used in the invention, including liquid crystal display (LCD) screens 60. In another aspect of the invention, the display means are located external to the x-ray device. In this aspect, a separate imaging plate (such as a CMOS or TFT plate) for larger features (such as medical or veterinary imaging) can be used. The separate imaging plate can be connected to the remainder of the x-ray device as known in the art. In one aspect of the invention, the x-ray device 10 can contain both an integrated sensing means (such as a CCD sensor) and an integrated display means (such as the LCD screen 60) to minimize the size and optimize the portability of the x-ray device. These two components can be used to temporarily store images in the x-ray device. Once the storage capacity for these temporary images has been reached, an optional wired or wireless connection can then provide seamless update to an external electronic system, such as a permanent database or a personal computer as known in the art. The wired or wireless connection can be made as known in the art. In one aspect of the invention, this connection is wireless since it provides true portability and freedom from line voltage. The x-ray device of the invention can be made in any manner that provides the device with the components in this configuration described above. The housing, x-ray tube, sensing means, display means, control means, radiation shielding, power source, and conversion means can be provided as known in the art and as described in the publications disclosed above. The insulating material can be made by mixing the needed amount of high-Z substance (such as an oxide of a heavy metal) into the insulating material (such as the silicone potting material when the A and B parts of the silicone are mixed together). The resulting combination is thoroughly mixed, and then uniformly provided around the x-ray tube, such as by pouring into in an encapsulating mold. In this way, the insulating material containing the high-Z substance is uniformly distributed throughout the layer surrounding the x-ray tube. When making the power supply, the process will be illustrated with two individual power supplies. Each power supply is configured so that the grounded ends of each power supply are located near the center of the x-ray tube. The positive voltage from one supply is provided to one side of the x-ray tube, and the negative voltage from the other supply is provided to other end of the x-ray tube. In this configuration, the maximum voltage (i.e., the sum of both) can be isolated from each individual power supply along the full length of the x-ray tube and the isolation from ground only needs to be ½ of the total voltage. Consequently, the insulating paths need only be ½ the length. The x-ray device can be operated in any manner that provides a radiographic image. In one aspect of the invention, the x-ray device of the invention can be operated by first actuating the appropriate button on the control means to turn on the device. After setting the exposure time, an “enable” button is pressed. This “enable” acts as a safety switch, preventing initiation of the x-ray exposure until the operator has positioned the instrument in the correct location and prepares to pull the trigger. Then, on pulling the trigger (or pressing the “start” button) the high voltage (HV) supplied by the power supply 34 will increase up to about 70 kV (i.e., one power supply at about +35 kV and the other at about −35 kV). When this HV level is reached, the filament will energize at its full setpoint to supply the needed emission current to the x-ray tube. The filament will remain at this level for the time designated by the operator (i.e., by using the controls). The start indicator in the LED of the control means can illuminate upon pressing the trigger. The “x-rays on” indicator in the LED of the control means can illuminate during the entire time that the emission current for the x-ray tube is present. Additionally, an audible signal can be used to indicate that the x-rays are being emitted. During exposure after pressing the trigger 74, x-rays are emitted from the x-ray tube 30 and strike the object being analyzed, i.e., the teeth of a patient when the x-ray device is being used for dental purposes. To meet x-ray equipment standards, the button or trigger 74 must be held down during the full length of the exposure. During exposure, the x-rays are used for analysis of the object as known in the art by using the sensing means. The operator can then view the results of the analysis in the display means and optionally download the images to an external storage device. Following the exposure of a patient with the x-rays, the filament will turn off (along with the “x-rays on” indicator) and the HV will ramp down. Once the HV is off, the start indicator in the LED of the controller will turn off and the x-ray device will return to a standby condition. In one aspect of the invention, the operator may need to re-enter the exposure time before starting the next exposure. This re-entering process can be accomplished with a “ready” indicator in the LED of the control means after the exposure time has been set. The x-ray device of the invention can be modified to contain additional optional features, including any of those described in the publications mentioned above. For example, to increase battery life, the x-ray device can contain an automatic shut off feature that shuts the device off after 2 minutes without an x-ray exposure. Another feature that can be added, for example, is to manufacture the housing or chassis 20 of a high-impact material (such as ABS or a plastic alloy of ABS and other materials, designed for high-impact resistance) to reduce the risk of damage. The x-ray device of the invention can also be made as part of a system for x-ray analysis. The system could contain any components that aid in the operation of the x-ray device or the x-ray analysis, including those mentioned above such as an external means for storing the radiographic images. As well, the system could also include a hard-side carrying case, an “industrial strength” tripod, a 3 meter long umbilical cord to a remote control panel 76, or the like. The system could also contain a back-up power source 40. Finally, the system could also contain any of those components described in the publications mentioned above. Using the x-ray device of the invention provides several improvements over conventional devices. First, the x-ray device of the invention contains an integrated power system. The power system can be battery-operated, yet still provide a continuous high voltage, rather than Marx generators (pulsed) or capacitively-pulsed systems. Thus, the x-ray device can maintain a continuous DC high voltage supply and can generate a high voltage for a few seconds with each high current discharge. The high storage capacity provided by the batteries allows hundreds of discharges, anywhere from about 10 to about 20 amps for a few seconds. For most applications, including for dental purposes, the x-ray devices of the invention need less than a second for each exposure. Most conventional x-ray devices, however, have external power supplies. Those conventional x-ray devices that do have integrated power supplies, still don't have the high current load described above. Thus, the power system of the invention can provide a constant radiation output and improved image quality while reducing the x-ray dosage to which the object (i.e., patient) is exposed. Another improvement in the x-ray devices of the invention are in the shielding for the x-ray tubes. Conventional x-ray tubes are shielded with a liquid oil encasement and lead shielding, both of which are bulky and heavy. Both of these components are eliminated in the x-ray tube shielding of the invention. Instead, the shielding of the invention contains a low-density insulating material that contains high-Z, substances. This configuration leads to reduced material count and generally lower weight. In addition to any previously indicated variation, numerous other modifications and alternative arrangements may be devised by those skilled in the art without departing from the spirit and scope of the invention and appended claims are intended to cover such modifications and arrangements. Thus, while the invention has been described above with particularity and detail in connection with what is presently deemed to be the most practical and preferred aspects of the invention, it will be apparent to those of ordinary skill in the art that numerous modifications, including but not limited to, form, function, manner of operation and use may be made without departing from the principles and concepts set forth herein.
<SOH> BACKGROUND OF THE INVENTION <EOH>Typical x-ray tubes and x-ray devices (device containing x-ray tubes) have been known and used for some time. Unfortunately, they are usually bulky and are powered by heavy, high-voltage power supplies that restrict mobility. As well, they are often difficult and time-consuming to use. In many instances, a sample for analysis must be sent to an off-site laboratory for analysis by the x-ray device. These limitations can be very inconvenient for many popular uses of x-ray devices containing them. Such uses include x-ray fluorescence (XRF) of soil, water, metals, ores, well bores, etc., as well as diffraction and plating thickness measurements. Typical x-ray imaging applications require the sample to be imaged to be brought to the x-ray device. These limitations have led to an increased interest in making x-ray devices portable. See, for example, U.S. Pat. Nos. 6,661,876, 6,459,767, 6,038,287, and 6,205,200; U.S. Published Patent Applications 2003/0048877, 2003/0002627, and 2003/0142788; and European Patent Nos. EP0946082, EP0524064, EP0247758, EP0784965, and EP0488991; the entire disclosures of which are incorporated herein by reference. Many of these existing designs increase the portability of x-ray devices. At the same time, however, these designs are limited for several reasons. First, most of the designs are not truly portable since they have an external power source (i.e., require utility-supplied line voltage). Second, while some of the portable designs, especially the XRF systems, have internal or “integrated” power supplies, they don't have the high x-ray tube current load that is often necessary for x-ray imaging. For example, energy-dispersive XRF typically requires x-ray beam currents of less than 1 milliampere while x-ray imaging typically requires greater than about 2 milliamperes. Third, high-quality imaging displays for displaying the results of the x-ray analysis are not present. Finally, the radiation shielding for the x-ray tubes usually comprises lead, which is quite heavy and limits the portability of the device. A further limitation on design of the increased portability is the image collection and display components. Many of the portable designs have the image collection component and the image display component external to the chassis or housing containing the x-ray tube. Such a configuration, however, increases the size of the device and the number of system components, and consequently decreases the portability of the device.
<SOH> SUMMARY OF THE INVENTION <EOH>The invention relates to portable x-ray devices and methods for using such devices. The devices have an x-ray tube powered by an integrated power system. The x-ray tube is shielded with a low-density insulating material containing a high-Z substance. The devices can also have an integrated display component. With these components, the size and weight of the x-ray devices can be reduced, and the portability of the devices enhanced. Thus, the portable x-ray devices are especially useful for applications where portability is an important feature such as in field work, remote operations, and mobile operations such nursing homes, home healthcare, teaching classrooms. This portability feature can be particularly useful in multi-suite medical and dental offices where a single x-ray device can be used in multiple offices instead of single using an x-ray device in each office.
20050801
20090224
20071122
68672.0
H05G110
2
KIKNADZE, IRAKLI
PORTABLE X-RAY DEVICE
SMALL
0
ACCEPTED
H05G
2,005
10,529,806
ACCEPTED
Digital x-ray camera
Portable x-ray devices and methods for using such devices are described. The devices have an x-ray tube powered by an integrated power system. The x-ray tube is shielded with a low-density insulating material containing a high-Z substance. The devices can also have an integrated display component. With these components, the size and weight of the x-ray devices can be reduced and the portability of the devices enhanced. The x-ray devices also have an x-ray detecting means that is not structurally attached to the device and therefore is free standing. Consequently, the x-ray devices can also be used as a digital x-ray camera. The portable x-ray devices are especially useful for applications where portability is an important feature such as in field work, remote operations, and mobile operations such as nursing homes, home healthcare, or teaching classrooms. This portability feature can be particularly useful in multi-suite medical and dental offices where a single x-ray device can be used as a digital x-ray camera in multiple offices instead of requiring a separate device in every office.
1. A portable x-ray device, comprising: a housing containing an x-ray source and an integrated power system; and detecting means structurally unattached to the housing. 2. The device of claim 1, wherein the detecting means is electrically coupled to the x-ray device. 3. The device of claim 1, wherein the detecting means electrically communicates with the x-ray device using wireless technology. 4. The device of claim 1, wherein the device comprised integrated display means. 5. The device of claim 4, wherein the display means comprises an LCD screen. 6. The device of claim 1, wherein the housing is shaped substantially in the form of a camera. 7. The device of claim 1, wherein the power system comprises a plurality of low voltage power supplies with each power supply providing a power ranging from about 20 to about 50 kV. 8. The device of claim 1, wherein the x-ray source is shielded with a low-density insulating material containing a high-Z substance. 9. A portable x-ray device, comprising: a housing containing an x-ray source, an integrated power system, and integrated display means; and detecting means structurally unattached to the housing. 10. The device of claim 9, wherein the housing is shaped substantially in the form of a camera. 11. The device of claim 9, wherein the power system comprises a plurality of low voltage power supplies with each power supply providing a power ranging from about 20 to about 50 kV. 12. The device of claim 9, wherein the x-ray source is shielded with a low-density insulating material containing a high-Z substance. 13. A digital x-ray camera, comprising: housing containing an x-ray source, an integrated power system, and integrated display means; and detecting means structurally unattached to the housing. 14. The device of claim 13, wherein the power system comprises a plurality of low voltage power supplies with each power supply providing a power ranging from about 20 to about 50 kV. 15. The device of claim 13, wherein the x-ray source is shielded with a low-density insulating material containing a high-Z substance. 16. A system for x-ray analysis, the system containing a digital x-ray camera with a housing containing an x-ray source and an integrated power system, and detecting means structurally unattached to the housing. 17. The system of claim 16, wherein the power system comprises a plurality of low voltage power supplies with each power supply providing a power ranging from about 20 to about 50 kV. 18. The system of claim 16, wherein x-ray source is shielded with a low-density insulating material containing a high-Z substance. 19. A method for making a portable x-ray device, the method comprising: providing a housing with an x-ray source and an integrated power system; and providing detecting means structurally unattached to the housing. 20. The method of claim 19, including: providing the power system with a plurality of low voltage power supplies with each power supply providing a power ranging from about 20 to about 50 kV; and providing the x-ray source with a shielding comprising a low-density insulating material containing a high-Z substance. 21. A method for analysis, comprising: providing a digital x-ray camera with a housing containing an x-ray source and an integrated power system, with detecting means structurally unattached to the housing; and powering the x-ray source using the integrated power system. 22. The method of claim 21, including: providing the power system with a plurality of low voltage power supplies with each power supply providing a power ranging from about 20 to about 50 kV; and providing the x-ray source with a shielding comprising a low-density insulating material containing a high-Z substance. 23. A method for dental imaging, comprising: providing a digital x-ray camera with a housing containing an x-ray source and an integrated power system, with detecting means structurally unattached to the housing; and powering the x-ray source using the integrated power system so that x-rays impinge in the teeth of a patient. 24. The method of claim 23, including: providing the power system with a plurality of low voltage power supplies with each power supply providing a power ranging from about 20 to about 50 kV; and providing the x-ray source with a shielding comprising a low-density insulating material containing a high-Z substance. 25. The device of claim 1, further comprising a controllable display means. 26. The device of claim 25, wherein the controllable display means is integrated into the housing. 27. The device of claim 25, wherein the controllable display means is external to the x-ray device. 28. The device of claim 25, wherein the controllable display means comprises a portable electronic device. 29. The device of claim 28, wherein the portable electronic device enhances the image analysis of the x-ray device. 30. A portable x-ray device, comprising: a housing containing an x-ray source; controllable display means; and detecting means structurally unattached to the housing.
CROSS-REFERENCE TO RELATED APPLICATION This application claims priority of U.S. Patent Application Ser. No. 60/546,575, filed on Feb. 20, 2004, the entire disclosure of which is incorporated herein by reference. FIELD OF THE INVENTION The invention generally relates to x-ray devices and methods for using the same. More particularly, the invention relates to portable x-ray devices that contain an unattached x-ray detector, methods for using such portable x-ray devices as a digital x-ray camera, and systems containing such portable x-ray devices. BACKGROUND OF THE INVENTION Typical x-ray tubes and x-ray devices (device containing x-ray tubes) have been known and used for some time. Unfortunately, they are usually bulky and are powered by heavy, high-voltage power supplies that restrict mobility. As well, they are often difficult and time-consuming to use. In many instances, a sample for analysis must be sent to an off-site laboratory for analysis by the x-ray device. These limitations can be very inconvenient for many popular uses of x-ray devices containing them. Such uses include x-ray fluorescence (XRF) of soil, water, metals, ores, well bores, etc., as well as diffraction and plating thickness measurements. Typical x-ray imaging applications require the sample to be imaged to be brought to the x-ray device. These limitations have led to an increased interest in making x-ray devices portable. See, for example, U.S. Pat. Nos. 6,661,876, 6,459,767, 6,038,287, and 6,205,200; U.S. Published Patent Applications 2003/0048877, 2003/0002627, and 2003/0142788; and European Patent Nos. EP0946082, EP0524064, EP0247758, EP0784965, and EP0488991; the entire disclosures of which are incorporated herein by reference. Many of these existing designs increase the portability of x-ray devices. At the same time, however, these designs are limited for several reasons. First, most of the designs are not truly portable since they have an external power source (i.e., require utility-supplied line voltage). Second, while some of the portable designs, especially the XRF systems, have internal or “integrated” power supplies, they don't have the high x-ray tube current load that is often necessary for x-ray imaging. For example, energy-dispersive XRF typically requires x-ray beam currents of less than 1 milliampere while x-ray imaging typically requires greater than about 2 milliamperes. Finally, the radiation shielding for the x-ray tubes usually comprises lead, which is quite heavy and limits the portability of the device. A further limitation on design of the increased portability is the image display components. High-quality imaging displays for displaying the results of the x-ray analysis are difficult to integrate into the design of the housing of the portable x-ray device. Consequently, many of the portable designs have the image display component external to the chassis or housing containing the x-ray tube. SUMMARY OF THE INVENTION The invention relates to portable x-ray devices and methods for using such devices. The x-ray devices have an x-ray tube powered by an integrated power system. The x-ray tube is shielded with a low-density insulating material containing a high-Z substance. The x-ray devices can also have an integrated display component. With these components, the size and weight of the x-ray devices can be reduced and the portability of the devices enhanced. The x-ray devices can also have detecting means that is not structurally attached to the device and therefore is free standing. Consequently, the x-ray devices can also be used as a digital x-ray camera. The portable x-ray devices are especially useful for applications where portability is an important feature such as in field work, remote operations, and mobile operations such as nursing homes, home healthcare, or teaching classrooms. This portability feature can be particularly useful in multi-suite medical and dental offices where a single x-ray device can be used as a digital x-ray camera in multiple offices instead of requiring a separate device in every office. BRIEF DESCRIPTION OF THE DRAWINGS The following description of the invention can be understood in light of the Figures, in which: FIGS. 1-2 depict the x-ray device in one aspect of the invention; FIG. 3 depicts the x-ray device in another aspect of the invention; FIG. 4 depicts the x-ray device in another aspect of the invention; FIG. 5 depicts the x-ray tube and power supply of the x-ray device in one aspect of the invention; FIGS. 6-7 depict the power source of the x-ray device and method for connecting the power source to the x-ray device in one aspect of the invention; FIG. 8 depicts the x-ray tube of the x-ray device in one aspect of the invention; FIG. 9 depicts a conventional x-ray tube in a conventional configuration; FIGS. 10-12 depicts the x-ray device in one aspect of the invention; and FIGS. 13-17 depicts the x-ray in another aspect of the invention. FIGS. 1-17 illustrate specific aspects of the invention and are a part of the specification. In the Figures, the thickness and configuration of components may be exaggerated for clarity. The same reference numerals in different drawings represent the same component. Together with the following description, the Figures demonstrate and explain the principles of the invention. DETAILED DESCRIPTION OF THE INVENTION The following description provides specific details in order to provide a thorough understanding of the invention. The skilled artisan, however, would understand that the invention can be practiced without employing these specific details. Indeed, the invention can be practiced by modifying the illustrated method and resulting product and can be used in conjunction with apparatus and techniques conventionally used in the industry. While the invention is described for use in x-ray imaging for dental purposes, it could be used in other medical applications such as medical imaging, veterinary, and bone densitometry. As well, it could be used for non-dental and non-medical applications such as industrial imaging, metal fatigue inspections, weld-inspection for cracks/voids and pipes, for security inspections allowing random inspection of parcels and carry-on baggage, and the like. As described above, the invention includes a portable x-ray device that is used primarily for remote and/or office applications, including in multi-suite office locations. The x-ray device can be designed to be either handheld or temporarily fixed to a given location, such as a tripod-mount operation. As well, the invention could be mounted on any other semi-stable apparatus, such as an articulating arm or C-arm as commonly used in radiology applications and described in the publications mentioned above. The x-ray device of the invention is portable in that it can be transported by hand carrying it from one location to a second location without support by any mechanical apparatus. Because it uses an integrated power system, the location of its use can be independent of any external fixed power source, such as utility-supplied AC voltage often required in the home or office. As well, the x-ray device contains detecting means that is not structurally attached to the device and therefore is free standing. This independence from an external power source and free-standing detecting means are particularly useful features of the x-ray devices of the invention. In the aspect of the invention shown in FIGS. 1-2, the x-ray device 10 of the invention contains a housing or chassis 20 to contain all the internal components of the device. The housing 20 encloses an x-ray tube 30 for producing the x-rays. The x-ray device 10 contains a power system (including power source 40) to provide power for the device 10 and means for detecting the x-rays, such as film, CCD sensors, or imaging plates (not shown). The x-ray device 10 also contains means for displaying the results of the analysis such as an integrated image display screen 60 (shown in FIG. 4); control means such as controller 70; and radiation shielding 80 to shield the operator of the device from backscattered radiation from the sample. The x-ray device 10 also contains any other components known in the art for efficient operation (such as x-ray collimator 32), including those components described in the documents mentioned above. The x-ray device 10 contains a unique system for providing power to the x-ray device. The power system of the x-ray device comprises a power source 40, power supply 34, and conversion means. The power source 40 used in the x-ray device of the invention can be any known in the art that can supply the desired amount of power, yet fit within the space limitations of the x-ray device. In one aspect of the invention, the power source comprises a battery, such as a 14.4V NiCd battery pack. The power source can be recharged by any suitable means, such as by connection to an appropriate voltage when using batteries that are re-chargeable. In one aspect of the invention, the power source 40 is removable from the remainder of the x-ray device 10. In this aspect of the invention, the power source 40 comprises mechanical and electrical means for connecting the power source 40 to the x-ray device 10. The electrical and mechanical connection means can be any of those known in the art. As depicted in FIG. 6, the electrical connection means can comprise an extension member 41 with an electrical connector 42 contained in an upper portion thereof. The mechanical connection means comprises a release mechanism 43a. As shown in FIG. 7, the x-ray device 10 contains a locking mechanism 43b. To connect the power source 40 to the x-ray device 10, the power source 40 is gently pushed into the bottom of the handle 15 of the x-ray device 10. When completely connected, the electrical connector 42 connects with the internal electronics of the x-ray device 10. The locking mechanism 43b is automatically engaged to retain the power source 40 connected to the x-ray device 10 in this position. To remove the power source 40, the release mechanism 43a is actuated to unlock the locking mechanism 43b, and the power source 40 can be gently slid out from the handle 15. The power source 40 is electrically connected to the conversion means using any connection means known in the art, including those described in the publications above. The conversion means converts the initial voltage supplied by the power source 40 to a converted voltage that is provided to the power supply 34. The conversion means generally converts the 14.4V (or similar voltage) provided by the power source 40 to a voltage ranging from about 80 to about 200V. In one aspect of the invention, the initial voltage is converted to a converted voltage of about 100V. Any conversion means known in the art that operates in this manner can be used in the invention, including the power management boards 36. The conversion means is electrically connected to the power supply 34. The power supply 34 steps up the converted voltage (i.e., the 100V) provided by the conversion means to a voltage that can be used by the x-ray tube 30. The power produced by the power supply 34 and input into the x-ray tube 30 via connection 35 (shown in FIG. 8) depends on the power needed to operate the x-ray tube, and the maximum power available from the power source. Generally, the power provided by the power supply 34 to the x-ray tube 30 can range from about 20 to about 150 kV. Typically, this power provided by the power supply can range from about 40 kV to about 100 kV. In one aspect of the invention, the power provided by the power supply is provided by a plurality of individual power supplies. The number of individual power supplies used depends on the voltage needed for the x-ray tube, the space needed for the power supply 34, the total power available from the power source, and the number of electron-accelerating grids in the x-ray tube. In one aspect of the invention, the plurality of individual power supplies is two (as represented in FIG. 5 by 45, 46) where 45 supplies positive voltage to the anode and 46 supplies negative voltage to the cathode. The power provided by each individual power supply depends on the number of individual power supplies used, the maximum power available from the power source, and the heat-dissipating capability of the x-ray tube. Generally, the power supplied by each individual power supply is the total power needed to operate the x-ray tube divided by the number of individual power supplies. For example, the power provided by each individual power supply (when there are 2) can range from about 20 kV to about 50 kV. In one aspect of the invention, the power provided by each individual power supply (when there are 2) is about +35 kV and −35 kV. In this embodiment, the +35 kV is attached to the anode of the x-ray tube and the −35 kV is attached to the cathode of the x-ray tube. A filament transformer is included in the cathode power supply to provide current to the x-ray tube filament and generate an electron beam at the cathode of the tube. The total power produced by the power supply is therefore the sum of the individual anode power supply and the individual cathode power supply. When such individual low voltage power supplies are used, the x-ray tube 30 of the invention becomes more portable. Conventional x-ray tubes operate at much higher voltages in the range of 70 kV and higher. Because of these high voltages, and the need for the high voltage standoff, the conventional x-ray tube 300 is often encased in insulating oil 302 (or a similar material) within a liquid-tight case 306 as shown in FIG. 9. The oil 302 also has the advantage of dissipating the high temperatures that existed during operation. By splitting the needed operation voltage into 2 (or more) individual power supplies, the individual power. supplies only need to provide (and also stand off) half of the higher voltage. With these lower voltages, the x-ray tube 30 of the invention can be encapsulated in materials other than high-density oil. These other materials need only insulate proportionately to the reduced voltage, i.e., these other materials need only insulate half as much as oil since the voltage produced is about half of that conventionally used. Any known material that can insulate in this manner can be used in the invention, including low-density materials like insulating gel, silicone rubber, epoxy, or combinations thereof. The insulating material is provided in a layer 33 that substantially encapsulates the x-ray tube 30 except for that portion of the tube where x-rays are actually emitted by the tube (i.e., into the x-ray collimator 32). The thickness of the layer of insulating material 33 need only be sufficient for the purpose indicated above. Generally, the thickness of the insulating material can range from about ¼ inch to about 1 inch. In one aspect of the invention, such as where silicone rubber is used, the thickness of the insulating material can range from about ⅓ inch to about ½ inch. In another aspect of the invention, the insulating material comprises a dual-layer around the x-ray tube with the first layer comprising one of the insulating materials and the second layer comprising another of the insulating materials. Eliminating the need to use the high-density oil provides a significant reduction in the weight of the unit. An added advantage is that there is no need for a liquid-tight case 306 to hold the liquid oil 302. Indeed, when a solid material is used such as silicone rubber, there is no need for any case, even though one can optionally be used. In one aspect of the invention by removing the case, and instead using silicon rubber that is conformal with the x-ray tube, the total volume of the insulating material is reduced significantly. As shown in FIG. 9, conventional x-ray tubes 300 also contain a shielding to absorb stray x-rays that are emitted from the x-ray tube. The shielding usually was made of lead and incorporated into the liquid-tight case 306. Lead is conventionally used because of its excellent x-ray absorption properties. But lead shielding is quite heavy and consequently limits the portability of the x-ray device. With the x-ray device of the invention, this lead shielding has been eliminated, thereby increasing the portability by reducing the need for an additional component in the x-ray device. Instead, the insulating material (i.e., silicone rubber) has dispersed,within it a high-Z material. The high-Z material absorbs any stray x-rays that are emitted. Any high-Z material known in the art can be used, including compounds of Pb, W, Ta, Bi, Ba, or combinations thereof. The concentration of the high-Z material in the insulating material need only be sufficient to absorb the expected amount of stray x-rays. Typically, the concentration of the high-Z material can range from about 30 wt % to about 60 wt %. In one aspect of the invention, the concentration of the high-Z material can range from about 45 wt % to about 50 wt %. In one aspect of the invention, the insulating material also contains substances that are known to optimize the thermal conductivity, such as metallic particles, or inclusions of high-thermal-conductivity materials. The x-ray device of the invention optionally contains shielding 80 for the operator. When in operation, x-rays can often backscatter from the object being analyzed, such as the teeth of a patient, and strike the operator. The shielding 80 is used to protect the operator from such aberrant radiation. In one aspect of the invention, the shielding used is a Pb-filled acrylic radiation scatter shield. The x-ray device of the invention also contains control means for operating the x-ray device. Any controls known in the art can be used in the control means of the invention. Examples of such controls include up and down arrow membrane switches with an LED readout to adjust exposure time. Indicators can include “power on,” “start,” and “x-rays on” LEDs. In the aspect of the invention illustrated in FIG. 1, the control means (controller 70) is integrated into the housing 20 of the device. In another aspect of the invention, the control means (such as controller 76) is external to the device and is connected to remainder of the device using any known electronic connection, such as cable 72 (See FIG. 3). In either instance, the control means also contains a trigger 74 that is incorporated into the handle 15 and used by the operator to begin (and conclude) the x-ray exposure. The invention also contains means for detecting or sensing the x-rays. Any detecting means known in the art that is sensitive to x-ray radiation can be used in the invention. Examples of such detecting means include x-rays receptors, x-ray film, CCD sensors, CMOS sensors, TFT sensors, imaging plates, and image intensifiers. In one aspect of the invention, and as illustrated in FIG. 10, a CCD sensor 50 is used as the detecting means in the x-ray devices of the invention. The x-ray device may also contain means for displaying the x-rays detected by the detecting means. Any display means that displays the detected x-rays in a manner that can be understood by the operator of the device can be used for the invention. Examples of displaying means that can be used include film, imaging plates, and digital image displays such as cathode ray tubes (CRT) or liquid crystal display (LCD) screens. In one aspect of the invention, the display means can be used as a densitometer for the x-ray absorption. In one aspect of the invention, the display means is integrated into the housing of the x-ray device. Such integration, however, will limit the size of the display means since too large a display means will detract from the portability of the device. In this aspect of the invention, any small display means with sufficient resolution can be used in the invention, including liquid crystal display (LCD) screens 60. In another aspect of the invention, the display means are located external to the x-ray device. In this aspect, a separate imaging plate (such as a CMOS or TFT plate) for larger features (such as medical or veterinary imaging) can be used. The separate imaging plate can be connected to the remainder of the x-ray device as known in the art. In one aspect of the invention, and as illustrated in FIG. 10, the x-ray device 10 can contain both a detecting means (such as CCD sensor 50), integrated display means (such as the LCD screen 60), and well as control means (such as controller 70). With these components, the size of the x-ray device can be minimized and the portability and uses of the x-ray device can be optimized. The detecting means and the display means can be used to temporarily store images in the x-ray device. Once the storage capacity for these temporary images has been reached, an optional wired or wireless connection can then provide seamless update to an external electronic device or system, such as a permanent database or a desktop computer as known in the art. The wired or wireless connection can be made as known in the art. In one aspect of the invention, this connection is wireless since it provides true portability and freedom from line voltage. In FIG. 10, the detecting means (CCD sensor 50) is not structurally attached to the x-ray device 10. Thus, in this aspect of the invention, the detecting means is free standing. With some of the known portable x-ray devices, the detecting means is structurally attached to the x-ray devices. Accordingly, the position of the detecting means is fixed relative to the rest of the x-ray device and when the x-ray device moves, so must the detecting means. This movement presents a problem for portable x-ray devices because any motion of the detecting means relative to the subject to be imaged result in distortion and blurring of the image. Because the detecting means of the invention is free-standing, any minor movements of the x-ray device of the invention will not result in distortion or blurring. As well, when the detecting means (i.e., a CCD sensor) is structurally attached, the x-ray device is typically configured to work with that specific type (e.g., size, shape) of the CCD sensor. The free-standing detecting means, however, can be interchanged with any given x-ray device without having to substantially modify the x-ray device. In FIG. 10, the detecting means (i.e., CCD sensor 50) communicates with the x-ray device 10 by any known wireless transmission mechanism. Examples of some wireless transmission mechanisms include 802.11 protocols, wireless application protocols (WAP), Bluetooth technology, or combinations thereof. In one aspect of the invention, Bluetooth technology is used as the wireless transmission mechanism. The radiographic image detected by the detecting means (CCD sensor 50) is transmitted to the x-ray device 10 and then viewed via the display means 60. The free-standing detecting means can be customized for analyzing any type of object. In one aspect of the invention, the CCD sensor can have non-flat configurations. In other aspects of the invention, the CCD sensor can have different types of shapes (other than the square illustrated in the Figures), such as rectangular, circular, oblong, polygonal, etc. . . . To achieve larger image areas, arrays of multiple detecting means can be assembled with electronics to resemble a single detecting means with the desired larger area. With the free-standing detecting means in this aspect of the invention, the x-ray device 10 is especially useful in the dental industry. As illustrated in FIG. 11, the x-ray device 10 can be used to analyze a tooth 90 (or multiple teeth) of a patient by placing the tooth 90 between the x-ray device 10 and the CCD sensor 50 and then operating the device. In FIG. 11, the CCD sensor 50 is connected to the x-ray device 10 by using any known wiring 55 (or cable) for that sensor to transmit the radiographic image to the x-ray device 10. A similar aspect of the invention is illustrated in FIG. 12, except that the wiring 55 has been replaced with wireless technology. In a similar aspect of the invention, the x-ray device can be modified slightly to be used in medical industry. In this aspect of the invention, the size of the detecting means (i.e., CCD sensor or CMOS imaging plate) is increased to capture a larger radiographic image. The larger size would depend on the part of the body that is being analyzed, as well as the maximum field size of the x-ray device. Typically, the size of the detecting means can range up to about 24 inches. In one aspect of the invention, the size of the detecting means can range from about 10 to about 14 inches. The x-ray device of the invention can also be configured differently in another aspect of the invention as shown in FIG. 13-16. In this aspect of the invention, the x-ray device 10 contains the same components as x-ray device 10, has been configured to look substantially like a traditional camera. This gives the impression to the operator of the x-ray device 10 that it operates like it looks: a camera, but for capturing digital radiological images. As shown in FIG. 13-16, the x-ray device 10 contains housing 120 that is substantially rectangular in shape. In this aspect of the invention, the housing 120 does not contain a handle. Rather, the housing 120 can contain a protruding shape 122 that provides the operator with a better grip than a flat surface. Of course, the x-ray device 110 could contain similar features for the handling and operation of the device, such as texturing the surface for easier gripping or by providing indentations. Like the x-ray device 10, the x-ray device 110 contains similar internal components such as an x-ray tube and an integrated power system. These internal components operate in substantially the same manner as x-ray device 10, but have been configured within the housing 120 to accommodate a different shape. As well, the x-ray device 110 contains control means (not shown), including trigger 174, radiation shielding 180, and any other components known in the art for efficient operation (such as x-ray collimator 132), including those components described in the documents mentioned above. The x-ray device 110 also contains means for displaying the results of the analysis. In this aspect of the invention, the x-ray device 110 contains an integrated display means, like LCD screen 160. As shown in FIG. 16, the removeable LCD screen 160 is configured to fit easily within a hollow portion 176 in the rear of the device 110 where it can be easily viewed by the operator. Of course, external display means could also be used in the invention. In one aspect of the invention, the display means and the control means are combined into a single means: a controllable display means. The controllable display means controls the operation of the x-ray device, as well as controls and manipulates the image display. The controllable display means can be either integrated into the x-ray device 110 or can be external to the x-ray device 110. Any controllable display means known in the art that operates in this manner can be used in the invention. One example of a controllable display means comprises a portable electronic device 165, such as a personal digital assistant (PDA), a handheld computer (like an IPAQ), or a conventional camera-style LCD screen. Using the portable electronic device with the x-ray device provides improved flexibility. For example, the portable electronic device—including both the hardware and the software—can be upgraded without needing to change the x-ray device itself. As well, the software in the portable electronic device can be used for image analysis, image enhancement, and for diagnosis at the point of image capture. Further, the x-ray device can be upgraded or modified with having to change the portable electronic device. Indeed, the portable electronic device could be customized so that any individual could take the customized settings and use them with any similar x-ray device. The controllable display means can be connected to the x-ray device 110 by wired or wireless technology. As shown in FIG. 17, the x-ray device 110 (including hollow portion 176) could be adapted to contain conventional interfaces in the hollow portion 176 for a portable electronic device 165. Thus, the portable electronic device 165 is mechanically and electrically connected to the x-ray device when placed in hollow portion 176. As well, the portable electronic device 165 could be electrically connected to the x-ray device 110 using conventional wiring. Finally, the portable electronic device 165 could be remotely connected to the x-ray device using any conventional wireless technology. Using the portable electronic device with the x-ray device 110 also increases the functionality of the x-ray device. For example, the portable electronic device could contain a temporary patient database. With flash memory storage devices, the patient database could be located on the portable electronic device and accessed when using the x-ray device. In another example, imaging software on the portable electronic device could allow for determining and manipulating features in the image, such as dental carries (cavities), breaks in bones, cracks in welds or pipes, identification of suspect shapes in security imaging, etc. . . . Indeed, any function currently performed on a desktop computer or workstation could be performed right at the x-ray device, including contrast enhancement, image sharpening, smoothing, reverse shading, assignment of colors for different density materials, determination of relative densities,. etc. . . . All of these functions, as well as others, could be performed with the portable electronic device attached to the x-ray device, or with it operating remotely. The portable electronic device could then interface with any known external electronic device (such as a storage device, office computer, or workstation) using wired or wirelessly technology to transfer data and/or information. As well, the portable electronic device (and therefore the x-ray device) could utilize the additional capabilities provided by the external electronic device. The x-ray devices of the invention can be made in any manner that provides the device with the components in this configuration described above. The housing, x-ray tube, detection means, display means, control means, radiation shielding, power source, and conversion means can be provided as known in the art and as described in the publications disclosed above. The insulating material can be made by mixing the needed amount of high-Z substance (such as an oxide of a heavy metal) into the insulating material (such as the silicone potting material when the A and B parts of the silicone are mixed together). The resulting combination is thoroughly mixed, and then uniformly provided around the x-ray tube, such as by pouring into an encapsulating mold. In this way, the insulating material containing the high-Z substance is uniformly distributed throughout the layer surrounding the x-ray tube. When making the power supply, the process will be illustrated with two individual power supplies. Each power supply is configured so that the grounded ends of each power supply are located near the center of the x-ray tube. The positive voltage from one supply is provided to one side of the x-ray tube, and the negative voltage from the other supply is provided to other end of the x-ray tube. In this configuration, the maximum voltage (i.e., the sum of both) can be isolated from each individual power supply along the full length of the -x-ray tube and the isolation from ground only needs to be ½ of the total voltage. Consequently, the insulating paths need only be ½ the length. The x-ray device can be operated in any manner that provides a radiographic image. In one aspect of the invention, the x-ray device 10 (or 110) of the invention can be operated by first actuating the appropriate button on the control means to turn on the device. After setting the exposure time, an “enable” button is pressed. This “enable” acts as a safety switch, preventing initiation of the x-ray exposure until the operator has positioned the instrument in the correct location and prepares to pull the trigger. Then, on pulling the trigger (or pressing the “start” button) the high voltage (HV) supplied by the power supply 34 will increase up to about 70 kV (i.e., one power supply at about +35 kV and the other at about −35 kV). When this HV level is reached, the filament will energize at its full setpoint to supply the needed emission current to the x-ray tube. The filament will remain at this level for the time designated by the operator (i.e., by-using the controls). The start indicator in the LED of the control means can illuminate upon pressing the trigger. The “x-rays on” indicator in the LED of the control means can illuminate during the entire time that the emission current for the x-ray tube is present. Additionally, an audible signal can be used to indicate that the x-rays are being emitted. During exposure after pressing the trigger 74 (or 174), x-rays are emitted from the x-ray tube 30 and strike the object being-analyzed, i.e., the teeth of a patient when the x-ray device is being used for dental purposes. To meet x-ray equipment standards, the button or trigger 74 (or 174) must be held down during the full length of the exposure. During exposure, the x-rays are used for analysis of the object as known in the art by using the detection means. The operator can then view the results of the analysis in the display means and optionally download the images to an external electronic device. Following the exposure of a patient with the x-rays, the filament will turn off (along with the “x-rays on” indicator) and the HV will ramp down. Once the HV is off, the start indicator in the LED of the controller will turn off and the x-ray device will return to a standby condition. In one aspect of the invention, the operator may need to re-enter the exposure time before starting the next exposure. This re-entering process can be accomplished with a “ready.” indicator in the LED of the control means after the exposure time has been set. The x-ray device of the invention can be modified to contain additional optional features, including any of those described in the publications mentioned above. For example, to increase battery life, the x-ray device can contain an automatic shut off feature that shuts the device off after 2 minutes without an x-ray exposure. Another feature that can be added, for example, is to manufacture the housing or chassis 20 (or 120) of a high-impact material (such as ABS or a plastic alloy of ABS and other materials, designed for high-impact resistance) to reduce the risk of damage. The x-ray device of the invention can also be made as part of a system for x-ray analysis. The system could contain any components that aid in the operation of the x-ray device or the x-ray analysis, including those mentioned above such as an external means for storing the radiographic images. As well, the system could also include a hard-side carrying case, an “industrial strength” tripod, a 3 meter long umbilical cord to a remote control panel 76, or the like. The system could also contain a back-up power source 40. Finally, the system could also contain any of those components described in the documents mentioned above. Using the x-ray device of the invention provides several improvements over conventional devices. First, the x-ray device of the invention contains an integrated power system. The power system can be battery-operated, yet still provide a continuous high voltage, rather than Marx generators (pulsed) or capacitively-pulsed systems. Thus, the x-ray device can maintain a continuous DC high voltage supply and can generate a high voltage for a few seconds with each high current discharge. The high storage capacity provided by the batteries allows hundreds of discharges, anywhere from about 10 to about 20 amps for a few seconds. For most applications, including for dental purposes, the x-ray devices of the invention need less than a second for each exposure. Most conventional x-ray devices, however, have external power supplies. Those conventional x-ray devices that do have integrated power supplies, still don't have the high current load described above. Thus, the power system of the invention can provide a constant radiation output and improved image quality while reducing the x-ray dosage to which the object (i.e., patient) is exposed. Another improvement in the x-ray devices of the invention exists in the shielding for the x-ray tubes. Conventional x-ray tubes are shielded with a liquid oil encasement and lead shielding, both of which are bulky and heavy. Both of these components are eliminated in the x-ray tube shielding of the invention. Instead, the shielding of the invention contains a low-density insulating material that contains high-Z substances. This configuration leads to reduced material count and generally lower weight. Other improvements result from the free-standing detecting means and the portable electronic device. With the free-standing detecting means, better images can be obtained even if the x-ray device moves. As well, the free-standing detecting means is more interchangeable with the x-ray device. When the portable electronic device is used with the x-ray device, the functionality (i.e., image display and manipulation) and interchangeability of the devices is greatly improved. In addition to any previously indicated variation, numerous other modifications and alternative arrangements may be devised by those skilled in the art without departing from the spirit and scope of the invention and appended claims are intended to cover such modifications and arrangements. Thus, while the invention has been described above with particularity and detail in connection with what is presently deemed to be the most practical and preferred aspects of the invention, it will be apparent to those of ordinary skill in the art that numerous modifications, including but not limited to, form, function, manner of operation and use may be made without departing from the principles and concepts set forth herein.
<SOH> BACKGROUND OF THE INVENTION <EOH>Typical x-ray tubes and x-ray devices (device containing x-ray tubes) have been known and used for some time. Unfortunately, they are usually bulky and are powered by heavy, high-voltage power supplies that restrict mobility. As well, they are often difficult and time-consuming to use. In many instances, a sample for analysis must be sent to an off-site laboratory for analysis by the x-ray device. These limitations can be very inconvenient for many popular uses of x-ray devices containing them. Such uses include x-ray fluorescence (XRF) of soil, water, metals, ores, well bores, etc., as well as diffraction and plating thickness measurements. Typical x-ray imaging applications require the sample to be imaged to be brought to the x-ray device. These limitations have led to an increased interest in making x-ray devices portable. See, for example, U.S. Pat. Nos. 6,661,876, 6,459,767, 6,038,287, and 6,205,200; U.S. Published Patent Applications 2003/0048877, 2003/0002627, and 2003/0142788; and European Patent Nos. EP0946082, EP0524064, EP0247758, EP0784965, and EP0488991; the entire disclosures of which are incorporated herein by reference. Many of these existing designs increase the portability of x-ray devices. At the same time, however, these designs are limited for several reasons. First, most of the designs are not truly portable since they have an external power source (i.e., require utility-supplied line voltage). Second, while some of the portable designs, especially the XRF systems, have internal or “integrated” power supplies, they don't have the high x-ray tube current load that is often necessary for x-ray imaging. For example, energy-dispersive XRF typically requires x-ray beam currents of less than 1 milliampere while x-ray imaging typically requires greater than about 2 milliamperes. Finally, the radiation shielding for the x-ray tubes usually comprises lead, which is quite heavy and limits the portability of the device. A further limitation on design of the increased portability is the image display components. High-quality imaging displays for displaying the results of the x-ray analysis are difficult to integrate into the design of the housing of the portable x-ray device. Consequently, many of the portable designs have the image display component external to the chassis or housing containing the x-ray tube.
<SOH> SUMMARY OF THE INVENTION <EOH>The invention relates to portable x-ray devices and methods for using such devices. The x-ray devices have an x-ray tube powered by an integrated power system. The x-ray tube is shielded with a low-density insulating material containing a high-Z substance. The x-ray devices can also have an integrated display component. With these components, the size and weight of the x-ray devices can be reduced and the portability of the devices enhanced. The x-ray devices can also have detecting means that is not structurally attached to the device and therefore is free standing. Consequently, the x-ray devices can also be used as a digital x-ray camera. The portable x-ray devices are especially useful for applications where portability is an important feature such as in field work, remote operations, and mobile operations such as nursing homes, home healthcare, or teaching classrooms. This portability feature can be particularly useful in multi-suite medical and dental offices where a single x-ray device can be used as a digital x-ray camera in multiple offices instead of requiring a separate device in every office.
20050801
20070529
20060511
71354.0
H05G110
1
MIDKIFF, ANASTASIA
DIGITAL X-RAY CAMERA
SMALL
0
ACCEPTED
H05G
2,005
10,530,202
PENDING
Vodka and a process for the production of vodka
An improved process is provided to prepare vodka with exellent properties includes mixing water and absolute alcohol, treating the mixture with activated coal followed by filtration, adding sugar, aroma compounds and optionally other ingredients characterized in that the mixture of water and alcohol after the treatment with activated coal is cooled down to a temperature of about −10° C. to −15° C., at which temperature the mixture is maintained for about 4-8 hours, after which the resulting mixture is filtered, gradually adapted to room temperature, aroma and optionally other ingredients are added to the filtrate and optionally the resulting mixture at room temperature is filtered again before bottling. A new vodka is provided having a percentage of absolute alcohol in water of about 35-50 vol %, 4-6 mMol/l sugar, 0.05-0.2 mMol/l of sodium bicarbonate, and 0.02-0.04 vol % of extract of flax seeds of first discharge.
1. Vodka, comprising a percentage of absolute alcohol in water of about 35-50 vol %, 4-6 mM sugar 0.05-0.2 mM of bicarbonate, preferably sodium bicarbonate 0.02-0.04 vol % of extract of flax seeds of first discharge. 2. Vodka according to claim 1 with an amount of impurities/1 absolute alcohol of acetic aldehyde lower than 3 mg fusel oil lower than 6 mg ester lower than 5 mg methyl alcohol lower than 0.2 ml and with an alkalinity characteristic of less than 3 meq. 3. Vodka according to claim 1 comprising a percentage of absolute alcohol in water of about 40 vol %, 5.3 mM of sugar, 0.12 mM of sodium bicarbonate and 0.032 vol % of extract of flax seeds. 4. Process to prepare vodka comprising mixing water and absolute alcohol, treating the mixture with activated coal followed by filtration, adding sugar, aroma compounds and optionally other ingredients characterized in that the mixture of water and alcohol after the treatment with activated coal is cooled down to a temperature of about −10 C to −15 C, at which temperature the mixture is maintained for about 4-8 hours, after which the resulting mixture is filtered, gradually adapted to room temperature, aroma and optionally other ingredients are added to the filtrate and optionally the resulting mixture at room temperature is filtered again before bottling. 5. Process to prepare vodka according to claim 4 whereby the filtrate is adapted to room temperature by pumping the filtrate to a non-isolated tank until room temperature has been attained. 6. Process to prepare vodka according to claim 4 whereby the aroma compounds comprise extract of flax seeds. 7. Process to prepare vodka according to claim 4 whereby water with an alkalinity of less than 3 meq/l is applied. 8. Process to prepare vodka according to claim 4 whereby the cooled down mixture is filtered through a carbon filter. 9. Process to prepare vodka according to claim 4 whereby the resulting mixture at room temperature is filtered over a series of micro filters before bottling.
The present invention relates to vodka and to a process to prepare vodka comprising mixing water and absolute alcohol, treating the mixture with activated coal followed by filtration, adding sugar, aroma compounds and optionally other ingredients. At present, a widely known method of production of vodka is consecutive mixing of water-alcohol liquid with sugar syrup, various aroma compounds like for instance synthetic aromatizers for disguising the fusel odor of alcohol, optionally other ingredients and subsequent filtering of the mixture [Retseptury likerno-vodochnykh izdelii i vodok (Formulas of alcoholic beverages and vodkas) Moscow: Legkaya promyshlennost, 1981]. Such method is rather simple technologically, however, the vodka produced by this method has insufficiently high organoleptic parameters. Sugar settles on the surface of activated coal decreasing its activity and adsorbability. It decreases the filtration level of the mixture and the ready vodka manifests the residual traces of fusel oils. In addition, the vodka produced by the known method has a strong odor of the introduced aromatizer and the beverage has an unnatural “synthetic” odor. The aromatizer evaporates with time and, accordingly, alcoholic aftertaste increases in the odor and taste. In addition, such vodka has usual ordinary taste and insufficiently high organoleptic parameters. Russian patent no. 2171283 discloses a method of production of vodka by obtaining water-alcohol liquid, filtration, mixing of the water-alcohol liquid with sugar syrup and other ingredients. According to this method the obtained water-alcohol liquid is filtered in a column with activated coal, then sugar and other ingredients of the formula of vodka are introduced in the obtained purified water-alcohol liquid, it is mixed, kept until it becomes homogeneous, and filtered prior to bottling (Russian Patent 2171281). Organoleptic parameters of this vodka are better than in the vodka produced by the method first mentioned. However, fusel oils present in the water-alcohol liquid still form a film on the surface of activated coal and this retards the technological process, as the flow rate through the column is slowing down. The lower filtration rate impairs, accordingly, the taste of vodka. It is an object of the present invention to provide a process which makes it possible to improve organoleptic parameters of vodka. The present invention provides a process as mentioned in the preamble characterized in that the mixture of water and alcohol after the treatment with activated coal is cooled down to a temperature of about −10° C. to −15° C., at which temperature the mixture is maintained for about 4-8 hours, after which the resulting mixture is filtered, gradually adapted to room temperature, aroma and optionally other ingredients are added to the filtrate and optionally the resulting mixture at room temperature is filtered again before bottling. Normally room temperature will be in the range of about 18° C.-25° C. Preferably, the filtrate is adapted to room temperature by pumping the filtrate to a non-isolated tank until room temperature has been attained. More preferably, the aroma compounds applied in said process comprise extract of flax seeds. Still more preferred, water with an alkalinity of less than 3 meq/l is applied for the process of the present invention. In a preferred embodiment of the process of the invention the mixture after cooling down is filtered through a carbon filter, preferably a Z-carbon filter. In still a preferred embodiment of the process of the invention the resulting mixture at room temperature is filtered over a series of micro filters before bottling, preferably immediately before bottling. Preferably, water for the water-alcohol liquid is obtained by mixing softened water and water treated by the method of reverse osmosis, normalized by the alkalinity parameter within about 2-3 meq/l. Furthermore, the water-alcohol liquid is preferably treated with activated coal in the coal column at a filtration rate of 40-50 decaliters/hour. The present invention further provides a vodka comprising a percentage of absolute alcohol in water of about 35-50 vol %, 4-6 mM sugar 0.05-0.2 mM of bicarbonate, preferably sodium bicarbonate and 0.02-0.04 vol % of extract of flax seeds of first discharge. Preferably said vodka comprises a minor amount of impurities per 1 absolute alcohol of acetic aldehyde lower than 3 mg fusel oil lower than 6 mg ester lower than 5 mg methyl alcohol lower than 0.2 ml and with an alkalinity characteristic of less than 3 meq, more preferably less than 2 meq. Throughout this patent application the wording alkalinity characteristic has been defined as volume in ml of hydrochloric acid with a concentration 0.1 M (viz. 0.1 Mol/l) of HCl used for titration of 100 ml of vodka. Still more preferred the vodka of the present invention comprises a percentage of absolute alcohol in water of about 40 vol %, 5.3 mM of sugar, 0.12 mM of sodium bicarbonate and 0.032 vol % of extract of flax seeds. The objects of the present invention are accomplished in the following way: to prepare water for water-alcohol liquid the mixture is composed of softened water and water treated by the method of reverse osmosis, normalized by the parameter of alkalinity within 2-3 meq/l. Then the obtained water is mixed with ethyl alcohol, then the obtained water-alcohol liquid is passed through the coal column with activated coal at the filtration rate of 40-50 decaliters/hour. The treated mixture is directed to the heat isolated cooler for cooling to −10° C.-−15° C., then it is pumped at this temperature to a heat isolated tank and kept there during 4-8 hours. After keeping, the cooled mixture is filtered through a Z-carbon filter and pumped to a non-heat isolated tank for “rest” until the room temperature of about 18° C.-25° C. is gradually attained. Sugar syrup is added to the obtained water-alcohol liquid and if desired, other ingredients of the vodka to be prepared and for instance aromatic alcohol. Prior to bottling, the produced vodka is consecutively filtered through a series of microfilters. Sugar can be added at any moment of the process, the other ingredients are preferably added after the mixture hab be brought to room temperature. Profound cooling to the temperature of −10°-−15° C. considerably increases the density of the water-alcohol liquid, and leads to formation on walls of the cooler of a fine crystalline film being a mixture of aldehydes, fusel oils, and methanol. Filtration at such low temperature still better purifies the water-alcohol liquid while not destroying the molecular system water-alcohol formed at cooling of the water-alcohol liquid. The same aim is attained by gradual natural warming of the mixture after filtration with an appropriate time lag. The present invention will be exempified further by the following example which is not to be considered as restricting the scope of the invention in any way. EXAMPLE Vodka “Stolichnaya Elit” is prepared using alcohol “Lux” and water obtained by mixing softened water with water preliminarily treated by the method of reverse osmosis, normalized by a parameter of alkalinity within 2-3 meq/l. Alcohol or spirit “Lux” has been described in the State Standard of the Russian Federation, no. P 51652-2000. With regards to its physical and chemical indicators spirit “lux” must conform the requirements in the table below. Norm for the Indicator spirit Volume of ethyl spirits, %, not less 96.3 than Sulphuric acid test for Passed identification of purity Oxidability test, min., 20° C., not 22 less than Mass concentration of aldehydes to 2 absolute alcohol, mg/dm3, no more than Mass concentration of fusel oil: - 1 6 propanol, 2-propanol, isobutyl alcohol, 1-butanol, isoamyl alcohol to absolute alcohol, mg/dm3, no more than Isoamyl and isobutyl alcohols (3:1) 2 to absolute alcohol, mg/dm3, no more than Mass concentration of ester to 5 absolute alcohol, mg/dm3, no more than Volume of methyl spirit to absolute 0.03 alcohol, %, no more than Mass concentration of free acids 8 (with no CO2) to absolute alcohol, mg/dm3, no more than Mass concentration of solid residual — to absolute alcohol, mg/dm3, no more than Mass concentration of basic volatile — nitrogens to nitrogen, in 1 dm3 of absolute alcohol, mg, no more than Spirit “Lux” is produced from various sorts of grains and mix of grain and potatoes, volume of starch in the mix should not exceed 35% for production of spirit “Lux”. In a mixing tank the alcohol and water are mixed to obtain the mixture of 40%, then the mixture is passed through the column with activated coal at the filtration rate of 40-50 decaliters/hour. The filtered water-alcohol mixture is passed through the heat exchanger to decrease its temperature to −10°° C.-−15° C., the cooled mixture is kept in the heat isolated tank during 4-8 hours depending on the rate of formation of the crystalline film on walls of the tank. The cooled mixture is filtered through a Z-carbon filter, the temperature of the mixture is increased by 6° C.-10° C., the obtained filtrate is pumped to a non-isolated tank for “rest” until the room temperature of 18° C.-25° C. is gradually attained. To the obtained water-alcohol liquid 65.8% sugar syrup is added and, other ingredients of the vodka and aromatic alcohol. To the other ingredients belongs the use of grains for production of extract of flax for 1000 dal. of vodka as given in the following tabel: Extract of the first discharge Liquid of (filtered) water and % from spirit Time of Vol- water Name of Use, Volume extrac- ume, Vol- and raw in in Volume tion in ume spirits material kilos liters in % in days liters in % liquid Seeds of 0.4 4.0 50 5 3.2 49 80 flax The obtained composition is kept for 1-5 hours and then the produced vodka is, prior to bottling, consecutively filtered through a series of micro filters and bottled. The ready for use vodka has the following parameters: Strength (volume %) 40.0 Appearance Transparent, colorless liquid with glitter Taste Soft, harmonious, with rounded vodka shades Aroma Characteristic of vodka, without admixture of fusel oil odor The produced vodka received 9.8 points from tasters. The following tabel gives more characteristics: Compounding of Vodka Stolichnaya Elit Indices of Vodka Physicochemical Volume, % 40.0 Alkalinity- volume of hydrochloric acid with 2.0 concentration with (HCL) = 0.1 molecule/dm3, used for titration of 100 cm3 of vodka, cm3, not exceeding Mass concentration of acetic aldehyde in 1 dm3 3.0 of absolute alcohol, mg, not exceeding Mass concentration of fusel oil (1-propanol, 2-propanol, 6.0 iso-butanol, 1-butanol, iso-amilol) in 1 dm3 of absolute alcohol, mg, not exceeding Mass concentration of ester, in 1 dm3 of absolute 5.0 alcohol, mg, not exceeding Volumetric share of methyl alcohol, absolute alcohol 0.02 equivalent, %, not exceeding Organoleptic Appearance clear liquid without extraneous impurities and sediment Color colorless Taste soft, peculiar to vodka Aroma specific vodka aroma Mixing for 1000 Dal Measuring Name of component unit Quantity Ethyl spirit rectified L Spirit and water equivalent to “Lux” Potable water improved L volume of 40% Sugar syryp, 68% L 20.7 Extract of flax seeds of L 3.2 1st discharge SodiumBicarbonate kg 0.1 Consumption of Ingredients for 1000 Dal of Vodka Name of Ingredients Quantity (kg) Sugar granulated purified 18.0 Sodium bicarbonate 0.1 Oil Flax (seeds) 0.4 The present invention provides a process which makes it possible to produce vodka with improved organoleptic parameters.
20051101
20060622
69327.0
C12H114
0
STULII, VERA
Vodka and a process for the production of vodka
UNDISCOUNTED
0
PENDING
C12H
2,005
10,530,203
ACCEPTED
Microcircuit card whereof the performances can be modified after customization
The invention concerns a microcircuit card comprising means (RX) for receiving a command and means for modifying at least one performance of the card capable of being implemented after a step of personalization of the card.
1. Microcircuit card (100) including means (RX) for receiving a command (200) and means for modifying at least one characteristic of the performance of said card on reception of said command, the modification means being characterized in that they can be used after a step (E10) of customization personalization of said card. 2. Microcircuit card according to claim 1, characterized in that it further comprises means for authenticating the sender of said command (200). 3. Microcircuit card according to claim 2, characterized in that the authenticating means comprise a secret authentication key. 4. Microcircuit card according to claim 1, characterized in that the modification means are adapted to determine said at least one performance characteristic as a function of a predetermined instruction (210) received in said command (200). 5. Microcircuit card according to claim 1, characterized in that said receiver means (RX) are adapted to receive said command (200) in accordance with an SMS protocol. 6. Microcircuit card according to claim 1, characterized in that said means for modification of at least one performance characteristic are adapted to modify the size of a usable area (110) of a physical memory (EEPROM) of said card. 7. Microcircuit card according to claim 6, characterized in that said modification of the size of a usable area (110) of a physical memory (EEPROM) is effected by creating, destroying at least one specific file (VOID_FILE) or by modifying the size of at least one specific file (VOID_FILE) comprised in said physical memory. 8. Microcircuit card according to claim 1, characterized in that said means for modification of at least one performance characteristic are adapted to modify a clock frequency of said card, reversibly or not. 9. Microcircuit card according to claim 1, characterized in that said means for modification of at least one performance characteristic are adapted to allow or prevent the use of at least one software function (f) of said card, reversibly or not. 10. Microcircuit card according to claim 1, characterized in that said means for modification of at least one performance characteristic are adapted to allow or prevent the use of all or part of an electronic circuit (120) of said card, reversibly or not. 11. Microcircuit card according to claim 10, characterized in that said electronic circuit (120) is a cryptographic unit. 12. Microcircuit card according to claim 1, characterized in that it further comprises synchronization means (130) adapted to verify that said command (200) is unique. 13. Method of configuring a microcircuit card (100) characterized in that it comprises the following successive steps: customization personalization (E10) of said card; reception (E20) of a command (200); and modification (E40, E60, E70, E80) of at least one characteristic of the performance of the card on reception of said command (200). 14. Method of configuring according to claim 13, characterized in that said reception step (E20) is followed by a step (E30) of authentication of the sender of said command (200). 15. Method of configuring according to claim 13, characterized in that, during said modification step (E40, E60, E70, E80), said at least one performance characteristic is determined as a function of a predetermined instruction (210) received in said command (200). 16. Method of configuring according to claim 13, characterized in that said step (E20) of reception of a command (200) conforms to an SMS protocol. 17. Method of configuring according to claim 13, characterized in that, during said step (E40) of modification of at least one performance characteristic, the size of a usable area (110) of a physical memory (EEPROM) of said card is modified. 18. Method of configuring according to claim 17, characterized in that during said modification of the size of a usable area (110) of a physical memory (EEPROM) at least one specific file (VOID_FILE) included in said physical memory is created, or destroyed or the size of at least one specific file (VOID_FILE) included in said physical memory is modified. 19. Method of configuring according to claim 13, characterized in that, during said step (E60) of modification of at least one performance characteristic, a clock frequency of said card is modified, reversibly or not. 20. Method of configuring according to claim 13, characterized in that, during said step (E70) of modification of at least one performance characteristic, the use of at least one software function (f) of said card is allowed or prevented, reversibly or not. 21. Method of configuring according to claim 13, characterized in that, during said step (E80) of modification of at least one performance characteristic, the use of all or part of an electronic circuit (120) of said card is allowed or prevented, reversibly or not. 22. Method of configuring according to claim 21, characterized in that said electronic component (120) is a cryptographic unit. 23. Method of configuring according to claim 13, characterized in that it comprises, before said step (E40) of modification of at least one performance characteristic, a step (E35) of verification that said command (200) is unique.
The present invention concerns a microcircuit card whereof the performance can be modified after a step of customization of the card, and a method for configuring this kind of card. In the remainder of this document, the term “customization” will be understood in the sense in which it is routinely used by the person skilled in the microcircuit card art, or as defined by W.Rankl and W.Effing in the document “Smart Card Handbook, Second Edition, Ed. John Wiley & Sons, Ltd.” in the following terms: “The term customization, in its widest sense, means that the data specific to a card or to a person is entered in the card. This data may for example, be a name, an address, and also includes keys associated with the card. The only thing that is important is that this data is specific to this card.” The invention finds one special but nonlimiting application in the field of mobile telecommunication microcircuit cards such as SIM cards conforming to the GSM standard and cards conforming to similar standards such as the CDMA, TDMA or UMTS standards. In this context, the invention enables modification of the performance of a customized mobile telecommunication card already allocated to a user subscribing to a mobile telephone service. Modifying the clock frequency of a microcircuit card before the step of customization of the card is already known to the person skilled in the art. This kind of process is used in particular during the phases of developing a microcircuit card, during which the cards are tested at different clock frequencies, the clock frequency of the card then being fixed before the end of the customization process. However, in the prior art, the performance of the card cannot be modified after the customization of the card. It would nevertheless be desirable to be able to modify the performance of a microcircuit card after customization, in particular after it is sold, or more generally after it has been allocated to a user. To this end, the invention relates to a microcircuit card including means for receiving a command and means for modifying at least one characteristic of the performance of said card on reception of said command, it being possible for the modification means to be used after a step of customization of said card. In a complementary manner, the invention relates according to a second aspect to a method of configuring a microcircuit card comprising the following successive steps: customization of said card; reception of a command; and modification of at least one characteristic of the performance of the card on reception of said command. In the context of the present invention, a characteristic of “performance” of a microcircuit card that can be modified by a configuration method conforming to the present invention must be understood as referring to any hardware or software characteristic pre-existing in the card and not accessible after customization. The invention thus enables the performance of a microcircuit card to be enhanced or degraded by sending the command cited above after customization, the card having been already allocated to a user. In contrast, without the present invention, a user requiring to use a card with new performance must necessarily change the microcircuit card. Thus, on reception of the appropriate command, the user of a microcircuit card including a physical EEPROM of 64 kbytes but in which the size of the usable area has been limited to 32 kbytes before customization, can use all of the 64 kbytes of the physical memory, without having to change the card. According to one advantageous feature, the microcircuit card further comprises means for authenticating the sender of the command. In a preferred embodiment, those authenticating means comprise cryptographic means for verifying if the command was encrypted with a predetermined authentication key. These verification means may use a hashing function of an MD4, MD5 or SHA-1 algorithm. Thus, according to this advantageous feature, modification of the performance of the card necessitates a knowledge of the authentication key, which may be kept secret by an operator, the manufacturer of the card or any third party, thereby reserving the possibility of modifying the performance of the card. In a variant, the above authentication key is associated with the modification of a predetermined characteristic of the performance of a predetermined card. According to another feature, the modification means are adapted to determine which characteristic of the performance of the card must be modified as a function of a predetermined instruction received in the command. This feature enables, in accordance with the predetermined instruction received in the command, modification of one or several characteristics of the card. In a particularly advantageous embodiment, the receiver means are adapted to receive the command in accordance with the SMS protocol or a similar protocol such as the MMS (MultiMedia Service) protocol. This embodiment therefore allows the modification of at least one characteristic of the performance of the card via a mobile telecommunication network. Of course, in other embodiments, the command may be received by the receiver means through a cable network or locally. According to a preferred embodiment of the card according to the invention, the modification means are adapted to modify the size of a usable area of a physical memory of the card. This feature therefore allows the memory capacity of the card to be increased, for example to allow the downloading of new applications into the card. In a preferred variant of this embodiment, the size of the usable area of the physical memory is modified by creating or by destroying at least one specific file contained in the physical memory or by modifying the size of at least one specific file contained in the physical memory. This file may be a file specifically created to occupy space in the physical memory or a data file used by an application of the microcircuit card. In another preferred embodiment, the means for modification of at least one characteristic of performance are adapted to modify a clock frequency of the card, reversibly or not. According to this particular feature, the calculation speed of a processor or a cryptographic component of the card may be accelerated, enabling more complex processing to be carried out on digital data received by the microcircuit card. In another embodiment, the means for modification of at least one characteristic of performance are adapted to allow or prevent the use of at least one software function of the card, reversibly or not. This particular feature thus allows validation of software applications initially provided on the card but invalidated before the end of its customization. This kind of software function may for example be a cryptographic function, such as a function for checking a digital data signature. Similarly, in another embodiment, the means for modification of the performance of the card are adapted to allow or prevent the use of the whole or part of an electronic circuit of the card, reversibly or not, that electronic circuit being a cryptographic unit, for example. The cryptographic processes that were performed by software can advantageously be accelerated by the use of this cryptographic unit. In a preferred embodiment, the microcircuit card according to the invention further comprises synchronization means adapted to verify that the command is unique. This particular feature advantageously avoids dishonest use of the microcircuit card by preventing a second execution of a command already received and fraudulently copied. The advantages and particular features specific to the configuration method of the invention will not be reviewed here, because they are similar to those explained above in relation to the microcircuit card according to the invention. Other characteristics and advantages of the present invention will appear more clearly on reading the following descriptions of a particular embodiment that follows, given by way of nonlimiting example and with reference to the appended drawings, in which: FIG. 1 is a diagram of the architecture of a microcircuit card according to the invention; FIG. 2 represents a command conforming to the present invention in a preferred embodiment ; and FIG. 3 is a flowchart of the main steps of a preferred embodiment of a configuration method according to the invention. FIG. 1 is a diagram of the architecture of a microcircuit card 100 according to the invention. The microcircuit card 100 principally comprises a processor CPU associated in the conventional way with a certain number of memories of RAM, ROM and EEPROM type. The memory ROM comprises in particular the instructions of a computer program adapted to implement a configuration method conforming to the present invention, the main steps of which are described later with reference to FIG. 3. Similarly, the random access memory RAM comprises registers necessary for the execution of this program. The microcircuit card 100 also comprises a physical memory, for example a memory of EEPROM type, whereof the size of a usable area 110 may be modified after customization. The microcircuit card 100 also comprises an electronic circuit 120 that in the embodiment described here is a cryptographic unit. In a manner that is known in the art, the microcircuit card 100 also receives a signal from a clock CLOCK external to the card, this clock signal being supplied to the various components of the card. In the particular embodiment described here, the microcircuit card 100 includes a PLL (phase-locked loop) component known to the person skilled in the art for deriving signals at various clock frequencies from the external clock signal CLOCK. To be more precise, in the embodiment described here, the usable area 110 of the memory EEPROM comprises a register mult_clk for storing a multiplier factor that is applied to the frequency of the signal from the external clock CLOCK. When the microcircuit card is powered up, the processor CPU reads this register mult_clk and programs the PLL component with the value contained in this register, the clock signal at the output of the PLL component then being applied to certain components of the card. In the embodiment described here, the PLL component modifies the calculation speeds of the processor CPU and the cryptographic unit 120. The microcircuit card 100 according to the invention comprises means RX for receiving a command 200, a preferred embodiment of which is described next with reference to FIG. 2. The command 200 comprises a field 210 comprising a predetermined instruction that is analyzed to determine which characteristics of the performance of the card 100 must be modified. In the embodiment described here, the characteristics of the performance of the microcircuit card 100 that can be modified after customization are the size of the usable area 110 of the physical memory EEPROM, the frequency of the clock signal, and a software function f used by the processor CPU and the electronic circuit 120. In the preferred embodiment described here, the instruction 210 consists of a byte in which: the first bit (bit1) and the second bit (bit2) represent an instruction for creating or destroying a usable area 110 or an instruction for modifying the size of the usable area 110 of the physical memory EEPROM of the microcircuit card 100; the third bit (bit3) and the fourth bit (bit4) constitute a multiplier factor for the frequency of the clock signal supplied by the external clock CLOCK; the fifth bit (bit5) represents an instruction for use or non-use of a software function f of the card; the sixth bit (bit6) represents an instruction for use or non-use of the electronic circuit 120; and the seventh and eighth bits are not used. In the preferred embodiment described here, the receiver means RX are adapted to receive the command 200 in accordance with the SMS protocol, for example by means of the ENVELOPE command of that protocol, and to store the command 200 in an area of the random access memory RAM. The microcircuit card 100 also comprises means for authenticating the sender of the command 200. In a preferred embodiment, the authenticating means comprise cryptographic means for verifying if the command 200 was encrypted with a predetermined authentication key AUTH stored in a portion AUTH of the usable area 110 of the memory EEPROM at the time of customization of the card. These cryptographic means may consist in a processing program that is executed by the processor CPU and comprises instructions for implementing a public key decrypting algorithm such as the RSA algorithm known to the person skilled in the art. In the preferred embodiment described here, to prevent unauthorized execution a second time of a command 200 already received and fraudulently copied, the microcircuit card 100 further comprises synchronization means 130 adapted to verify that the command 200 is unique. The synchronization means 130 may in particular consist of an electronic circuit implementing the verification test E35 described later with reference to FIG. 3. In a preferred embodiment, the processor CPU determines, from the command 200, the characteristics(s) of the performance of the microcircuit card 100 that must be modified. In particular, if the pair (bit1, bit2) consisting of the first bit bit1 and the second bit bit2 of the instruction 210 is equal to (1,1), this means that the size of the usable area 110 of the physical memory EEPROM must be increased, if possible. In practice, and in the preferred embodiment described here, the microcircuit card 100 comprises, before customization, a computer file VOID_FILE in the physical memory EEPROM and, when the pair (bit1, bit2) is equal to (1,1), the processor CPU destroys this file VOID_FILE, thereby freeing up a part of the physical memory EEPROM. In a variant form, if the pair (bit1, bit2) is equal to (1,1), the size of the usable area of the physical memory EEPROM is, if possible, increased , by a reduction in the size of the file VOID_FILE, in a predetermined manner, for example by 16 kbytes. Similarly, in the preferred embodiment described here, if the pair (bit1, bit2) is equal to (0,0), this means that the size of the usable area 110 of the physical memory EEPROM must, if possible be reduced, by increasing, (if possible) the size of the file VOID_FILE in a predetermined manner, for example by 16 kbytes. In a variant form, if the pair (bit1, bit2) is equal to (0,0), this means that a file VOID_FILE must be created, if possible, at a predetermined address and of predetermined size in the physical memory EEPROM. In the embodiment described here, the reception of a command 200 whereof the pair (bit1, bit2) is equal to (1,0) or (0,1) is without effect. According to the IS07816 standard, modifying the characteristics of the file VOID_FILE (creation, destruction, change of size) may necessitate a specific key KEY 220 received in the command 200 (as represented in FIG. 2). In another preferred embodiment, a plurality of files of the same type may be provided before customization of the card, which progressively increases the size of the usable area of the physical memory EEPROM by destroying these files. Moreover, when the microcircuit card 100 receives the instruction 210, the processor CPU obtains a clock multiplier factor by reading the third bit bit3 and the fourth bit bit4 of this instruction 210. In the preferred embodiment described here, this clock multiplier factor is respectively equal to 1, 2 and 3 for values of the pairs (bit3, bit4) respectively equal to (0,1), (1,0), (1,1). In the particular embodiment described here, this multiplier factor is stored in the register mult_clk of the usable area 110 of the memory EEPROM, this register being read by the processor CPU on power up to set the parameters of the PLL component. In the embodiment described here, the microcircuit card comprises modification means adapted to allow or prevent the use of a software function f of the card. In practice, the read only memory ROM comprises a computer program able to invoke this software function f when a soft register of the usable area 110 of the non-volatile memory EEPROM contains the value 1. On reception of the command 200, the processor CPU reads the value of the fifth bit bit5 of the predetermined instruction received in the command 200 and then writes it in the soft register. In the example described here, the software function is a cryptographic function or a digital data signature checking function received by the receiver means RX. The microcircuit card 100 also comprises modification means adapted to allow or prevent the use of all or part of an electronic circuit 120 of the card. In the embodiment described here, this electronic circuit 120 comprises a cryptographic unit. In practice, the use of this electronic circuit 120 is possible after writing of the value 1 in a hard register of this component, the value of this register being modified by the processor CPU with the content of the sixth bit bit6 of the predetermined instruction. In the example described here, modifying the clock frequency and allowing or preventing use of the software function or the electronic component are reversible operations. In another embodiment, at least one of these operations could be non-reversible. The main steps of a preferred embodiment of a configuration method conforming to the invention are described next with reference to FIG. 3. The configuration method comprises a first step E10 of customization. This step is known to the person skilled in the art and is not described in detail here. Be this as it may, this customization step consists in writing data specific to the card or to a user of the card in a memory of the card, for example in the EEPROM. In the example described here, this customization step comprises in particular writing the value of the authentication key AUTH in a memory EEPROM of the microcircuit card 100. This customization step also includes the creation of the file VOID_FILE and its key 220 in the memory EEPROM. The step E10 is followed by a step E20 of receiving the command 200 described previously with reference to FIG. 2. The step E20 is followed by a verification step E30 during which the processor CPU authenticates the sender of the command 200. In the embodiment described here, this authentication step is effected by verifying if the command 200 was encrypted with a predetermined authentication key AUTH being stored in a register of the memory EEPROM at the time of customization of the card. If this is not the case, the result of the test E30 is negative. This test is then followed by the step E20 already described of receiving a command. On the other hand, if the sender of the command 200 is authenticated, as authorized to send the command 200, the result of the test E30 is positive. This test is then followed by a test E35 which verifies that the command 200 is unique. This verification test E35 avoids unauthorized execution for a second time of a command 200 already received and fraudulently copied. As is known in the art, this verification test E35 may be implemented by incorporating in each command 200 a message number that is incremented for each command and comparing the number received in a particular command 200 with the value of the number received in the preceding command 200. If the command 200 has already been received, the result of the verification test E35 is negative. This test is then followed by the step E20 already described of receiving a command 200. On the other hand, if the command 200 is received for the first time, the result of the verification test E35 is positive. This test is then followed by a step E40 during which the size of the usable area 110 of the physical memory EEPROM is modified as a function of the values of the first and second bits (bit1, bit2) of the predetermined instruction 210 received in the command 200. In the various embodiments described above with reference to FIG. 1, this step E40 is performed by creating, by destroying the file VOID_FILE contained in the physical memory EEPROM or by modifying the size of this file VOID_FILE. The step E40 of modifying the size of the usable area 110 of the physical memory EEPROM is followed by a step E60 during which the multiplier factor for the frequency of the external clock CLOCK is stored in the register mult_clk of the usable area 110 of the memory EEPROM; this register is read by the processor CPU on power up to set the parameters of the component PLL, the effect of which is to modify reversibly the clock frequency of the card. As previously described, the clock frequency multiplier factor is determined by the value of the third bit bit3 and the fourth bit bit4 of the predetermined instruction 210. The step E60 of modifying the clock frequency is followed by a step E70 during which the processor CPU writes the value of the fifth bit bit5 of the instruction 210 in the soft register of the non-volatile memory EEPROM. As described above, when this soft register stores the value 1, a software function f for example a cryptographic function such as a digital data signature checking function is rendered accessible in the sense that it can be invoked by a computer program stored in the memory ROM or in the memory EEPROM. The step E70 is followed by a step E80 during which the processor CPU stores the value of the sixth bit bit6 of the predetermined instruction in the hard register of the electronic circuit 120. If this hard register holds the value 1, the use of this electronic circuit 120 is authorized. In the preferred embodiment described here, this electronic circuit 120 is a cryptographic unit. The step E80 is followed by a step E20 already described of reception of a command.
20060306
20100629
20061019
67906.0
G06K1906
0
HAUPT, KRISTY A
MICROCIRCUIT CARD WHEREOF THE PERFORMANCES CAN BE MODIFIED AFTER PERSONALIZATION
UNDISCOUNTED
0
ACCEPTED
G06K
2,006
10,530,301
ACCEPTED
Receiving device comprising an adjustable covering element
The invention relates to a holding device (1) with a holding container (2) for a holding vessel, in particular a blood sample collecting tube, in which the holding container (2) surrounds a holding chamber (7) with a container wall (6), and in the direction of a longitudinal axis (8) comprises a proximal and a distal end (9, 10) spaced part from one another, with a needle holder (4) for a needle arrangement (14) that can be attached thereto, with a first adjusting device (15) for the needle holder (4) and with a cover element (3) for the needle arrangement (14) mountable on the needle holder (4) in the disposal position of the needle holder (4). The cover element (3) is arranged in the position of use of the needle holder (4) adjacent thereto on the side furthest from the proximal end (9) in the holding chamber (7) and is arranged with an if necessary releasable locking device (16) between the cover element (3) and the holding container (2) in the position of use relative to the latter, whereby between the needle holder (4) and the cover element (3) a further adjusting device (17) is arranged.
1-71. (canceled) 72. Holding device (1) with a holding container (2) for a holding vessel, in particular a blood sample collecting tube, wherein the holding container (2) surrounds a holding chamber (7) with a container wall (6), and in the direction of a longitudinal axis (8) comprises a proximal and a distal end (9, 10) spaced apart from one another, whereby the container wall (6) is delimited by an inner surface (11) facing the holding chamber (7) and an outer surface (12) facing away therefrom, with a needle holder (4) for a needle arrangement (14) which can be secured thereon, in particular a double-ended cannula needle (5), whereby the needle holder (4) in the holding chamber (7) of the holding container (2) is designed to be displaceable relative to the latter from a position of use in the region of the proximal end (9) to a disposal position in the direction of the distal end (10), with a first adjusting device (15) for the needle holder (4) for the displacement from the position use into the disposal position, with a cover element (3) for the needle arrangement (14) securable to the needle holder (4) in the disposal position of the needle holder (4) and with a releasable locking device (16), wherein the cover element (3) is formed by a disc-shaped main body (21) aligned in a plane (20) perpendicular to the longitudinal axis (8), whereby the cover element (3) in the position of use of the needle holder (4) is arranged adjacent thereto on the side pointing away from the proximal end (9) in the holding chamber (7), and in that the releasable locking device (16) is arranged between the cover element (3) and the holding container (2), with which the cover element (3) in the position of use of the needle holder (4) is held relative to the holding container (2), and in that between the needle holder (4) and the cover element (3) an additional adjusting device (17) is arranged formed by an elastically deformable spring element (19), in particular a compression spring, whereby on releasing the locking device (16) the cover element (3) is displaced relative to the needle holder (4) in the direction of the longitudinal axis (8) by the additional adjusting device (17) in the direction of the distal end (10) of the holding container (2). 73. Holding device according to claim 72, wherein the first adjusting device (15) is in the form of an elastically deformable spring element (18), in particular a compression spring. 74. Holding device according to claim 72, wherein the additional adjusting device (17) is designed to expand conically from the needle holder (4) up to the cover element (3). 75. Holding device according to claim 72, wherein the first and the additional adjusting device (15, 17) are in the form of a one-piece component. 76. Holding device according to claim 72, wherein the disc-shaped main body (21) of the cover element (3) has an external diameter (30) in the plane (20) perpendicular to the longitudinal axis (8), which corresponds approximately to an inner diameter (31) of the holding chamber (7) in the same plane (20) or is only slightly smaller. 77. Holding device according to claim 72, wherein the cover element (3) in the region of the longitudinal axis (8) has an opening (22) for feeding through a portion of the cannula (5). 78. Holding device according to claim 77, wherein in the region of the opening (22) a component (23) is arranged for suctioning or absorbing liquid. 79. Holding device according to claim 72, wherein the locking device (16) comprises at least one, preferably two, diametrically opposite locking elements (25) and locking recesses (26) cooperating therewith. 80. Holding device according to claim 79, wherein the locking element or elements (25) are arranged on the disc-shaped main body (21) of the cover element (3). 81. Holding device according to claim 72, wherein on the main body (21) of the cover element (3), several, preferably four, locking elements (25) are arranged distributed evenly around the circumference and in the holding container (2) several, preferably two, diametrically opposite locking recesses (26) are arranged to form the locking device (16). 82. Holding device according to claim 79, wherein the locking recesses (26) are arranged in the container wall (6) of the holding container (2). 83. Holding device according to claim 79, wherein the locking recesses (26) penetrate the container wall (6) of the holding container (2). 84. Holding device according to claim 79, wherein the locking element or elements (25) project in radial direction, from the inner surface (11) to the outer surface (12) of the container wall (6), only partially into the locking recesses (26). 85. Holding device according to claim 79, wherein the locking element or elements (25) is or are spring-connected to the disc-shaped main body (21) of the cover element (3). 86. Holding device according to claim 79, wherein the locking element or elements (25) is or are arranged on a holding arm (57) projecting from the main body (21) of the cover element (3) in the direction of the needle holder (4) or the proximal end (9). 87. Holding device according to claim 79, wherein the locking element or elements (25) is or are arranged in the region of the outer circumference of the cover element (3). 88. Holding device according to claim 72, wherein on the region of the main body (21) facing the proximal end (9) at least one first centring element (51) for the additional adjusting device (17) is arranged. 89. Holding device according to claim 72, wherein between the cover element (3) and the inner surface (11) of the container wall (6) at least one first guiding arrangement (27) is provided, which is aligned in the direction of the longitudinal axis (8) of the holding container (2). 90. Holding device according to claim 89, wherein the guiding arrangement (27) extends at least over the entire displacement path (58) of the cover element (3) between its maintenance position in the region of the proximal end (9) and its cover position in the region of the distal end (10). 91. Holding device according to claim 89, wherein the first guiding arrangement (27) is formed by at least one guiding groove (28) indented in the container wall (6) and running in the direction of the longitudinal axis (8) and at least one guiding extension (29) on the cover element (3) engaging with the guiding groove (28). 92. Holding device according to claim 91, wherein several guiding grooves (28) are arranged evenly distributed around the circumference of the holding container (2). 93. Holding device according to claim 91, wherein a groove base of the guiding groove (28) over its longitudinal extension relative to the longitudinal axis (8) runs parallel to the latter. 94. Holding device according to claim 72, wherein the diametrically opposite locking devices (16) viewed in the direction of the longitudinal axis (8) are arranged around the circumference of the holding container (2) symmetrically between the guiding grooves (28). 95. Holding device according to claim 72, wherein between the holding container (2) and the cover element (3) a further guiding arrangement (52) is provided. 96. Holding device according to claim 72, wherein in order to form at least one part of a guiding arrangement (27, 52) a partial section (53, 54) of the inner surface (11) of the container wall (6) is designed as a guide track (55, 56) and is aligned over its longitudinal extension relative to the longitudinal axis (8) in parallel to the latter. 97. Holding device according to claim 96, wherein the partial section (53, 54) of the inner surface (11) or the inner surface (11) is designed to be cylindrical relative to the longitudinal axis (8). 98. Holding device according to claim 89, wherein the first guiding arrangement (27) is formed by the bearing or cooperation of the locking element (25) on the guide track (55) arranged on the holding arm (57). 99. Holding device according to claim 98, wherein the locking element or elements (25) lie with a predeterminable bearing force aligned radially in the direction of the guide track (55). 100. Holding device according to claim 99, wherein the bearing force is almost equal over the entire displacement path (58) of the cover element (3). 101. Holding device according to claim 95, wherein the additional guiding arrangement (52) in the region of the holding container (2) comprises at least one guide element (59), such as a web, a rib, arranged on the inner surface (11) thereof and projecting in the direction of the longitudinal axis (8) and projecting over the inner surface (11). 102. Holding device according to claim 101, wherein the guide element or elements (59) is or are aligned in the direction of the longitudinal axis (8). 103. Holding device according to claim 101, wherein two guide elements (59) arranged next to one another around the circumference form a portion of the additional guiding arrangement (52). 104. Holding device according to claim 103, wherein several guide elements (59) are provided, distributed evenly in pairs around the circumference, in particular arranged in the form of a cross. 105. Holding device according to claim 95, wherein the additional guiding arrangement (52) comprises at least one further guide track (56) which is arranged between the two adjacently arranged guide elements (59). 106. Holding device according to claim 95, wherein the additional guiding arrangement (52) in the region of the needle holder (4) comprises at least one guide extension (60) cooperating with the guide element or elements (59). 107. Holding device according to claim 106, wherein the guide extension or extensions (60) is or are arranged respectively between the two adjacent guide elements (59). 108. Holding device according to claim 72, wherein the first and the additional guide tracks (55, 56) arranged in the form of a cross relative to one another are offset relative to one another in circumferential direction by 90°. 109. Holding device according to claim 72, wherein at least one guide element (59) projects into at least one partial section (62) formed in the circumferential region of the cover element (3) or is in engagement with the latter. 110. Holding device according to claim 72, wherein the container wall (6) in the plane (20) aligned perpendicular to the longitudinal axis (8) has a circular cross section, and an external diameter (30) of the disc-shaped main body (21) corresponds approximately to an inner diameter (31) of the holding chamber (7) in this plane or is slightly smaller than the latter. 111. Holding device according to claim 72, wherein the holding container (2) is designed to be open in the region of the distal end (10) and closed in the region of the proximal end (9) partially by an end wall (13). 112. Holding device according to claim 111, wherein the end wall (13) has an opening (32) in the region of the longitudinal axis (8) which corresponds in its inner cross sectional dimension (33) approximately to an outer cross sectional dimension (34) of the needle holder (4). 113. Holding device according to claim 111, wherein in the end wall (13) there is a holding chamber (35) for the first adjusting device (15) or the one-piece component formed by the adjusting devices (15, 17). 114. Holding device according to claim 72, wherein the needle holder (4) is formed by a roughly sleeve-shaped supporting body (36). 115. Holding device according to claim 114, wherein on the sleeve-shaped supporting body (36) in the plane (20) aligned perpendicular to the longitudinal axis (8) at least one support element (37) projecting radially outwards over the carrier body is arranged. 116. Holding device according to claim 115, wherein on the support element (37) the adjusting devices (15, 17) are supported at the end regions facing one another. 117. Holding device according to claim 116, wherein at least one of the end regions is secured firmly to the support element (37). 118. Holding device according to claim 115, wherein the support element (37) in a one piece design of the adjusting device (15, 17) is arranged in a transition region thereof and is secured thereto. 119. Holding device according to claim 115, wherein the support element (37) is designed as a support element (48) running around the circumference and projecting over the supporting body (36) radially. 120. Holding device according to claim 114, wherein on the region of the support element (48) facing the proximal end (9) at least one first centring element (49) is arranged. 121. Holding device according to claim 114, wherein in the region of the needle holder (4) facing the distal end (10) a tubular depression (49) is arranged in the sleeve-shaped supporting body (36). 122. Holding device according to claim 114, wherein in the sleeve-shaped supporting body (36) a thread arrangement (43) is provided for the needle arrangement (14). 123. Holding device according to claim 122, wherein the thread arrangement (43) is aligned in such a way, that with an opposite arrangement and horizontal alignment of the releasable locking device (16) for the cover element (3) a tapering (45) on a cannula tip (44) is provided on an upper side of the cannula (5). 124. Holding device according to claim 72, wherein between the needle holder (4) and the holding container (2) an anti-rotational means (38) is arranged, which in the position of use of the needle holder (4) is in engagement and prevents a relative pivoting or rotation between the latter about the longitudinal axis (8). 125. Holding device according to claim 72, wherein the cover element (3) with the needle holder (4) located in the disposal position is secured in the region of the distal end (10) relative to the holding container (2) in its longitudinal movement in the direction of the longitudinal axis (8) by means of a locking device (39). 126. Holding device according to claim 125, wherein the locking device (39) comprises at least one retaining element (40) arranged on the holding container (2) and facing the distal end (10) and at least one locking element (41) cooperating therewith on the cover element (3). 127. Holding device according to claim 125, wherein the retaining element (40) is formed by a spring element of the container wall (6), which is designed at least over a portion of its longitudinal extension in the direction of the longitudinal axis (8) to project over the inner surface (11) in the direction of the longitudinal axis (8). 128. Holding device according to claim 125, wherein the retaining element or elements (40) are arranged in the region of the guiding arrangement (27), in particular in the guiding groove (28). 129. Holding device according to 124, wherein the locking device (39) comprises at least one stop element (42) for the cover element (3) arranged on the holding container (2) and facing the distal end (10). 130. Holding device according to claim 129, wherein the stop element or elements (42) are arranged in the region of the guiding arrangement (27), in particular in the guiding groove (28). 131. Holding device according to claim 72, wherein in the region of the distal end (10) of the holding container (2) on the latter at least one securing element (46) is arranged. 132. Holding device according to claim 131, wherein the securing element (46) is inserted into the holding container (7) and is locked onto the holding container (2). 133. Holding device according to claim 131, wherein the securing element (46) comprises a sleeve-shaped support element (63) and a flange-shaped step (64) connected therewith, which projects over the support element (63) in the direction away from the longitudinal axis (8). 134. Holding device according to claim 131, wherein on the sleeve-shaped support element (63) at least one positioning element (66) aligned in parallel direction to the longitudinal axis (8) is arranged, which projects over the support element (63) in the direction of the proximal end (9). 135. Holding device according to claim 134, wherein several, preferably four positioning elements (66) are provided distributed evenly around the circumference, in particular arranged in the form of a cross relative to one another. 136. Holding device according to claim 72, wherein the positioning element (66) projects into the additional guide track (56) arranged between the two adjacent guide elements (59). 137. Holding device according to claim 72, wherein in the disposal position the guide extension (60) of the needle holder (4) is supported at the end of the positioning element (66) facing the proximal end (9). 138. Holding device according to claim 72, wherein the locking device (39) comprises at least one retaining element (69) arranged on the securing element (46) and closer to the proximal end (9) and at least one locking element (25) on the cover element (3) interacting therewith, in particular the locking element (25) arranged on the holding arm (57). 139. Holding device according to claim 72, wherein the locking device (39) also comprises at least one stop element (68) for the cover element (3) arranged on the securing element (46) and facing the distal end (10). 140. Holding device according to claim 72, wherein in the disposal position an anti-rotational means (72) is in engagement between the securing element (46) and the cover element (3).
The invention relates to a holding device with a longitudinal, outer holding container for a holding vessel, in particular a blood sample collecting tube, in which the holding container surrounds a holding chamber with a container wall, and in the direction of a longitudinal axis comprises a proximal and distal end spaced apart from one another, and the container wall is delimited by an inner surface facing the holding chamber and an outer surface facing away therefrom, with a needle holder for a needle arrangement that can be mounted therein, in particular a double-ended cannula needle, whereby the needle holder in the holding chamber of the holding container is designed to be displaceable relative to the latter as required from a position of use in the region of the proximal end to a disposal position in the direction of the distal end, with a first adjusting device for the needle holder for the required displacement from the position of use to the disposal position with a cover element for the needle arrangement which can be mounted on the needle holder in the disposal position of the needle holder. From U.S. Pat. No. 5,810,775 A a holding device for medical blood sample collecting tubes is known, in which by means of a pivot movement of the closing element relative to the holding container an adjustment element arrangement in its holding chamber is adjusted by adjustment elements provided on the closing element in the direction of the longitudinal axis towards the proximal end, whereby the needle holder mounted in the region of the proximal end is released from its locked position in the adjustment element and after its release is returned by a preloaded spring element into the inner chamber of the holding device together with the needle arrangement. Because of the pivotal movement of the closing element in this embodiment there is, on the one hand, a longitudinal adjustment of the adjusting element in the direction of the longitudinal axis and, on the other hand, after releasing or unlocking the needle holder from the adjustment element the inner chamber of the holding device is sealed, whereby the operator is prevented from coming into contact with the needle arrangement. The disadvantage of this embodiment is that the connection between the needle holder and the adjusting element in the form of a locking fit is very expensive and has to be carried out precisely, in order, on the one hand, to obtain sufficient locking fit for the collection process, and, on the other hand, to make sure the necessary releasing force for unlocking the connection is not too great. In addition, due to the spring preloading of the needle holder, if there is an unintentional release of the locked connection between the needle holder and the adjustment element, caused by the rapid return of the needle into the inner chamber, there is a high risk of injury to the user of this holding device. A further holding device for blood collecting devices is known from U.S. Pat. No. 5,769,826 A or WO 98/41249 A1, in which a needle holder preloaded by a spring is held locked in the holding container by a slide in the position of use, and after the correctly performed collection procedure the lock between the slide and the needle holder can be released, whereby the latter is returned due to the spring preloading with the needle arrangement into the inner chamber of the holding device. The distal end of said holding device is designed to be closable as necessary by a sealing element arranged pivotably on the holding container. The disadvantage here is that on activating the slide and the restoring movement associated therewith, due to the force of the spring preloading there is a return adjustment of the needle holder into the inner chamber, whereby if the cap or sealing element is not closed operating personnel are at risk of needle sticks. From the patent U.S. Pat. No. 5,407,436 A and WO 93/23098 A1 a holding container is known with a holding device for a needle holder and a double needle inserted therein, in which the needle holder equipped with the double needle can be retracted automatically into the inside of the holding container of the holding device after releasing a retaining device into the holding chamber. The needle holder is hereby fixed by securing elements at one end of the holding container, whereby between the front end and the needle holder a compressed and thus preloaded spring is arranged, which exerts force running parallel to the longitudinal axis of the holding container onto the needle holder. By means of this force the needle holder is pressed against the holding catches of several securing elements. The securing elements are designed as finger-like projections of the holding container running parallel to the middle longitudinal axis, and are arranged in such a way that they surround a disc-like shaped part of the needle holder over its circumference, and their holding catches aligned inwards in the direction of the middle longitudinal axis project, so far over the edge of the disc-shaped part of the needle holder, that the latter is secured against the effect of the spring. In order to trigger the automatic return of the needle a tube-like plunger is used, which at the end to be inserted into the holding container of the holding device has an outwards pointing truncated-cone shaped tapering part. If said plunger is pushed so far into the holding device that the truncated-cone shaped tapering is in contact with the holding catches, the securing elements with the holding catches are pressed apart to the side pointing away from the longitudinal axis, whereby the needle holder is released and displaced due to the spring force into the holding chamber. The disadvantage of this is that a separate component is needed for the release and single-handed operation is therefore not possible. A further collecting device is known from U.S. Pat. No. 5,423,758 A and WO 95/16389 A1, in which the removal needle is held together with the needle holder in an adjustment sleeve and is surrounded by an additional protective sleeve, so that the removal needle is completely protected from the collecting process. A spring device is arranged between the needle holder and the outer protective sleeve. The needle holder is held by means of a clamping fit in the adjustment sleeve, whereby for appropriate use the adjustment sleeve is displaced relative to the outer protective sleeve, and then the spring device is preloaded. At the same time one end of the collecting needle moves out of the protective sleeve so that the collecting procedure can be performed. In this case the spacings or stops between a grip arranged on the adjustment sleeve and the protective sleeve interacting therewith are defined, so that for a correctly performed collecting procedure the spring device is only preloaded sufficiently that the secure fit of the needle holder in the adjustment sleeve is not released. In this position there is a mutual locking between the protective sleeve and the adjustment sleeve, in order to avoid repeated pulling apart between the latter. After the collection procedure the displaceable grip on the adjustment sleeve is moved into a further position spaced apart from the protective sleeve, whereby due to this spacing there can be a further relative displacement between the protective sleeve and the adjustment sleeve, and the secure fit of the needle holder is achieved by the preloaded spring device, and after releasing the secure fit the needle holder returns into the inner chamber of the adjustment sleeve. The disadvantage of this is that a large number of adjustment procedures need to be carried out between the individual components of the collecting device in order to ensure reliable functioning. At the same time it is possible to reach into the inside of the adjustment sleeve, which can result in unwanted needle stick injuries for the operating personnel. A further safety collecting device is known from US 2002/0099355 A1 in which the entire needle holder with the injection needle for the blood sample collecting tube arranged thereon and arranged at an angle in a separate longitudinal guide can be returned by an operator from the position of use to the disposal position. The disadvantage of this is that in the disposal position it is still possible to reach into the inner chamber of the holding device. The objective of the present invention is to create a holding device, in which after appropriate use the needle holder can be adjusted by the operator into the inner chamber of the holding device, and the inner chamber is automatically closed off preventing undesirable contact with the returned collecting needle. The objective of the invention is achieved in that the cover element is arranged in the position of use of the needle holder adjacent to the latter on the side in the holding chamber pointing away from the proximal end, and is held by a releasable locking device between the cover element and the holding container in the position of use relative to the latter, and a further adjusting device is arranged between the needle holder and the cover element, whereby on releasing the locking device the cover element is displaced by the additional adjusting device in the direction of the distal end of the holding container. The resulting surprising advantage of this is that by means of the immediately adjacent arrangement of the needle holder and the cover element inside the holding container, the entire holding device is ready for appropriate use without any need for preparative steps, and the locking device can be released by the respective operator single-handedly. This can be achieved very easily by the arrangement of the locking device on the holding container by the preloaded and locked cover element in cooperation with the also preloaded needle holder. In this way, on the one hand, a safe operation is ensured and once the collecting procedure has been completed a secure closure of the inner chamber by the cover element for the cannula end facing the inner chamber or the distal end is achieved. In this way unintentional access to the inner chamber and the risk of unwanted needle stick injury is prevented, whereby the risk of infection to the operator is much reduced, if not eliminated. At the same time however an inexpensive holding device is created which requires only a small number of components and at the same offers a high degree of operational safety. A further embodiment according to claim 2 is also advantageous as thereby the needle holder can also be returned safely into its disposal position even after a longer storage period, and thus a high degree of operational safety is ensured. A design according to claim 3 is also advantageous, as thereby, on the one hand, the needle holder is positioned in the direction of the longitudinal axis of the holding container in its position of use, and, on the other hand, after releasing the locking device the cover element is arranged by means of the further adjusting device with a simultaneous adjustment of the needle holder spaced apart from the latter in the disposal position inside the holding container, and thus the automatic covering of one needle end of the needle arrangement is ensured. By means of the design according to claim 4 it is possible to arrange the needle holder between both adjusting devices, whereby the insertion of the needle holder from the larger end to the smaller end is made possible. In a further design variant according to claim 5 a simple structural unit is created, inside which the needle holder can be clamped between the windings, and thus, on the one hand, there can be a precise longitudinal positioning in the direction of the longitudinal axis of the holding container, and, on the other hand, a compact structural unit is obtained. Furthermore, by means of the conically expanding additional adjusting devices the assembly of the needle holder with the adjusting device can be much simplified. A development according to claim 6 is also advantageous as thereby operation, in particular one-handed operation, is simplified, whereby due to the symmetrical release of the locking device no additional steps have to be carried out, and thus the end of the needle arrangement designed for removal or collection, for example from the arteries or veins of a patient, can be retracted by the first adjusting device without changing the position of the holding container relative to the patient. At the same time, the other end of the double-ended cannula can be covered in the region of the distal end, which prevents access and thereby the risk of needle stick injury from both ends of the cannula needle. In this way simple single-handed operation is made possible, whereby both ends of the needle arrangement are arranged additionally inside the holding container, and unintentional needle stick injury can also be prevented in the region of the distal end. In the design according to claim 7 it is an advantage, that with the least longitudinal extension in the direction of the longitudinal axis, on the one hand, the insertion of the blood sample collecting tube for the appropriate collection procedure and the injection procedure in one end of the cannula is made reliably possible and, on the other hand, in the disposal position an operationally secure covering of this cannula end is made possible. By means of the development according to claim 8, with the least space in the position of use the end of the cannula facing the blood sample collecting tube can penetrate the cover element, and in the disposal position despite this the cover element can securely cover this end. By means of the design according to claim 9 residue on the cannula needle or the protective sheath surrounding latter can be suctioned off or removed during the relative adjustment movement between the cover element and the needle holder, and thus infection caused by spraying out of individual particles, especially body fluids such as blood or the like, can be prevented. A design according to claim 10 is also advantageous as thereby, on the one hand, the cover element can be secured and in association with this the needle holder can be secured inside the holding container, and, on the other hand, the user can perform an even release by means of the diametrically opposite locking elements. In this way the tilting of the components to be adjusted inside the holding container is also prevented. According to the designs described in claims 11 to 13, a simple interaction of the locking elements on the cover element with the locking recesses arranged in the container wall can be achieved, whereby here a simple operation i.e. simple pressure in the direction of the longitudinal axis, i.e. the centre of the holding container, is performed for releasing the locking device. Due to the multiple arrangement of the locking elements on the cover element on releasing the locking device by means of the additional locking elements the cover element can be supported or centred relative to the holding container, whereby a secure release with a simultaneously associated guiding performed immediately afterwards is achieved during the entire adjustment up to the disposal position. The design according to claim 14 is also advantageous, as thereby a simple operation of the locking device is made possible from the outside of the holding container. As described in claim 15, on the one hand, an unintentional release due to the possible projection of the locking elements on the outer surface of the container wall is prevented, and, on the other hand, the required displacement path for triggering the locking device is set to a predeterminable path, in order to prevent misuse or unintentional triggering. A design according to claim 16 is advantageous, as thereby there is continuously a secure locking of the locking device in the position of use and thus a high degree of operational safety is achieved for the entire holding device. According to the designs described in claims 17 and 18, the main body is spaced apart from the inner surface of the holding container, whereby the guiding arrangement between the cover element and the holding container is reduced to a small area viewed in radial direction relative to the entire circumference and thus a smooth and tilt-free guiding arrangement is provided. A further development according to claim 19 is also advantageous, as in this way, on the one hand, for the assembly procedure and, on the other hand, over the entire displacement of the cover element between its two end positions, the adjusting device is constantly held in a predeterminable position on the main body and thereby a smooth sequence of movement is ensured. According to advantageous developments according to claims 20 to 23, during the relative adjustment of the cover element in the direction of the longitudinal axis relative to the holding container, a tilt-free longitudinal movement is ensured, without the cover element being able to rotate about the longitudinal axis. In the design according to claim 24 it is advantageous, that over the entire displacement path of the cover element the distance between the groove base of the guiding groove and the longitudinal axis is constant. In this way a secure longitudinal adjustment of the cover element is achieved between its two end positions. The design according to claim 25 ensures the aligned arrangement and releasing of the locking device with perfect guiding in the direction of the longitudinal axis. A further embodiment according to claim 26 is also advantageous, as thereby also the cover element is guided continually over its entire longitudinal movement in the direction of the longitudinal axis between its two end positions, and thus a high degree of operational safety of the entire holding device can be achieved. A development according to claim 27 is also advantageous, as in this way a parallel alignment of the guide tracks relative to the longitudinal axis is achieved, and thus over the entire displacement path the distance between the longitudinal axis and the guide tracks remains the same. By means of the design according to claim 28, it is possible to achieve perfect guiding between the position of use and the disposal position of the parts to be displaced inside the holding container, whereby a high degree of operational safety and sufficient protection for operating personnel is ensured. Further advantageous designs of the guiding arrangement are described in claims 29 to 31. The advantage in this case is that by means of the bearing force applied by the locking elements on the guide track, the cover element is always aligned centrally to the longitudinal axis, and due to the predeterminable bearing force constant frictional ratios, provided there is a consistent surface quality, can be achieved for the entire displacement. Further advantageous designs of the additional guiding arrangement are characterised in claims 32 to 34, whereby a predetermined, straight guiding arrangement has also been provided for the needle holder, by means of which a secure adjustment of the latter from the position of use to the disposal position is made possible. By means of the multiple arrangement of the guiding elements a tilt-free and mainly rotationally secure longitudinal movement is achieved. By means of the design according to claim 36, in addition to the guiding elements in the region of the inner surface of the holding container an additional further guiding possibility is created, whereby the needle holder can be adjusted more precisely in the direction of the longitudinal axis. By means of the further developments of the additional guide arrangement, according to claims 37 to 40, on the one hand, a precise and mainly rotationally secure longitudinal guiding of the needle holder is achieved in the region of the inner surface of the holding container, and, on the other hand, longitudinal movement into the disposal position is ensured, so that the risk of injury to the operating personnel is much reduced. The design according to claim 41 is advantageous, as thereby longitudinal displacement can occur in the region between the cover element and the inner surface of the holding container, whereby unintentional access to the inner chamber of the holding container closed off by the cover element is reliably prevented. According to claim 42 the simple insertion of the structural unit formed by the needle holder and the cover element into the holding container is made possible, whereby support is provided in the region of the other end for the structural unit spring-mounted there. In the design according to claim 43 in the region of the end wall a longitudinal guide for the needle holder is created, in order to absorb lateral loads during correct usage, and then after the correct usage to permit a simple sliding movement between said components. According to claim 44 for the adjusting device a holding chamber for the adjusting device separate from the needle holder is made possible, in order over the smallest area to store a sufficient restoring force applied by the adjusting device, and in addition to prevent clamping between the components during appropriate use. By means of the design according to claim 45 a double-ended collection needle can be inserted in the sleeve-shaped carrier body, whereby in the region of the outer surface there can be additional support on the holding container. In the design according to claim 46 it is advantageous that here the adjusting devices can be supported to secure the position of the entire needle holder during its correct usage in: the position of use. Advantageous designs and arrangements of the adjusting devices on the support element are described in claims 47 to 49, as thereby with defined positioning of the needle holder relative to the holding container, also during assembly, a simple and easily assembled structural unit is created. Further advantageous designs of the needle holder are described in claims 50 to 52, whereby all-round continuous support for the first adjusting device with simultaneous centring of the latter relative to the needle holder can be achieved. By means of the tubular depression for the additional adjusting device a predeterminable support position is created, whereby the needle holder is positioned between the two adjusting devices, and thus a high degree of operational safety can be achieved. Furthermore, the centring element can also be used for the oriented alignment of the needle holder for insertion into the holding container, in order to be able thus to secure the alignment of the needle arrangement to be used into the thread arrangement relative to the locking device. As described in claims 53 to 54 a predefined positioning of the cannula tip, in particular the tapered section for the insertion of the needle, can be created relative to the locking device, in order to permit simple one-handed use without the risk of a needle stick injury caused by otherwise necessary adjustment procedures. By means of the design according to claim 55 simple handling is achieved for the use of the collecting needle in the needle holder, as here the entire collecting container can be held simply, and the collecting needle can be simply screwed into the needle holder without requiring further fixing. Further advantageous designs of the cover element and the holding container are characterised in claims 56 to 59, whereby a repeat return of the cover element into the holding chamber of the holding container is prevented, and thus an undesired needle stick injury can be prevented along with the associated risk of possible infection. In the design according to claim 60 the undesirable exit of the cover element from the holding chamber of the holding container is prevented, whereby in cooperation with the restoring elements, there is a clear fixing of position in the direction of the longitudinal axis. Furthermore, in this way the spring force of the adjusting devices can be increased, as in this way an undesired exit is reliably prevented. A design as described in claim 61 is also possible, as in this way an additional anti-rotational means for the cover element about the longitudinal axis relative to the holding container is provided. By means of the developments according to claims 62 and 63 in the region of the distal end, on the one hand, the assembly is made simple with a not yet inserted securing element, and on the other hand, after the insertion of the securing element into the holding container the entire holding device has a high degree of operational safety. A design according to claim 64 is also advantageous, as thereby a precise insertion of the securing element into the distal end of the holding container is possible, and at the same time in cooperation with the flange-shaped step a definite positioning inside the holding container can be achieved. Developments according to claims 65 to 68 are also advantageous, as in this case, on the one hand, the insertion of the securing elements is made easy by the projecting positioning elements, and on the other hand, a stop for the displacement path of the needle holder, and thereby a secure positioning of the latter inside the holding container in is achieved in the disposal position. In this way the needle holder can be pressurised with a greater spring force by the adjusting device, by means of which the latter is then pressed securely against the positioning elements. Designs, as described in claims 69 to 70 are also possible, as thereby the cover element in the disposal position of the holding device in both directions is held in the direction of the longitudinal axis on the securing element. In this way the cover element can be pressurised by the additional adjusting device with a greater spring force, in order to achieve a secure adjustment of the latter to the disposal position. This is mainly significant for the locking elements arranged on the holding arm, as the latter have to be adjusted to obtain the disposal position by means of the retaining elements, in order to reach the disposal position. Finally, a development, as characterised in claim 71 is advantageous, as thereby even in the disposal position pivoting and rotation about the longitudinal axis is prevented, and thus subsequent manipulation is prevented. In this way, on the one hand, injury to the operating personnel can be prevented, and on the other hand, the reuse of the entire holding device with the already unlocked locking device can also be prevented. The invention is explained in more detail in the following with reference to the embodiments illustrated in the drawings. FIG. 1 shows a side view of the holding device according to the invention in cross section, and in a simplified schematic view, in its position of use; FIG. 2 shows the holding device according to FIG. 1 in the disposal position of the needle holder and simplified schematic view; FIG. 3 shows the holding container for the holding device according to FIGS. 1 and 2, in diagrammatically simplified view; FIG. 4 shows the holding container according to FIG. 3 in a different, diagrammatically simplified view; FIG. 5 shows the needle holder for the holding device according to FIGS. 1 and 2 with a needle arrangement inserted therein in a diagrammatically simplified view; FIG. 6 shows the cover element for the holding device according to FIGS. 1 and 2 in diagrammatically simplified view; FIG. 7 shows an additional holding device in the position of use, in cross section in side view and simplified schematic view; FIG. 8 shows the holding device according to FIG. 7 in the disposal position, in cross section in side view, but rotated by 90° compared to FIG. 7; FIG. 9 shows the holding container according to FIGS. 7 and 8 in simplified perspective view; FIG. 10 shows the holding container according to FIG. 9 in a different simplified perspective view; FIG. 11 shows the cover element according to FIGS. 7 and 8 in simplified perspective view; FIG. 12 shows the cover element according to FIG. 11 in a different simplified perspective view; FIG. 13 shows the needle holder according to FIGS. 7 and 8 in simplified perspective view; FIG. 14 shows the needle holder according to FIG. 13 in a different simplified perspective view; FIG. 15 shows the securing element according to FIGS. 7 and 8 in simplified perspective view; FIG. 16 shows the securing element according to FIG. 15 in a different simplified perspective view; FIG. 17 shows the holding device according to FIGS. 7 and 8 in a view of the distal end but with a removed securing element; FIG. 18 shows the holding device according to FIGS. 7 and 8 in a simplified perspective view in its disposal position, but with removed holding container and a modification of the anti-rotational means in the region of the needle holder compared to the view in FIGS. 13 and 14. First of all, it should be mentioned that in the various embodiments described the same parts are allocated the same reference numbers and the same component names, whereby the disclosures contained in the entire description can be applied to the same parts with the same reference numbers or same component names. In addition, the descriptions of positions such as e.g. top, bottom, side etc. refer to the drawing currently being described, and when the position changes should be understood to apply to the new position. Furthermore, individual features or combinations of features from the various embodiments shown and described can represent independent, inventive solutions of the invention. In FIGS. 1 to 6 a holding device 1 for a holding vessel, not shown here in detail, such as a generally known blood sample tube, is illustrated in a simplified manner, and the latter comprises an outer holding container 2 and cover element 3 inserted therein and a needle holder 4 with a mostly double-ended cannula needle 5. The holding container 2 has a longitudinal shape and defines a holding chamber 7 with its container wall 6. In the direction of the longitudinal axis 8 the holding device 1 or the holding container 2 comprises a proximal end 9 and a distal end 10 spaced apart from one another. The container wall 6 is delimited by an inner surface 11 facing the holding chamber 7 and an outer surface 12 facing away from the latter. In the embodiment shown here one of the two ends—in the present embodiment the distal end 10 is designed to be open and the other end—here the proximal end 9—is designed to be at least partly closed. The proximal end 9, which is partly closed here, is partially closed by an end wall 13. In general, it should be pointed out that the two ends 9, 10 have been named from the perspective of the patient. Thus the proximal end 9 faces the patient and the distal end 10 is furthest away from the latter. In the position of use of the needle holder 4 and a needle arrangement 14 mountable therein shown in FIG. 1, which in the present embodiment is in the form of a double-ended cannula 5, one end, which is designed for inserting into a living being or a collecting vessel, projects over the end wall 13 in the direction opposite the holding chamber 7. The other end of the cannula 5 projects over a partial section into the holding chamber 7 of the holding container 2, whereby in a known manner a holding vessel not shown in more detail here, in particular a blood sample collecting tube is inserted into the holding chamber 7 and the sealing device of the blood sample collecting tube is pierced by this end of the cannula 5, and thus a connection via the cannula 5 can be made with the inner chamber of the blood sample collecting tube. Furthermore, the needle holder 4 in the holding chamber 7 of the holding container 2 is designed to be displaceable relative to the latter, as required from the position of use shown in FIG. 1 in the region of the proximal end 9 in the direction of the distal end 10 into a disposal position according to FIG. 2. In addition, a first adjusting device 15 for the displacement from the position of use into the disposal position is allocated to the needle holder 4. The cover element 3 is arranged in FIG. 1—the position of use of the needle arrangement 14—immediately adjacent to the needle holder 4 on the side facing away from the proximal end 9 in the holding chamber 7. Between the cover element 3 and the holding container 2 of the holding device 1 it is also shown in FIG. 1, that here a releasable locking device 16 is arranged, by which the cover element 3 is held in the position of use relative to the holding container. Furthermore, between the needle holder 4 and the cover element 3 a further adjusting device 17 is arranged, whereby on releasing the locking device 16 the cover element 3 is adjusted by the additional adjusting device 17 in the direction of the distal end 10 of the holding container 2. Thus, on the one hand, on the side facing the end wall 13 the first adjusting device 15 and, on the other hand, on the side facing the cover element 3 the additional adjusting device 17 is allocated to the needle carrier 4 and by means of these two adjusting devices 15, 17 is mounted in the position use in the direction of the longitudinal axis 8. The additional adjusting device 17, as already described above, is arranged between the needle holder 4 and the cover element 3, whereby by means of the locking device 16 the cover element 3 is secured in position relative to the holding container 2, if necessary detachably. Advantageously, the first adjusting device 15 and/or the additional adjusting device 17 are both formed by an elastically deformable spring element 18, 19, in particular a compression spring. Said compression springs can be made from various different materials and have various different deformation and spring properties, whereby preferably spiral springs are used. It is also advantageous if the additional adjusting device 17 is designed to expand conically from the needle holder 4 to the cover element 3, as is shown in a simplified view in FIG. 2. Regardless of this it is also possible to design the first and the additional adjusting device 15, 17 as a one-piece component, as in this way the assembly cost and the number of individual parts can be reduced. Due to the arrangement of the two adjusting devices 15, 17 both the needle holder 4 and the cover element 3 are adjusted simultaneously from the position of use into the disposal position after releasing the locking device 16. The cover element 3 is in this embodiment in the form of a roughly disc-shaped main body 21 lying in a plane 20 perpendicular to the longitudinal axis 8. As already described, the end of the cannula 5 facing the blood sample collecting tube and thereby the holding chamber 7 in the region of the longitudinal axis 8 passes through an opening 22. Furthermore, it is shown in simplified manner in FIG. 2, that in the region of the opening 22 a component 23 for suctioning or absorbing a fluid can be arranged, which can be penetrated by the cannula 5 or the protective sleeve 24 arranged over the latter and shown in simplified form. Said component 23 serves to absorb or suction up any possible residue found in the region of the cannula 5 or on the protective sleeve 24, in particular drops of blood, during the relative displacement between the needle holder 4 and the cover element 3, determined by the displacement device 17, in order to avoid spraying out and possible infection of the operator. The locking device 16 comprises at least one, preferably two, diametrically opposite locking elements 25 and locking recesses 26 cooperating with the latter. In this embodiment the locking element or elements 25 is or are arranged on the disc-shaped main body 21 of the cover element 3, whereby the locking recesses 26 are arranged in the container wall 6 of the holding container 2, and pass through the latter to release the locking elements 25 from outside the holding container 2. In order to prevent the unintentional release of the locking elements 25 from the locking recesses 26, it is advantageous if the locking element or elements 25 project in radial direction from the inner surface 11 to the outer surface 12 of the container wall only partially into the locking recesses 26. In this way the release path is reduced in radial direction to the longitudinal axis 8 and at the same time the risk of incorrect use or unintentional release is reduced. The locking element or elements 25 are resiliently connected, for example by a web, with the disc-shaped main body 21 of the cover element 3. In this case the locking elements 25 project by means of the resilient web in the direction of the needle holder 4 from a disc-shaped main body 21. Furthermore, between the cover element 3 and the inner surface 11 of the container wall 6 at least one guiding arrangement 27 can be provided, by means of which the cover element 3 can be displaced in an exclusively longitudinal movement in the direction of the longitudinal axis 8 from the position of use into the disposal position in the region of the distal without rotation occurring about the longitudinal axis 8. Said guiding arrangement 27 is formed by at least one guiding groove 28 indented in the container wall 6 and running in the direction of the longitudinal axis 8, and forms at least one guide extension 29 on the cover element 3 engaging in the guiding groove 28. In order to achieve a tilt-free longitudinal adjustment in the direction of the longitudinal axis 8 it is advantageous if several guiding grooves 28 are arranged, distributed evenly around the circumference of the holding container 2, with which several guide extensions 29 of the cover element 3 engage. With a diametrically opposite arrangement of the locking devices 16 the latter are arranged viewed in the direction of the longitudinal axis 8 around the circumference of the holding container 2 symmetrically between the guiding grooves 28, as thus, on the one hand, a perfect release and, on the other hand, an unhindered longitudinal adjustment of the cover element 3 can be achieved in the direction of the longitudinal axis 8 inside the holding container 2. It is also advantageous if a groove base of the guiding groove 28 over its longitudinal extension relative tot the longitudinal axis 8 runs parallel to the latter. The container wall 6 has a circular cross section in the plane 20 perpendicular to the longitudinal axis 8, whereby an outer diameter 30 of the disc-shaped main body 21 corresponds approximately to an inner diameter 31 of the holding chamber 7 in the same plane or is only slightly smaller. In this way it is ensured that, on the one hand, there can be an unrestricted longitudinal displacement of the cover element 3 in the direction of the longitudinal axis 8 inside the holding chamber 7, and on the other hand, at the same time the holding chamber 7 is covered by the cover element 3 over a large part of the cross section surface. The holding container 2 is open in the region of the distal end and in the region of the proximal end 9 is partially closed by the end wall 13. In this way, in the region of the proximal end 9 it is possible to support the compression forces exerted by the adjusting device 15 on the end wall 13. Furthermore, an opening 32 is arranged in the end wall 13 in the region of the longitudinal axis 8, which in its cross sectional dimension 33 corresponds approximately to an outer cross sectional diameter 34 of the needle holder 4. In this way, as can best be seen from FIG. 1, a partial section of the needle holder 4 can project into the opening 32, whereby the insertion of the needle arrangement 14, in particular the cannula 5, into the needle holder 4 can be made easier. Furthermore, in the end wall 13 there is a holding chamber 35 for the first adjusting device 15 or the one-piece component formed by the adjusting devices 15, 17. In this way in the smallest space both the needle holder in its bearing, guided in the direction of the longitudinal axis 8, and the adjusting device 15 or the component formed by the latter, can be mounted and secured separately therefrom. The needle holder 4 is in the form of a sleeve-shaped supporting body 36, whereby in the plane 20 perpendicular to the longitudinal axis 8 at least one support element 37 is arranged thereon which projects radially outwards over the latter. Said support element 37 is preferably designed to be continuous around the circumference and is used, so that the adjusting devices 15, 17 are supported on the respectively facing end regions. It is also possible however to arrange several support elements 37 around the circumference on the supporting body 36. For better securing of the needle holder 4 relative to the adjusting devices 15, 17 it is advantageous if at least one of the end regions is secured to the support element 37. In this way the cost of final assembly can be reduced. With a one-piece design of the adjusting device 15, 17 the support element 37 is arranged in a transition region of the latter and mounted on the one-piece component. If, as already described, the additional adjusting device 17 or the part of the one piece component forming the latter is designed to be conical in the direction of the distal end 10, the use of the needle holder 4 with the support element arranged thereon is possible up to the transition area, whereby then the support element 37 can be inserted and secured accordingly between the windings of the adjusting device. Furthermore, it can also be seen from FIG. 3, that in the region of the opening 32 in the end wall 13 between the latter and the portion of the needle holder 4 projecting into the opening 32 (cf. FIG. 1) an anti-rotational means 38 is arranged, which is in engagement in the position of use of the needle holder 4, and prevents relative pivoting or rotation between the holding container 2 and the needle holder 4 about the longitudinal axis 8. This anti-rotational means 38 is in the present embodiment in the form of a flattened section on the supporting body 36, and in the region of the opening 32 has corresponding, mutually designed stop surfaces. In this way a longitudinal movement of the needle holder 4 in the direction of the longitudinal axis 8 is possible but rotation is prevented about the longitudinal axis 8 in the position of use. Furthermore, as can be seen from an overview of FIGS. 1, 2 and 4, if the needle holder 4 is in the disposal position, the cover 3 element is moved into the region of the distal end—according to drawing FIG. 2—by the interaction of the adjusting devices 15, 17 and is secured there relative to the holding container 2 in its longitudinal movement in the direction of the longitudinal axis 8 by means of a locking device 39. In this embodiment the locking device 39 is formed by at least one retaining element 40 arranged on the holding container 2 and facing the distal end 10, and at least one locking elements 41 cooperating therewith on the cover element 3. In this way the retaining element or elements 40 can be formed respectively by a spring section of the container wall 6, which are designed to project over at least a portion of their longitudinal extension in the direction of the longitudinal axis 8 over the inner surface 11 in the direction of the longitudinal axis 8. Due to the resilient design of this retaining element 40 movement of the cover element 3 from the proximal end 9 towards the distal end 10 is made possible, whereby the retaining elements 40 are displaced radially outwards against their spring effect to the side facing away from the longitudinal axis 8 and thus the passage of the cover element 3 is made possible up to the renewed expansion of the retaining elements 40. If the retaining elements 40 are returned or expanded to their original position, movement of the cover element 3 in the direction of the proximal end 9 is prevented. In this way unintentional access to the holding chamber 7 of the holding container 2 and the needle arrangement 14 located therein is reliably prevented. In order to avoid the exit of the cover element 3 during the displacement movement into the disposal position out of the holding chamber 7 of the holding container 2, the locking device 39 also comprises at least one stop element 42 for the cover element 3 arranged on the holding container 2 and facing the distal end 10. In this way the cover element 3, viewed in the direction of the longitudinal axis 8, is secured on both sides from moving, and is thus secured in the disposal position. The retaining element or elements 40 is or are arranged in the region of the guiding arrangement 27, in particular in the guiding groove 28 in the end region facing the distal end 10. At the same time however the stop element or elements 42 are arranged in the region of the guiding arrangement 27, in particular in the guiding groove 28. As is generally known, in the sleeve-shaped supporting body 36 of the needle holder 4 a thread arrangement 43 for the needle arrangement 14 is arranged, whereby the thread arrangement 43 is aligned, so that with an opposite arrangement and horizontal alignment of the releasable locking device 16 for the cover element 3 a tapering 45 on a cannula tip 44 is arranged on an upper side of the cannula 5, as can best be seen from FIG. 1. In this way for the drawing procedure or appropriate use the entire holding device 1 can be held, for example in a right-handed operation, by the thumb and index finger and already in the region of the locking device 16, whereby at the same time the cannula 5 is arranged in the correct position for the collecting procedure, namely with the tapering on the visible side of the cannula 5 facing the user. In this way a continually aligned position is ensured after the insertion of the needle arrangement 14 into the needle holder 4 relative to the entire holding device 1. Any rotation or displacement or additional manipulation of the cannula and the associated risk of stick injury is thus very unlikely if not eliminated. In FIGS. 7 to 17 a further possibility of a design of the holding device 1 is shown in simplified form for a holding vessel, not shown in detail here, such as for example a generally known blood sample tube. At the same time the same reference numbers and names are used for the same parts. In order to avoid unnecessary repetition reference is made to the detailed description in the preceding FIGS. 1 to 6. FIG. 18 basically shows the components shown in FIGS. 7 to 17, but with a modification of the anti-rotational means 38 between the needle holder 4 and the holding container 2. The holding device 1 comprises in this embodiment the holding container 2, the cover element 3, the needle holder 4 with the needle arrangement 14 inserted or insertable therein, mostly the double-ended cannula 5. In addition, the holding device 1 comprises in the region of the distal end 10 of the holding container 2 at least one securing element 46 inserted therein, which is shown in simplified and schematic form in perspective view in FIGS. 15 and 16. FIG. 7 shows, as already illustrated in FIG. 1, the position of use in which the needle holder 4 with the cannula inserted or insertable therein and the cover element 3 in the region of the proximal end 9 of the holding container 2, and the two adjusting devices 15, 17 are in a preloaded position, from which the latter after unlocking the locking device 16 move or adjust the needle holder 4 and the cover element 3 into the disposal position by means of the spring force acting on said parts. Said adjustment procedure has already been described in detail in the preceding FIGS. 1 to 6 and is not discussed further at this point. The securing element 46 is inserted into the holding chamber 7 of the holding container 2 and can be locked or is locked onto the latter. In this way it is possible to insert the needle holder 4, the cover element 3, and if necessary the cannula 5, and the adjusting devices 15, 17 or an individual component formed from these two components into the holding chamber 7 of the holding container 2, and to position the locking device 16 in the region of the proximal end 9 in its locked position and only then use the securing element 46 afterwards. In this way the assembly is simplified, as over the entire insertion of the previously described individual parts in the region of the proximal end 9 the holding container 2 in the region of its distal end 10 has no retaining or stop elements, and thus the insertion procedure can be performed easily and mostly unhindered. As can be seen from the simplified illustration of the holding device 1 in FIGS. 7 and 8, the first adjusting device 15 is arranged between the end wall 13 and the needle holder 4. In order to centre or stabilise the adjusting device 15 in the region of the end wall 10 on the side facing the holding chamber there is a groove-shaped depression 47 in which one end of the adjusting device 15 is inserted. The other end of the adjusting device 15 is supported on at least one support element 37 projecting over the sleeve-shaped supporting body 36 radially outwards. In this embodiment the support element 37 is designed as a support element 48 that passes around the circumference and projects over the supporting body 36. In addition, it is also possible to have at least one first centring element 49 for the first adjusting device 15 arranged in the region of the support element 48 or the support element 37 facing the proximal end 9. By means of the interaction of the supporting body 36 with the centring element or elements 49 the first adjusting device 15 is positioned relative to the needle holder 4. Furthermore, the centring element 49 can also be used for prior orientation and subsequently for the correct positional insertion of the needle holder 4 into the holding chamber 7. As the thread arrangement 43, as already described in FIGS. 1 to 6, and explained again briefly in the following, has to adopt a definite predetermined position relative to the holding container 2 and the locking device 16 arranged between the latter and the cover element 3 for the alignment of the cannula tip, this predetermined insertion position is important for this procedure. In this way with a single-handed operation of the holding device 1 by a simple releasing of the locking device 16 the end of the cannula 5 located during appropriate use can be removed from the patient by the displacement forces applied by the adjusting devices 15, 17 without having to be held, and thus a change in position of the entire holding device 1 has to occur in relation to the patient. In this way, the removal of the cannula end from the patient is possible in a single-handed operation, for example by the interaction of the thumb and index finger, and the injection site can be covered with a swab by the other free hand. In this way the operating personnel experience a high degree of safety and the risk of injury from unintentional needle sticking and an associated infection is much reduced if not eliminated altogether. Furthermore, in the centre of the sleeve-shaped supporting body 36 is the thread arrangement 43 for the needle arrangement 14, which is aligned with the threads of the needle arrangement 14 in such a way, that in a completely screwed in position a shorter opening axis of the opening at the tapered cannula tip in the region of the proximal end 9 is aligned roughly parallel to the two opposite locking recesses 26. The thread arrangement 43 for the needle arrangement 14 can be a two-threaded thread, whereby the thread segments are aligned in such as way that with the opposite arrangement and horizontal alignment of the releasable locking device 16 for the cover element 3, a tapering 45 arranged on a cannula tip 44 is provided on an upper side of the cannula 5, as already explained in the description and illustration in the drawing of FIG. 1. Irrespective of this however, of course any other coupling device can be used to connect the needle arrangement 14 and the needle holder 4. At the same time the needle arrangement 14 can also comprise only one cannula 5 with a suitably designed retaining section, whereby the cannula 5 faces the proximal end 9 exclusively and does not project into the holding chamber 7. Thus a syringe needle could also be used. It can also be see from FIG. 8, that the locking device 16 in the region of the holding container 2 has at least one projection assigned to the locking elements 25 and projecting over the inner surface 11 in the direction of the longitudinal axis 8, whereby said projection forms the end of the locking recess 26. Said locking recess 26 is in the present case only designed to be recessed in the container wall 6 and is closed in the region of the outer surface 12. In this region the container wall only has a very low strength which enables the locking device 16 to be activated. By means of the covered design of the locking recess 26 additional protection from the leaking of fluids to the outside from the holding container 7 is provided. This would otherwise be possible more easily by the displacement of the cannula tip into the holding chamber 7. The additional adjusting device 17 between the needle holder 4 and the cover element 3 is supported, on the one hand, in the region of the needle holder 4 in the region of the supporting body 36, or if necessary the support element 37 facing the distal end 10, and on the other hand, is supported on the main body 21 of the cover element 3. Preferably, in the region of the needle holder 4 facing the distal end 10, in particular the supporting body 36, in the latter a further tubular depression 50 is formed, into which one end of the additional adjusting device 17 can be inserted. In this way a good centring of the latter can be achieved. A further centring element 51 for the additional adjusting device 17 can also be arranged on the cover element 3 on the region of the main body 21 facing the proximal end. Said centring element 51 is here in the form of a tubular step on the main body 21, and can serve as an internal or external centring for the spring element, preferably formed by a compression spring made of metal or plastic material. From an overview of FIGS. 7 to 9 and 17 and 18, it can be seen that between the holding container 2, in particular its container wall 6 and the cover element 3, at least the first guiding arrangement 27 is provided, and between the needle holder 4 and the collecting container 2 a further guiding arrangement 52 is provided. In order to form at least one part of the guide arrangement 27, 52 a partial section 53, 54 of the inner surface 11 of the container wall 6 is designed respectively as a guide track 55, 56. Preferably, the guide tracks 55, 56 or the partial sections 53, 54 are aligned over their longitudinal extension, relative to the longitudinal axis 8, parallel thereto. It is particularly preferable if the partial sections 53, 54 of the inner surface 11 or the entire inner surface 11 are cylindrical in relation to the longitudinal axis 8—i.e. at a constant distance from the longitudinal axis 8. It would also be possible however to design the entire inner surface 11 or only at least one of the partial sections 53, 54 to have a manufacturing-defined tapering. The latter can e.g. be a maximum of 0.5° and is dependent on the selected manufacturing method and the materials used. As already described above in FIGS. 1 to 6 the first guiding arrangement 27 is designed between the cover element 3 and the holding container 2. The locking device 16 comprises at least one locking element 25 and at least one locking recess 26 interacting therewith in the holding container 2. The locking recess 26 can either be arranged in the container wall 6 or in the region of the end wall 13. In the embodiment shown here on the main body 21 of the cover element 3, several, preferably four, locking elements 25 are provided arranged evenly around the circumference, whereby in the holding container 2 several, preferably two, diametrically opposite locking recesses 26 are arranged or cut out which cooperate with two of the locking elements 25 to form the locking device 16. It is also possible that the locking element or elements 25 is or are arranged on a holding arm 57 projecting from the main body 21 of the cover element 3 in the direction of the needle holder 4 or the proximal end 9, as can best be seen from FIGS. 11 and 12. In this way the locking elements 25, and if necessary the holding arm or arms 57 are arranged in the region of the outer circumference of the cover element 3. The first guiding arrangement 27 extends at least over the entire displacement path 58 of the cover element 3 between the position of use or its maintenance position in the region of the proximal end 9 and the disposal position or its cover position in the region of the distal end 10. In this way, it is ensured that the cover element 3 during its entire adjustment movement is adjustable continually in the direction of the longitudinal axis 8. The first guiding arrangement 27 is here formed by the bearing or interaction of the locking element or elements 25 arranged on the holding arm 57 on the guide track or tracks 55. It is advantageous in this case, if the locking element or elements 25 bear with the interconnection of the holding arm 57 with a predeterminable or predetermined bearing force radially in the direction of the guide track 55. If as already described above the partial section 53 of the guide track 55 is aligned parallel to the longitudinal axis 8 over the entire displacement path 58 of the cover element 3 an almost equally high bearing force is achieved. The additional guiding arrangement 52 between the holding container 2 and the needle holder 4 comprises in the region of the holding container 2 at least one guide element 59 arranged on the inner surface 11 of the latter and projecting in the direction of the longitudinal axis 8, projecting over the inner surface 11, such as e.g. a web, a rib or the like. In order to achieve a straight-line adjustment the guide element or elements 59 is or are aligned in the direction of the longitudinal axis 8. Preferably, two guide elements 59 arranged next to one another, as viewed around the circumference, form a part of the additional guiding arrangement 52 between the holding container 2 and the needle holder 4. In order to achieve a more even and more tilt-free guiding, preferably several guide elements 59 are distributed evenly in pairs around the circumference, and in particular are arranged in the form of a cross relative to one another. As already described above, the additional guiding arrangement 52 comprises at least one further guide track 56, which is arranged between the two adjacent guide elements 59. As can best be seen from FIGS. 7, 8 and 13 and 14 the additional guiding arrangement 52 in the region of the needle holder 4 comprises at least one guide extension 60 interacting with the guide element or elements 59. The guide extension 60 is hereby designed to be roughly web-shaped and extends in parallel to the longitudinal axis 8. In the embodiment shown here the guide extension or extensions 60 are connected with the interconnection of a support arm 61, illustrated in simplified form, with the support element 37 or support part 48 and connected with the supporting body 36. Preferably, the entire needle holder 4 is made from a one-piece component, in particular by injection moulding. In the assembled state the guide extension or extensions 60 are arranged in the region of the holding container 2 between the two adjacent guide elements 59, and are guided on the one hand in radial direction by the partial section 54 forming the guide track 56 and viewed in the direction of the longitudinal axis 8, by at least one guiding element, but preferably between the two guide elements 59. The guide extensions 60 and if necessary the support arms 61 are arranged relative to one another on the support element 37 or support element 48 according to the circumferential arrangement of the guide elements 59, preferably distributed evenly around the circumference, in particular in the form of a cross relative to one another. With an even number of guide tracks 55, 56 arranged on the inner surface the latter are arranged in a cross shape—i.e. at 90° to one another—around the circumference. Furthermore, the guide tracks 55 are arranged offset in relation to the guide tracks 56 by an equal amount around the circumference, whereby an angle of 90° has proved to be preferable. The first guiding arrangement 27 described above, between the cover element 3 and the holding container 2, is formed at least by the locking elements 25 brought to bear on the inner surface 11. To achieve the rotation-fastness of the cover element 3 about the longitudinal axis 8 it is advantageous, if at least one of the guide elements 59 projects into at least one partial cut-out 62 formed in the circumferential region of the cover element 3, or is in engagement with the latter, whereby the partial cut-out 62, viewed in the circumferential region, is arranged in the main body 21 between the locking elements 25 or holding arms 57. This can best be seen in the simplified drawing of FIG. 17. As described in the introduction to the Figures, in this embodiment in addition in the region of the distal end 10 of the holding container 2, at least one securing element 46 is arranged on the latter, which can best be seem from an overview of FIGS. 15, 16 and 18. Said securing element 46 is designed for subsequent insertion into the holding chamber 7 and held locked on the holding container 2. In the embodiment shown here the securing element 46 comprises a sleeve-shaped support element 63 and flange-shaped step 64 associated therewith, which projects over the support element 63 in the direction pointing away from the longitudinal axis 8. For better positioning it can be advantageous if the flange-shaped step 64 comprises diametrically opposite flattened sections 65, and the latter can be inserted in cooperation with the step 64 into a depression of the holding container 2 arranged in the region of the distal end 10. On the sleeve-shaped support element 63 at least one positioning element 66 aligned parallel to the longitudinal axis can be arranged which projects over the support element 63 in the direction of the proximal end 9 of the holding container 2. Advantageously several, preferably four, positioning elements 66 are distributed evenly around the circumference, in particular in the form of a cross. This arrangement corresponds in terms of angle to the arrangement of the partial sections 54 of the inner surface 11 of the holding container 2, as can best be seen from FIG. 9. During the assembly the positioning elements 66 project in the direction of the proximal end 9 and are in addition still arranged between the guide elements 59 arranged next to one another in pairs. Said positioning elements 66 project thus into the part section 54 or guide tracks 56 for the guide extensions 60 arranged on the needle holder 4 and delimit a displacement path 67 of the needle holder 4 from the proximal end 9 in the direction of the distal end 10. In this way it is possible for the adjusting device 15 to be provided with correspondingly high preloading force, in order to ensure a secure adjustment of the needle holder 4 and thus of the needle arrangement 14 into the disposal position and to press the needle holder 4 by the stop of the guide extensions 60 against the ends of the positioning elements 66 facing the proximal end 9. In order to restrict the displacement path 58 of the cover element 3 and thus prevent the exit of the latter out of the holding chamber 7 of the holding container 2, in this embodiment instead of the stop element 42, described in FIGS. 1 to 6, which was arranged directly on the holding container 2, here on the securing element 46 at least one, preferably several, stop elements 68 are arranged around the circumference. Said stop elements 68 project in this embodiment, from the flange-like step 64 in the direction of the longitudinal axis 8, and are thus secure in cooperation with the locking element or elements 41 on the cover element 3, its longitudinal movement from the proximal end 9 in the direction of the distal end. In order to prevent the cover element 3 from being pressed in from the distal end 10 in the direction of the proximal end 9 in the disposal position, on the securing element 46 at least one, preferably several, retaining elements 69 can be arranged, which in turn form with at least one, preferably several, cooperating further stop elements on the cover element 3, in particular the locking element or elements 25 arranged on the holding arm 57, a part of the locking device 39. The retaining elements 69 are in the installed position of the securing element 46 in the holding container 2 closer to the proximal end 9 and in order to facilitate the intersliding or mutual locking with the allocated locking elements 25 comprise a tapered running surface 70, which is designed to taper from the outer edge of the support element 63 closer to the proximal end 9 and immediately adjacent to the inner surface 11 of the holding container 2 in the direction of the longitudinal axis 8 and the distal end 9. For the mutual locking with the locking element 25 on the retaining element 69 an interacting locking catch 71 is arranged which projects over the tubular support element 63 in the direction of the longitudinal axis 8 and with the running surface 70 forms the locking catch 71. The locking elements 25, preferably two diametrically opposite ones, on the one hand form the locking device 16with the locking recess 26 in the position of use in the region of the proximal end 9, and in the region of the distal end 10 in cooperation with retaining elements 69 form a portion of the locking device 39. In the region of the locking device 39 for a better securing of the cover element 3 the locking elements 25 distributed evenly around the circumference act together with the retaining elements 69. In the present embodiment four locking elements 25 and retaining elements 69 are provided distributed evenly around the circumference. Of course, it is also possible to provide any number of locking elements 25, locking recesses 26, retaining elements 69, stop elements 68 and locking elements 41. This depends on the size, design and the purpose of the holding device 1, and can be selected freely according to the requirements made of the holding device 1. At the same time, it is also possible, as already described in FIGS. 1 to 6, for the cover element 3 in the region of the longitudinal axis 8 to comprise an opening 22 for guiding through a portion of the cannula 5, whereby in addition in the region of the opening 22, a fluid suctioning or collecting component 23 can be arranged. The same is also true for the anti-rotational means 38 arranged between the needle holder 4 and the holding container 2. The latter is used when the needle holder 4 is located in the position of use, which on inserting the needle arrangement 14 prevents a relative pivoting or rotation about the longitudinal axis 8 between the needle holder 4 and the holding container 2. In the embodiments described in FIGS. 7 to 17, as can best be seen from an overview of FIGS. 9 and 13, a portion of the anti-rotational means 38 in the region of the end wall 13 of the collecting container 2 is formed by groove or web-shaped depressions and in the region of the needle holder 4 by locking projections projecting over the supporting body 36. In this way in the position of use of the needle holder 4 the locking projections are in engagement with the groove-shaped or web-shaped depressions. The anti-rotational means 38 can of course also be formed by any other arrangement or design of components in engagement with one another in the position of use, as already described and shown in FIGS. 1 to 6. In the drawing of FIG. 18 the needle holder 4 comprises opposite flattened sections, which can cooperate with correspondingly designed fitting surfaces. As can be seen from an overview of FIGS. 9, 12, 15, 16 and 18, the cover element 3 during its longitudinal movement from the position of use to the disposal position in the region of the holding container 2 is secured by the partial cut-out 62 arranged on the circumferential region in interaction with guide elements 59 from rotation about the longitudinal axis 8. In the region of the securing elements 46 in particular in the region of its support element 63, no such guide elements 59 are provided in the region of the inner surface 11 of the holding container 2, whereby rotation of the cover element 3 about a specific angle about the longitudinal axis 8 is possible, whereby the locking element or elements 25 can be brought by pivoting or rotation out of engagement with the retaining elements 69, and thus the cover element 3 can be readjusted and pushed in the direction of the proximal end 9 into the holding chamber 7. In this way a stick injury from the end of the cannula 5 arranged in the holding chamber 7 would be possible. In order to prevent the possibly undesired relative rotation of the cover element 3 relative to the holding container 2 in this embodiment between the latter or between the securing element 46 and the cover element 3 there is one, preferably several, anti-rotational means 72. In the region of the cover element 3 the anti-rotational means 72 is in the form of partial cut-out or cut-outs 62 in the circumferential region of the cover element 3. In the region of the holding container 2 or the securing element 46 the anti-rotational means 72 is formed for example by webs 72 arranged distributed around the circumference, which are arranged in the direction of the longitudinal axis 8 in extension to the guide elements 59 on the inside of the support element 63. In this way also in this position of the cover element 3 is definitely secured and held in position relative to the holding container 2 or the securing element 46 arranged therein both in the direction of the longitudinal axis 8 and about the longitudinal axis 8. Unintentional rotational and any associated injury and resulting infection is thus almost completely eliminated. For form's sake it should be pointed out that for a better understanding of the structure of the holding device the latter and its components have been illustrated partly untrue to scale and/or enlarged and/or reduced in size. The objective forming the basis of independent solutions according to the invention can be taken from the description. Most of all, the individual designs shown in the FIGS. 1 to 6; 7 to 17; 18 can form the subject matter of independent solutions according to the invention. The objectives and solutions relating thereto can be taken from the detailed descriptions of said Figures.
20050404
20090421
20051229
81742.0
0
KILPATRICK, BRYAN T
RECEIVING DEVICE COMPRISING AN ADJUSTABLE COVERING ELEMENT
UNDISCOUNTED
0
ACCEPTED
2,005
10,530,445
ACCEPTED
Wavelength-division-multiplexing passive optical network utilizing fiber fault detetors and/or wavelength tracking components
Various methods, systems, and apparatuses is described in which a passive-opticalnetwork includes a first multiplexer/demultiplexer, a second multiplexer/demultiplexer, a wavelength tracking component, and a transmission wavelength controller. The first multiplexer/demultiplexer is located in a first location. The second multiplexer/demultiplexer is located in a second location remote from the first location. The wavelength tracking component determines the difference between the transmission band of wavelengths of the first multiplexer/demultiplexer and the second multiplexer/demultiplexer to provide a control signal to match the transmission band of wavelengths of the first multiplexer/demultiplexer and the second multiplexer/demultiplexer. The transmission wavelength controller alters an operating parameter of the first multiplexer/demultiplexer based on the control signal to control the transmission band of wavelengths of the first multiplexer/demultiplexer.
1. An apparatus; comprising: a wavelength tracking component to determine a difference between transmission band of wavelengths of a first multiplexer/demultiplexer and a second multiplexer/demultiplexer in order to provide a control signal to match the transmission band of wavelengths of the first multiplexer/demultiplexer and the second multiplexer/demultiplexer, wherein the first multiplexer/demultiplexer is located in a first location and the second multiplexer/demultiplexer is located in a second location remote from the first location; and a transmission wavelength controller to alter an operational parameter of the first multiplexer/demultiplexer based on the control signal to control the transmission band of wavelengths of the first multiplexer/demultiplexer. 2. The apparatus of claim 1, wherein the wavelength tracking component further comprises: a lock-in detector coupled to the first multiplexer/demultiplexer and an oscillator. 3. The apparatus of claim 1, wherein the transmission wavelength controller comprises a temperature controller to alter an operating temperature of the first multiplexer/demultiplexer based on the control signal. 4. The apparatus of claim 2, wherein the wavelength tracking component further comprises: a power summing device to measure a strength of an output signal from one or more optical receivers, wherein the power summing device electrically couples to the temperature controller; and the temperature controller alters the operating temperature of the first multiplexer/demultiplexer to achieve substantially a maximum power output from the power summing device. 5. The apparatus of claim 4, wherein the power summing device is an electrical power summing device. 6. The apparatus of claim 3, wherein the temperature controller dithers the operating temperature of the first multiplexer/demultiplexer in a first direction and then measures whether a strength of the control signal changes, and adjusts the operating temperature of the first multiplexer/demultiplexer based upon the detected change. 7. A passive optical network, comprising: a first multiplexer/demultiplexer located in a first location; a second multiplexer/demultiplexer located in a second location remote from the first location; a wavelength tracking component that determines a difference between the transmission band of wavelengths of the first multiplexer/demultiplexer and the second multiplexer/demultiplexer to provide a control signal, wherein the wavelength tracking component couples to a port of the first multiplexer/demultiplexer; and a transmission wavelength controller to alter an operational parameter of the first multiplexer/demultiplexer based on the control signal to control the transmission band of wavelengths of the first multiplexer/demultiplexer. 8. The passive optical network of claim 7, further comprising: a first broadband light source to supply an optical signal containing a first band of wavelengths to the second multiplexer/demultiplexer; a second broadband light source to supply an optical signal containing a second band of wavelengths to the first multiplexer/demultiplexer, and an oscillator to modulate the second broadband light source at a known frequency to generate a modulated second band of wavelengths. 9. The passive optical network of claim 8, further comprising: a mirror coupled to the second multiplexer/demultiplexer to reflect a portion of the modulated second band of wavelengths to the wavelength tracking component. 10. The passive optical network of claim 9, wherein the wavelength tracking component measures a difference in the transmission band of wavelengths between the first multiplexer/demultiplexer and the second multiplexer/demultiplexer based upon a change detected in the reflected portion of the modulated second band of wavelengths. 11. The passive optical network of claim 9, wherein the wavelength tracking component further comprises: a lock-in detector to establish an amplitude of the reflected modulated signal by comparing the reflected modulated signal to a reference signal. 12. The passive optical network of claim 8, wherein the wavelength tracking component compares the known frequency and phase of a signal from the oscillator to the frequency and phase of a reflected signal to determine a temperature difference between the first multiplexer/demultiplexer and the second multiplexer/demultiplexer. 13. The passive optical network of claim 8, wherein the wavelength tracking component measures a difference in transmission band of wavelengths between the first multiplexer/demultiplexer and the second multiplexer/demultiplexer based upon a change detected in a transmitted signal from one or more subscribers, wherein the transmitted signal is derived from the modulated second band of wavelengths. 14. The passive optical network of claim 7, further comprising: a first group of optical transmitters to emit optical signals in a first band of wavelengths; a first group of optical receivers to accept optical signals in a second band of wavelengths, wherein the first group of optical transmitters and the first group of optical receivers couple to the first multiplexer/demultiplexer by a first group of band splitting filters; a second group of optical transmitters to emit optical signals in the second band of wavelengths; and a second group of optical receivers to accept optical signals in the first band of wavelengths, wherein the second group of optical transmitters and the second group of optical receivers couple to the second multiplexer/demultiplexer by a second group of band splitting filters. 15. The passive optical network of claim 14, further comprising: a first optical transmitter in the second group of optical transmitters, wherein the second multiplexer/demultiplexer spectrally slices the second band of wavelengths to lock an output wavelength of the first optical transmitter to within the bandwidth of the spectral slice. 16. The passive optical network of claim 7, wherein the transmission wavelength controller comprises a temperature controller to alter an operating temperature of the first multiplexer/demultiplexer based on the control signal. 17. The passive optical network of claim 16, wherein the first multiplexer/demultiplexer has a greater transmission wavelength change ratio per degree change in temperature than the second optical multiplexer/demultiplexer. 18. The passive optical network of claim 7, further comprising: a fiber fault detector to detect a defect in optical paths delivering optical signals to and from in the passive optical network. 19. A passive optical network, comprising: a first broadband light source to generate an optical signal having a first band of wavelengths; an optical multiplexer/demultiplexer to multiplex the optical signal having the first band of wavelengths to a plurality of subscribers; and a fiber fault detector to detect a fault in an optical path to the subscribers, wherein the fiber fault detector compares the optical signal having the first band of wavelengths going to the subscribers to a reflection of that signal. 20. The passive optical network of claim 19, further comprising: an optical coupler operating in both the first band of wavelengths and a second band of wavelengths, the optical coupler to route at least a portion of the optical signal having the first band of wavelengths and at least a portion of the reflection of that signal to the fiber fault detector. 21. The passive optical network of claim 19, further comprising: an optical band splitting filter coupled to the fiber fault detector as well as an optical terminator. 22. The passive optical network of claim 19, wherein the fiber fault detector includes a photo-detector, a low pass filter, a divider, and a comparator. 23. The passive optical network of claim 19, wherein the fiber fault detector compares a ratio of the reflected signal to the optical signal with a reference value to determine if the fault exists in the optical path going to the subscribers. 24. The passive optical network of claim 19, wherein the fiber fault detector compares total power of a transmitted signal from the subscribers to a reference value to determine if the fault exists in the optical path to and from the subscribers. 25. The passive optical network of claim 19, further comprising a plurality of receivers to receive a signal from the subscribers; wherein each receiver may compare the strength the received signal to a reference value and communicate with the fiber fault detector if that received signal falls below the reference value. 26. The passive optical network of claim 19, further comprising: a second optical multiplexer/demultiplexer to multiplex and demultiplex bi-directionally. 27. The passive optical network of claim 26, further comprising: a wavelength tracking component having a power combiner to measure total power of a transmitted signal from the subscribers after passing through the second optical multiplexer/demultiplexer; and a temperature controller to control an operating temperature of the second optical multiplexer/demultiplexer to maximize the output power of the power combiner. 28. The passive optical network of claim 19, wherein the optical multiplexer/demultiplexer is an athermal arrayed waveguide grating. 29. The passive optical network of claim 19, wherein the optical multiplexer/demultiplexer is an arrayed waveguide grating. 30. A method, comprising: supplying an optical signal containing a first band of wavelengths to a first multiplexer/demultiplexer in a passive optical network; supplying an optical signal containing a second band of wavelengths to a second multiplexer/demultiplexer in the passive optical network; measuring an optical power of the second band of wavelengths after passing through the first multiplexer/demultiplexer; and adjusting a transmission band of wavelengths passed by the first multiplexer/demultiplexer based upon achieving substantially maximum power for the measured optical power of the second band of wavelengths. 31. An apparatus, comprising: means for supplying an optical signal containing a first band of wavelengths to a first multiplexer/demultiplexer in a passive optical network; means for supplying an optical signal containing a second band of wavelengths to a second multiplexer/demultiplexer in the passive optical network; means for measuring an optical power of the second band of wavelengths after passing through the first multiplexer/demultiplexer; and means for adjusting a transmission band of wavelengths passed by the first multiplexer/demultiplexer based upon achieving substantially maximum power for the measured optical power of the second band of wavelengths. 32. A method, comprising extracting at least a portion of an optical signal having a first band of wavelengths going to subscribers in a passive optical network; filtering out wavelengths not in the first band of wavelengths; routing at least a portion of a reflection of the optical signal having the first band of wavelengths; and comparing the portion of the optical signal having the first band of wavelengths to the portion of the reflection of that signal to determine if a fault exists in an optical path going to the subscribers. 33. An apparatus, comprising: means for extracting at least a portion of an optical signal having a first band of wavelengths going to subscribers in a passive optical network; means for filtering out wavelengths not in the first band of wavelengths; means for routing at least a portion of a reflection of the optical signal having the first band of wavelengths; and means for comparing the portion of the optical signal having the first band of wavelengths to the portion of the reflection of that signal to determine if a fault exists in an optical path going to the subscribers.
RELATED APPLICATIONS This application claims the benefit of Korean Patent Application entitled “Bi-directional wavelength-division-multiplexing passive optical network utilizing wavelength-locked light sources by injected incoherent light,” Ser. No. 2002-60868, filed Oct. 7, 2002. FIELD Embodiments of this invention relate to wavelength-division-multiplexing-passive-optical-networks. More particularly, an aspect of an embodiment of this invention relates to wavelength-division-multiplexing passive-optical-networks using fiber fault detectors and/or wavelength tracking components. BACKGROUND Some wavelength-division-multiplexing-passive-optical-networks require precise wavelength alignment between the wavelengths of the signal from a transmitter in a central office to a device in a remote site distributing that signal to a subscriber. In a passive-optical-network, a remote node containing the signal-distributing device is typically located outdoors without any electrical power supply. The transmission band of wavelengths of the outdoor signal-distributing device can change according to the variation of the external temperature. Misalignment of the wavelength between the transmitted signal and the operating wavelength of the device distributing the signal introduces extra insertion loss in the signal. A possible way to minimize the misalignment can be to use a narrow-linewidth distributed feedback laser diode (DFB LD) that essentially always falls within the shifting bandwidths of the multiplexers as an optical transmitter to satisfy the wavelength alignment condition. However, this arrangement may not be an economic solution because of the high price of each DFB LD. Further, in systems having two or more wavelength division multiplexers located in different areas, misalignment of the transmission band of wavelengths between the two or more wavelength division multiplexers may occur due to the temperature variations at these different areas. The operating transmission band of wavelengths of these devices can vary depending on the temperature of the device. Complex channel selection and temperature control circuits could be employed to compensate for the large insertion loss in optical signals passing through optical multiplexer/demultiplexers located in different locations. However, the complexity of the channel selection circuit has the disadvantage that the complexity of the circuit becomes greater and greater as the number of input ports of the circuit increases. Thus, the more channels being distributed by a multiplexer/demultiplexer, then the more complex and expensive the channel selection and temperature control circuit becomes. SUMMARY Various methods, systems, and apparatuses are described in which a passive-optical-network includes a first multiplexer/demultiplexer, a second multiplexer/demultiplexer, a wavelength tracking component, and a transmission wavelength controller. The first multiplexer/demultiplexer is located in a first location. The second multiplexer/demultiplexer is located in a second location remote from the first location. The wavelength tracking component determines the difference between the transmission band of wavelengths of the first multiplexer/demultiplexer and the second multiplexer/demultiplexer to provide a control signal to match the transmission band of wavelengths of the first multiplexer/demultiplexer and the second multiplexer/demultiplexer. The transmission wavelength controller alters an operating parameter of the first multiplexer/demultiplexer based on the control signal to control the transmission band of wavelengths of the first multiplexer/demultiplexer. Other features and advantages of the present invention will be apparent from the accompanying drawings and from the detailed description that follows below. BRIEF DESCRIPTION OF THE DRAWINGS The present invention is illustrated by example and not limitation in the figures of the accompanying drawings, in which like references indicate similar elements and in which: FIG. 1 illustrates a block diagram of an embodiment of a wavelength-division-multiplexing passive-optical-network using a fiber fault detector and/or wavelength tracking component; FIG. 2 illustrates a block diagram of an embodiment of a fiber fault detector; FIG. 3 illustrates a block diagram of an embodiment of a wavelength-division-multiplexing passive-optical-network using a fiber fault detector and/or wavelength tracking component; and FIGS. 4a and 4b illustrate a flow diagram of an embodiment of the wavelength-division-multiplexing passive-optical-network. DETAILED DESCRIPTION In general, various wavelength-division-multiplexing passive-optical-network are described. For an embodiment, a passive-optical-network includes a first multiplexer/demultiplexer, a second multiplexer/demultiplexer, a wavelength tracking component, and a transmission wavelength controller. The first multiplexer/demultiplexer is located in a first location. The second multiplexer/demultiplexer is located in a second location remote from the first location such that the transmission band of wavelengths of the first and second multiplexer/demultiplexer may become mismatched due to changes in operational parameters. The wavelength tracking component, such as a detector, determines the difference between the transmission band of wavelengths of the first multiplexer/demultiplexer and the transmission band of wavelengths of the second multiplexer/demultiplexer to provide a control signal to match the transmission band of wavelengths of the first multiplexer/demultiplexer and the second multiplexer/demultiplexer. The transmission wavelength controller alters an operating parameter of the first multiplexer/demultiplexer based on the control signal to control the transmission band of wavelengths of the first multiplexer/demultiplexer. A fiber fault detector may also be in the passive optical network to detect a defect in the optical paths delivering optical signals to and from subscribers in the passive optical network. FIG. 1 illustrates a block diagram of an embodiment of a wavelength-division-multiplexing passive-optical-network using a fiber fault detector and/or a wavelength tracking component. The wavelength-division-multiplexing passive-optical-network 100 includes a first location such as a central office, a second location remote from the first location such as a remote node, and a plurality of subscriber locations. The example central office contains a first group of optical transmitters 101-103 emitting optical signals in a first band of wavelengths, a first group of optical receivers 104-106 to accept an optical signal in a second band of wavelengths, a first group of band splitting filters 107-109, a wavelength-tracking component 130, a first 1×n bi-directional optical multiplexer/demultiplexer 112, a first optical coupler 115, a second optical coupler 126, a fourth band splitting filter 127, a fifth band splitting filter 132, a fiber fault detector 131, a first broadband light source 114, and a second broadband light source 113. The first optical multiplexer/demultiplexer 112 spectrally slices a first band of wavelengths received from the first broadband light source 114 and demultiplexes a second band of wavelengths received from the second optical multiplexer/demultiplexer 116. Each optical transmitter in the first group of optical transmitters 101-103 receives a discrete spectrally sliced signal in the first band of wavelengths and aligns the operating wavelength of that optical transmitter to the wavelengths within the received spectrally sliced signal. Each optical receiver in the first group of optical receivers 104-106 receives a discrete demultiplexed signal in the second band of wavelengths. The first multiplexer/demultiplexer 112 couples to a first group of band splitting filters 107-109. A band splitting filter, such as the first broadband splitting filter 107, splits the first band of wavelengths and the second band of wavelengths signals to different ports. Each band splitting filter 107-109 couples to a given optical transmitter in the first group of optical transmitters 101-103 and a given optical receiver in the first group of optical receivers 104-106. For example, the first band splitting filter 107 couples a spectrally sliced signal in the first band of wavelengths to the first optical transmitter 101. Thus, if the wavelength of an input optical signal is in first band of wavelengths, the output signal from the first band splitting filter 107 is passed to the port parallel to the input port. The first band splitting filter 107 couples a demultiplexed signal in the second band of wavelengths to the first optical receiver 104. Thus, in the case that the wavelength of input signal is in the second band of wavelengths, the output port is, for example, orthogonal to the input direction. The wavelength tracking component 130 includes an electrical or optical power summing device 110 and a temperature controller 111. The power summing device 110 measures the strength of an output signal of one or more of the optical receivers 104-106 to determine the difference in the transmission band of wavelengths between the first multiplexer/demultiplexer 112 and the second multiplexer/demultiplexer 116. The temperature controller 111 controls the operating temperature of the first optical multiplexer/demultiplexer 112 to maximize the strength of the measured output signal from the optical receivers 104-106. When the transmission band of wavelengths of the first multiplexer/demultiplexer 112 and the second multiplexer/demultiplexer 116 are matched, then the strength of the measured output signal from the optical receivers 104-106 is at its maximum. The temperature controller 111 alters an operating parameter of the first multiplexer/demultiplexer, such as its temperature, based on the control signal to control the transmission band of wavelengths of the first multiplexer/demultiplexer. If the measured output signal from the optical receivers 104-106 falls below a preset reference level, then the temperature controller 111 starts altering the operating temperature of the first optical multiplexer/demultiplexer 112 in a first direction. For example, the temperature controller 111 changes the operating temperature of the first optical multiplexer/demultiplexer 112 in a higher direction. Similarly, the temperature controller 111 could change the operating temperature of the first optical multiplexer/demultiplexer 112 in a lower direction. The temperature controller 111 measures whether the strength of the optical output signal increases. If the strength of the measured output signal increases, then the temperature controller 111 continues to incrementally increase/decrease the operating temperature of the first optical multiplexer/demultiplexer 112 until the measured output signal starts decreasing. In an embodiment, the first multiplexer/demultiplexer 112 has a greater transmission wavelength change ratio per degree change in temperature than the second optical multiplexer/demultiplexer 116. For example, the first optical multiplexer/demultiplexer 112 may be built with a transmission wavelengths sensitivity to temperature changes ten times that of the second optical multiplexer/demultiplexer 116. Thus, if the transmission band of wavelengths of the second multiplexer/demultiplexer 116 changes because of a twenty degree temperature change, then the operating temperature of the first optical multiplexer/demultiplexer 112 needs merely to change by two degrees to match up the transmission wavelengths of the first multiplexer/demultiplexer 112 and the second multiplexer/demultiplexer 116. A benefit of increasing the sensitivity of the transmission wavelengths to temperature changes in the second multiplexer/demultiplexer 116 is that power consumption to match up the transmission band of wavelengths may be greatly reduced. Thus, the multiplexed/demultiplexed transmission wavelength of the optical multiplexer/demultiplexers 112, 116 located in the central office and the remote node can be locked to each other. The transmission band of wavelengths locking is accomplished by tracking the demultiplexed wavelength from the remote node and then altering the transmission wavelength of the optical multiplexer/demultiplexer located in the central office. The transmission band of wavelength is altered by, for example, moving the temperature of the optical multiplexer/demultiplexer in the direction of maximizing the strength of light measured at a specific port of the optical multiplexer/demultiplexer located at the central office. A second optical coupler 126, such as a 2×2 optical coupler, extracts a portion of input-output signals of the central office to route them to the optical fiber fault detector 131. A fourth band splitting optical filter 127 couples to the optical fiber fault detector 131 and a first optical terminator 129. A fifth band splitting optical filter 132 couples to the optical fiber fault detector 131 and a second optical terminator 134. The fiber fault detector 131 detects a defect in an optical path delivering optical signals to the subscribers. The second optical coupler 126 injects a portion of the downstream multiplexed first band of wavelengths and the incoherent light from the second broadband light source 113 to the fifth band splitting optical filter 132. The fifth band splitting optical filter 132 routes the incoherent light in the second band of wavelengths from the second broadband light source 113 to the second optical terminator 134. The second optical terminator 134 absorbs the position of light from the second broadband light source 113. The fifth band splitting optical filter 132 routes the downstream multiplexed first band of wavelengths to the optical cable fault detection device 131. The second optical coupler 126 routes a reflection of the downstream multiplexed first band of wavelengths and a portion of the upstream multiplexed signal in the second band of wavelengths to the fourth band splitting optical filter 127. The fourth band splitting optical filter 127 routes the upstream multiplexed signal in the second band of wavelengths to the second optical terminator 129. The second optical terminator 129 absorbs the light from upstream multiplexed signal in the second band of wavelengths. The fourth band splitting optical filter 127 routes the reflected downstream multiplexed first band of wavelengths to the optical cable fault detection device 131. The fiber fault detector 131 compares the transmitted signal going to subscribers to a reflection of that signal. The fiber fault detector 131 compares a reference value to the ratio of the reflected signal to transmitted signal in order to determine if a fault, such as a broken optical fiber, exists in the optical path going to the subscribers. Generally, when defects do not exist in the optical path, then the optical system does not generate a reflection of the downstream multiplexed signal in the first band of wavelengths. Therefore, if a reflection of the downstream multiplexed signal in the first band of wavelengths is detected above a certain ratio, then that indicates that one or more fibers going to the subscribers is broken. The fiber fault detector 131 may compensate for extracting different percentages of the reflected signal to transmitted signal when determining the ratio of the reflected signal to transmitted signal. The fiber fault detector 131 also receives a signal from the optical summing device 110. The fiber fault detector 131 compares the total power of the transmitted signal from the subscribers to a reference value to determine if a fault exists in the optical system. If the total power of the transmitted signal from the subscribers falls below a minimum threshold, then that indicates that one or more subscribers are no longer transmitting an optical signal back to the central office. Similarly, a degraded total power of the transmitted signal from the subscribers could indicate some other deflect such as an abnormal insertion loss in one or more optical components in the system. The example remote node contains the second 1×n bi-directional optical multiplexer/demultiplexer 116. The second 1×n bi-directional optical multiplexer/demultiplexer 116 connects to the central office via a single optical fiber 128. The second 1×n optical multiplexer/demultiplexer 116 multiplexes and demultiplexes bi-directionally both the broadband optical signal containing the first band of wavelengths and the broadband optical signal containing the second band of wavelengths. The second 1×n optical multiplexer/demultiplexer 116 spectrally slices the second band of wavelengths from the second broadband light source 113. Generally, multiplexing may be the combining of multiple channels of optical information into a single optical signal. Demultiplexing may be the disassembling of the single optical signal into multiple discrete signals containing a channel of optical information. Spectral slicing may be the dividing of a broad band of wavelengths into small periodic bands of wavelengths. Each example subscriber location, for example, the first subscriber location, contains a band splitting filter 117, an optical transmitter 123 to emit optical signals in the second band of wavelengths, and an optical receiver 120 to receive optical signals in the first band of wavelengths. The second multiplexer/demultiplexer 116 to demultiplex the first band of wavelengths and spectrally slice the second band of wavelengths. The second multiplexer/demultiplexer sends these signals to each band splitting filter 117-119. The band splitting filters 117-119 function to split the input signal to an output port according to the input signal band. Each optical transmitter, such as the second optical transmitter 123, receives the spectrally sliced signal in the second band of wavelengths and aligns its operating wavelength for that optical transmitter to the wavelengths within the spectrally sliced signal. Each subscriber communicates with central office with a different spectral slice within the second band of wavelengths. The broadband light sources 113, 114 may be natural emission light sources that generate incoherent light. A 2×2 optical coupler 115 operating in both the first band of wavelengths and the second band of wavelengths couples the first broadband light source 114 and the second broadband light source 113 to the single fiber 128. The optical power directed into the first broadband light source 114 is terminated, while the other power propagates along the optical fiber cable so that each subscriber's optical transmitter 123-125 gets the broadband of light sliced by the 1×n optical multiplexer/demultiplexer 116 at the remote node. The first broadband light source 114, such as an amplified-spontaneous-emission source, supplies the first band of wavelengths of light to a given optical transmitter in the first group of optical transmitters 101-103 in order to wavelength lock the transmission band of wavelengths of that optical transmitter. Thus, the range of operating wavelengths for the group of transmitters 101-103 in the central office is matched to the operating wavelengths of the first multiplexer/demultiplexer 112 in the central office via the injection of these spectrally sliced signals into each of these transmitters in the first group of optical transmitters 101-103. The wavelength locking of the each optical transmitter to the particular spectral slice passed through the band splitting filter solves the large power loss on up-stream signals in the 1×n optical multiplexer/demultiplexer 112 due to the wavelength detuning depending on the temperature variation in the device at the remote node. In this way, the large power loss due to the misalignment between the wavelength of the signal from an optical transmitter 101-103 and the transmission band of wavelengths of the multiplexer/demultiplexer 112 at the central office is minimized. Similarly, the second broadband light source 113 supplies the second band of wavelengths of light to a given optical transmitter 123-125 to wavelength lock the transmission band of wavelengths of that optical transmitter in the second group. Thus, the operating wavelengths of the second group of transmitters 123-125 in the subscriber's local is matched to the range of operating wavelengths for the second multiplexer/demultiplexer 116 via the injection of these spectrally sliced signal into each of these transmitters in the second group of optical transmitters. The wavelength locking of the each optical transmitter to the particular spectral slice passed through the band splitting filter solves the large power loss on up-stream signals in the 1×n optical multiplexer/demultiplexer 116 due to the wavelength detuning depending on the temperature variation in the device at the remote node. In this way, the large power loss due to the misalignment between the wavelength of the signal from an optical transmitter 123-125 and the transmission band of wavelengths of the multiplexer/demultiplexer 116 at the remote node is minimized. Analogously, as described above, the wavelength-tracking component 130 matches the transmission band of wavelengths of the first multiplexer/demultiplexer 112 to the transmission band of wavelengths of a second multiplexer/demultiplexer 116. The wavelength-tracking component measures the strength of the output signal received from the optical receivers 104-106 at central office after the second band of wavelengths passes through the first multiplexer/demultiplexer 112. The wavelength-tracking component measures the strength of a particular receiver or an average output power of a group of receivers. The temperature controller 111 may vary the operating temperature of the first multiplexer/demultiplexer 112 to achieve substantially a maximum power output of the power combiner 110. The maximum power output of the power combiner 110 represents substantially the best match of transmission band of wavelengths for both multiplexer/demultiplexers 112, 116. The temperature controller 111 acts to control the transmission wavelengths of the passband for each channel of the first multiplexer/demultiplexer 112. For an embodiment, the transmission wavelength controller to control the transmission wavelengths of the passband for each channel of the first multiplexer/demultiplexer 112 may be a strain controller, voltage controller, a temperature controller, or other similar device. The transmission wavelength controller alters an operating parameter of the first multiplexer/demultiplexer based on the control signal to control the transmission band of wavelengths of the first multiplexer/demultiplexer. For an embodiment, an optical-passive-network consists of non-power supplied passive optical devices without any active devices between the central office and optical subscribers. The topology structure of the optical distribution network may be a star topology that has the remote node with an optical multiplexer/demultiplexer placed near the subscribers, and plays a role to relay communications with the central office through a single optical fiber and to distribute signals to and from each of the subscribers through their own optical fiber. The second multiplexer/demultiplexer may be in a remote location such that the ambient conditions differ enough from the environment of the first multiplexer/demultiplexer to substantially alter the transmission band of wavelengths of the second multiplexer/demultiplexer when matched to the transmission band of wavelengths of the first multiplexer/demultiplexer. As discussed, the wavelength-division-multiplexing passive-optical-network 100 may use different wavelength bands in downstream signals, such as the first band of wavelengths, and up-stream signals, such as the second band of wavelengths. The down-stream signals may represent the signals from optical transmitters 101-103 in the central office to the subscribers and the up-stream signals may represent the signals from optical transmitters 123-125 in the subscribers to the central office. The wavelengths of the down-stream signals may be, for example, λ1, λ2, . . . λn and the upstream signals would be λ1*, λ2*, λn* but carried in a different band of wavelengths, where λ1 and λ1* are separated by the free spectral range of the multiplexer/demultiplexer. As discussed, the 1×n optical multiplexer/demultiplexer 116 has the function that an optical signal from a port in the left side is demultiplexed to the n number of ports in the right side. Further, the optical signals from the n-ports in the right side are multiplexed to a port in the left side simultaneously. The 1×n optical multiplexer/demultiplexer 116 spectrally splices the second band of wavelengths into narrow spectral widths of wavelengths. Because the optical multiplexer/demultiplexer can be operated on more than two bands of wavelengths, the bi-directionally propagated up-stream signals and down-stream signals in different bands can be multiplexed and demultiplexed at the same time. Each of the bands of wavelengths operated on by the optical multiplexer/demultiplexer may be offset by one or more intervals of the free spectral range of the optical multiplexer/demultiplexer. Each optical transmitter may be directly modulated by, for example, electrical current modulation to embed information onto the specific wavelength transmitted by that optical transmitter. For an embodiment, one or more of the optical transmitters may be a Fabry-Perot semiconductor laser that are injected with the spectrum-sliced broadband incoherent light from an amplified-spontaneous-emission light source. For an embodiment, one or more of the optical transmitters may be a wavelength-seeded reflective semiconductor optical amplifier (SOA). One or more of the optical transmitters support high bit-rate modulation and long-distance transmission. A reflective SOA may also as act as the modulation device. The optical transmitters may be modulated, wavelength locked using wavelength seeding, provide signal gain for the wavelengths within the spectral slice and increase the extinction ratio between the injected wavelengths and wavelengths outside the spectral slice. For an embodiment, a broadband light source may be a light source based on semiconductor optical amplifiers, a light source based on rare-earth ion-doped optical fiber amplifiers, a light emitting diode, or similar device. The broadband light source may provide light with any kind of characteristic such as coherent or incoherent light. For an embodiment, an optical multiplexer/demultiplexer can be achieved by an arrayed waveguide grating including an integrated waveguide grating, a device using thin-film filters, a diffraction grating, or similar device. The optical multiplexer/demultiplexer can also be a dielectric interference filter or similar device. For an embodiment, wavelength tracking between multiplexer/demultiplexers minimizes the loss of a portion of a signal because of the characteristic of a multiplexer/demultiplexer to pass only wavelengths within a set channel passband. The wavelength tracking of the operating wavelengths of both of the multiplexer/demultiplexers assists in minimizing due to wavelength misalignment between these devices. For an embodiment, the first band of wavelengths may be a standard band of wavelengths designated for telecommunications, such as the C band 1525-1560 nanometers. The second band of wavelengths may be a standard band of wavelengths designated for telecommunications that differs from the standard band of wavelengths designated for telecommunications being used by the first band of wavelengths, such as the L band 1570-1620 nanometers. Alternatively, the second band of wavelengths may be a band of wavelengths having a spectral separation of between 5-100 nanometers apart from a peak wavelength of the first band of wavelengths. The spectral separation between the first band of wavelengths and the second band of wavelengths should be great enough to prevent the occurrence of interference between the filtered spectrally sliced downstream signal to a subscriber and the filtered upstream signal from that subscriber. FIG. 2 illustrates a block diagram of an embodiment of a fiber fault detector. The fiber fault detector 231 may include photo-detectors 251, 252, lowpass filters 253, 254, 258, a divider 255, and comparators 256,257. As described above, the N×N optical coupler (not shown), such as a 2×2 optical coupler, routes a portion of the transmitted signal going to subscribers to the fiber fault detector 231 and the same percentage portion of any reflection of that transmitted signal to the fiber fault detector 231. Band splitting filter 232 separates the portion of the transmitted signal going to subscribers from wavelengths of light not being monitored. Band splitting filter 227 separates the portion of the reflected transmitted signal coming from subscribers from wavelengths of light not being monitored. The photo-detectors 251, 252 convert the incoming optical signals into electric signals. The first photo-detector 251 converts and passes the reflection of the transmitted signal through a low pass filter 253 to the divider 255. The second photo-detector 252 converts and passes the portion of the transmitted signal through a low pass filter 254 to the divider 255. The divider 255 divides the value of the two photo-detectors 251, 252 to check the return loss at the optical cable 128. The comparator 256 compares the output value of the divider 255 to a first reference value. The comparator 256 generates a warning signal indicating an optical cable fault with abnormal return loss if the output value of the divider 255 is higher than the reference value of V1 260. The second comparator 257 compares the output value of the optical summer 210 to a second reference value 262. Note, the output value of the optical summer 210 is in inverse proportion to the insertion loss of the optical cable. Therefore, the second comparator 257 generates a warning signal indicating optical cable fault with abnormal insertion loss if the output value of the optical summer 210 is lower than the second reference value of V2 262. FIG. 3 illustrates a block diagram of an embodiment of a wavelength-division-multiplexing passive-optical-network using a fiber fault detector and/or a wavelength tracking component. The example central office contains a first group of optical transmitters 301-303 emitting optical signals in a first band of wavelengths, a first group of optical receivers 304-306 to accept an optical signal in a second band of wavelengths, a first group of band splitting filters 307-309, a wavelength-tracking component 330, a first bi-directional optical multiplexer/demultiplexer 312, a first optical coupler 315, a second optical coupler 326, a fourth band splitting filter 327, a fifth band splitting filter 332, a fiber fault detector 331, an oscillator 369, a first broadband light source 314, and a second broadband light source 313. The first bi-directional optical multiplexer/demultiplexer 312 may have as many ports as there are subscribers plus one. The example remote node includes a second bi-directional optical multiplexer/demultiplexer 316 and a mirror 367 coupled to the second multiplexer/demultiplexer 316. The second bi-directional optical multiplexer/demultiplexer 316 may have as many ports as there are subscribers plus one. The oscillator 369 amplitude modulates the second broadband light source 313 at a known frequency to generate a modulated second band of wavelengths. The mirror 367 reflects a portion of the second band of wavelengths, such as a spectral slice narrow band signal, to the wavelength tracking component 330. The wavelength tracking component 330 couples to the first multiplexer/demultiplexer 312 such that the reflected signal has traveled through both multiplexer/demultiplexers 312, 316. The second multiplexer/demultiplexer 316 multiplexes light reflected by the mirror 367 along with the upstream signal from the optical subscribers and it is demultiplexed by the first multiplxer/demultiplxer 312. The demultiplxed signal is inputted to the lock-in detector 372. The wavelength tracking component 330 measures the difference in the transmission band of wavelengths between the first multiplexer/demultiplexer 312 and the second multiplexer/demultiplexer 316 based upon a change detected in the reflected portion of the modulated second band of wavelengths. The wavelength tracking component 330 may compare the known frequency and the phase of the oscillator 369 to the frequency and phase of the reflected signal to determine the temperature difference between the first multiplexer/demultiplexer 312 and the second multiplexer/demultiplexer 316. For example, if the phase of the reflected signal has shifted forward in time than that indicates an increase occurred in the operating temperature of the temperature of the second optical multiplexer/demultiplexer 316. Accordingly, the temperature controller 311 then acts to increase the operating temperature of the first multiplexer/demultiplexer 312 to match up transmission band of wavelengths between the first multiplexer/demultiplexer 312 and the second multiplexer/demultiplexer 316. For an embodiment, the lock-in detector 372 establishes the amplitude of the reflected modulated signal. The lock-in detector 372 compares the reflected modulated signal to a reference signal to determine when to activate the temperature controller 311. Also, the wavelength tracking between the first and second multiplexer/demultiplexers 312, 316 may be accomplished without a mirror 367. The wavelength tracking component 330 may measure the difference in the transmission band of wavelengths between the first multiplexer/demultiplexer 312 and the second multiplexer/demultiplexer 316 based upon a change detected in the transmitted signal from a subscriber derived from the modulated second band of wavelengths. The output signal of the lock-in detector 372 is in inverse proportion to the insertion loss of a particular optical cable to a subscriber or the optical cable from the remote mode. The output signal of the lock-in detector 372 couples to the fiber fault detector 331 to detect an optical cable fault that causes abnormal insertion loss. For an embodiment, the reference values of the various reference signals may be set after all of the connections are determined to be working properly. FIGS. 4a and 4b illustrate a flow diagram of an embodiment of the wavelength-division-multiplexing passive-optical-network. For an embodiment, the passive-optical-network passes upstream and down-stream signals between a first location and a second location remote from the first location. In block 402, the passive-optical-network supplies an optical signal containing a first band of wavelengths to a first multiplexer/demultiplexer from a source such as an amplified-spontaneous-emission light source. In block 404, the passive-optical-network spectrum slices the first broadband of wavelengths with the first multiplexer/demultiplexer. In block 406, the passive-optical-network supplies the spectrally sliced wavelengths to a first group of optical transmitters in order to control the transmission output wavelength in the first band of wavelengths that is generated by one or more optical transmitters in the first group. Each optical transmitter self-aligns the operating wavelength of that optical transmitter to the wavelengths within a spectral slice received from the first multiplexer/demultiplexer. For an embodiment, the transmitters in a first location, such as a supervisory node, generate the down-stream signals. The downstream signals pass through its band splitting filter. The 1×n optical multiplexer/demultiplexer in the supervisory node wavelength-division multiplexes the down stream signals. An n×n optical coupler splits those downstream signals. The signals forced into the first broadband light source are terminated, while the other signals are bound for each optical subscriber after being demultiplexed by the 1×n optical multiplexer/demultiplexer located at the remote node. At the subscriber side, the signals are passed through band splitting filters and reach the optical receivers. In block 408, the passive-optical-network supplies a broadband optical signal containing a second band of wavelengths to a second multiplexer/demultiplexer. In block 410, the passive-optical-network spectrally slices the second broadband of wavelengths with the second multiplexer/demultiplexer. In block 412, the passive-optical-network supplies the spectrally sliced wavelengths to a second group of optical transmitters in order to control the transmission output wavelength in the second band of wavelengths that is generated by one or more optical transmitters in the second group. Each optical transmitter self-aligns the operating wavelength of that optical transmitter to the wavelengths within a spectral slice received from the second multiplexer/demultiplexer. The first multiplexer/demultiplexer may be located in a first location such as supervisory node and the second multiplexer/demultiplexer may be located in a second location remote from the first location, such as a remote node. For an embodiment, the upstream-signals depart from the optical transmitters in the subscriber side, pass through band splitting filters and are multiplexed by a 1×n optical multiplexer/demultiplexer at the remote node. The n×n optical coupler splits the multiplexed signals after passing through the optical fiber cable. The upstream signals split into the second broadband light source are terminated, while the other up-stream signals continue to propagate to optical receivers at the supervisory node via a 1×n optical multiplexer/demultiplexer. In block 414, the passive-optical-network tracks the optical power of the second band of wavelengths received at the first location after passing through the first multiplexer/demultiplexer and adjusts the transmission band of wavelengths passed by the first multiplexer/demultiplexer based upon achieving substantially maximum power for that second band of wavelengths. In block 416, the passive-optical-network uses a n×n coupler to extract a portion of the optical signal having a first band of wavelengths going to subscribers. In block 418, the passive-optical-network filters out wavelengths not in the first band of wavelengths and delivers the optical signal having the first band of wavelengths to a fiber fault detector. In block 420, the passive-optical-network routs a portion of a reflection of the optical signal having the first band of wavelengths, if one exists, to the fiber fault detector. In block 422, the passive-optical-network compares the portion of the optical signal having the first band of wavelengths to the portion of the reflection of that signal to determine if a fault exists in the optical path going to the subscribers. Note, the specific numeric reference should not be interpreted as a literal sequential order but rather interpreted that the first band of wavelength is different than a second band of wavelengths. Thus, the specific details set forth are merely exemplary. Some additional embodiments may include: a single device may provide the function of both the first broadband light source and the second broadband light source; the WDM PON may use more than two different bands of wavelengths; each multiplexer/demultiplexer may be an athermal arrayed waveguide grating; each receiver may compare it's the strength the received signal to a reference value and communicate with the fault detector if that received signal falls below the reference value, each multiplexer/demultiplexer may merely divide an input light signal rather than spectrally slice the input light signal; more than one remote node may exist; an optical transmitter may be operated continuous wave and modulated by an external modulator, etc. In the forgoing specification, the invention has been described with reference to specific exemplary embodiments thereof. It will, however, be evident that various modifications and changes may be made thereto without departing from the broader spirit and scope of the invention as set fourth in the appended claims. The specification and drawings are, accordingly, to be regarded in an illustration rather then a restrictive sense.
<SOH> BACKGROUND <EOH>Some wavelength-division-multiplexing-passive-optical-networks require precise wavelength alignment between the wavelengths of the signal from a transmitter in a central office to a device in a remote site distributing that signal to a subscriber. In a passive-optical-network, a remote node containing the signal-distributing device is typically located outdoors without any electrical power supply. The transmission band of wavelengths of the outdoor signal-distributing device can change according to the variation of the external temperature. Misalignment of the wavelength between the transmitted signal and the operating wavelength of the device distributing the signal introduces extra insertion loss in the signal. A possible way to minimize the misalignment can be to use a narrow-linewidth distributed feedback laser diode (DFB LD) that essentially always falls within the shifting bandwidths of the multiplexers as an optical transmitter to satisfy the wavelength alignment condition. However, this arrangement may not be an economic solution because of the high price of each DFB LD. Further, in systems having two or more wavelength division multiplexers located in different areas, misalignment of the transmission band of wavelengths between the two or more wavelength division multiplexers may occur due to the temperature variations at these different areas. The operating transmission band of wavelengths of these devices can vary depending on the temperature of the device. Complex channel selection and temperature control circuits could be employed to compensate for the large insertion loss in optical signals passing through optical multiplexer/demultiplexers located in different locations. However, the complexity of the channel selection circuit has the disadvantage that the complexity of the circuit becomes greater and greater as the number of input ports of the circuit increases. Thus, the more channels being distributed by a multiplexer/demultiplexer, then the more complex and expensive the channel selection and temperature control circuit becomes.
<SOH> SUMMARY <EOH>Various methods, systems, and apparatuses are described in which a passive-optical-network includes a first multiplexer/demultiplexer, a second multiplexer/demultiplexer, a wavelength tracking component, and a transmission wavelength controller. The first multiplexer/demultiplexer is located in a first location. The second multiplexer/demultiplexer is located in a second location remote from the first location. The wavelength tracking component determines the difference between the transmission band of wavelengths of the first multiplexer/demultiplexer and the second multiplexer/demultiplexer to provide a control signal to match the transmission band of wavelengths of the first multiplexer/demultiplexer and the second multiplexer/demultiplexer. The transmission wavelength controller alters an operating parameter of the first multiplexer/demultiplexer based on the control signal to control the transmission band of wavelengths of the first multiplexer/demultiplexer. Other features and advantages of the present invention will be apparent from the accompanying drawings and from the detailed description that follows below.
20050405
20081223
20051229
65806.0
0
PHAN, HANH
WAVELENGTH-DIVISION-MULTIPLEXING PASSIVE OPTICAL NETWORK UTILIZING FIBER FAULT DETETORS AND/OR WAVELENGTH TRACKING COMPONENTS
UNDISCOUNTED
0
ACCEPTED
2,005
10,530,558
ACCEPTED
Dental coating kit
The invention provides a dental coating kit with high adhesiveness to teeth that contains a primer composition including an acidic group-containing polymeric monomer (a), water (b) and a water-soluble solvent (c) and a surface smoothing composition including a polyfunctional polymeric monomer (f), a volatile solvent (g) and a photopolymerization initiator (h); and a dental coating kit with high adhesiveness to teeth and minimally suffering from chipping and peeling off that contains a primer composition including an acidic group-containing polymeric monomer (a), water (b) and a water-soluble solvent (c), a coating composition including a polymeric monomer (d) and a photopolymerization initiator (e), and a surface smoothing composition including a polyfunctional polymeric monomer (f), a volatile solvent (g) and a photopolymerization initiator (h). Either dental coating kit is particularly useful as a kit for preventing stain and color return of a bleached tooth.
1. A dental coating kit comprising: a primer composition including an acidic group-containing polymeric monomer (a), water (b) and a water-soluble solvent (c); and a surface smoothing composition including a polyfunctional polymeric monomer (f), a volatile solvent (g) and a photopolymerization initiator (h). 2. The dental coating kit according to claim 1, wherein the primer composition includes the acidic group-containing polymeric monomer (a) in a ratio of 1 wt % through 90 wt %, the water (b) in a ratio of 0.1 wt % through 90 wt % and the water-soluble solvent (c) in a ratio of 1 wt % through 98 wt %, and the surface smoothing composition includes the polyfunctional polymeric monomer (f) in a ratio of 40 wt % through 98 wt %, the volatile solvent (g) in a ratio of 1 wt % through 59 wt % and the photopolymerization initiator (h) in a ratio of 0.01 wt % through 10 wt % based on a total weight of polymeric monomer(s) included in the surface smoothing composition. 3. The dental coating kit according to claim 1 or 2, wherein the photopolymerization initiator (h) is an acylphosphine oxide. 4. The dental coating kit according to claim 3, wherein the acylphosphine oxide is 2,4,6-trimethylbenzoyldiphenylphosphine oxide. 5. The dental coating kit according to any of claims 1 through 4, wherein the surface smoothing composition has viscosity at 30° C. of 30 cP through 3000 cP. 6. The dental coating kit according to any of claims 1 through 5, wherein the dental coating kit is used for a bleached tooth. 7. A dental coating method comprising the steps of applying, on a tooth, a primer composition including an acidic group-containing polymeric monomer (a), water (b), a water-soluble solvent (c) and, if necessary, a polymerization initiator; forming a primer layer by drying or polymerically curing the primer composition; applying, on the primer layer, a surface smoothing composition including a polyfunctional polymeric monomer (i), a volatile solvent (g) and a photopolymerization initiator (h); and forming a surface layer by polymerically curing the surface smoothing composition through light irradiation. 8. A dental coating kit comprising: a primer composition including an acidic group-containing polymeric monomer (a), water (b) and a water-soluble solvent (c); a coating composition including a polymeric monomer (d) and a photopolymerization initiator (e); and a surface smoothing composition including a polyfunctional polymeric monomer (f), a volatile solvent (g) and a photopolymerization initiator (h). 9. The dental coating kit according to claim 8, wherein the primer composition includes the acidic group-containing polymeric monomer (a) in a ratio of 1 wt % through 90 wt %, the water (b) in a ratio of 0.1 wt % through 90 wt % and the water-soluble solvent (c) in a ratio of 1 wt % through 98 wt %, the coating composition includes the polymeric monomer (d) in a ratio of 40 wt % through 99.99 wt % and the photopolymerization initiator (e) in a ratio of 0.01 wt % through 10 wt % based on the polymeric monomer (d), and the surface smoothing composition includes the polyfunctional polymeric monomer (f) in a ratio of 40 wt % through 98 wt %, the volatile solvent (g) in a ratio of 1 wt % through 59 wt % and the photopolymerization initiator (h) in a ratio of 0.01 wt % through 10 wt % based on a total weight of polymeric monomer(s) included in the surface smoothing composition. 10. The dental coating kit according to claim 8 or 9, wherein the coating composition further includes an inorganic filler with a refractive index of 1.9 or more and colloidal silica. 11. The dental coating kit according to any of claims 8 through 10, wherein the coating composition has viscosity at 30° C. of 300 cP through 50,000 cP. 12. The dental coating kit according to any of claims 8 through 11, wherein the polymeric monomer (d) includes a hydrophobic polymeric monomer and a hydrophilic polymeric monomer, and the coating composition includes the hydrophilic polymeric monomer in a ratio of 5 wt % through 50 wt %. 13. The dental coating kit according to claim 12, wherein the hydrophilic polymeric monomer is 2-hydroxyethyl methacrylate. 14. The dental coating kit according to any of claims 8 through 13, wherein the dental coating kit is used for a bleached tooth. 15. A dental coating method comprising the steps of applying, on a tooth, a primer composition including an acidic group-containing polymeric monomer (a), water (b), a water-soluble solvent (c), and, if necessary, a polymerization initiator; forming a primer layer by drying or polymerically curing the primer composition; applying, on the primer layer, a coating composition including a polymeric monomer (d) and a photopolymerization initiator (e); forming an intermediate layer by polymerically curing the coating composition through light irradiation; applying, on the intermediate layer, a surface smoothing composition including a polyfunctional polymeric monomer (f), a volatile solvent (g) and a photopolymerization initiator (h); and forming a surface layer by polymerically curing the surface smoothing composition through light irradiation.
TECHNICAL FIELD The present invention relates to a dental coating kit, and more particularly, it relates to a coating kit useful for preventing stain and color change of teeth and in particular, a coating kit useful for preventing stain and color return of bleached teeth. BACKGROUND ART Teeth are stained or changed in color due to deposit of a colored substance included in a cigarette, coffee and the like, or breeding of chromogenic bacteria. In general, women wish to make their teeth look white and beautiful by preventing the stain and color change of the teeth more strongly than men. This is the reason why the number of women, and particularly young women, that receive a bleaching treatment for teeth described below is recently rapidly increasing. The bleaching treatment for teeth is carried out not only as a part of beauty culture for making teeth look white and beautiful but also as means for restoring stained or color-changed teeth to former natural teeth. In the bleaching treatment, a bleaching agent including, as a principal component, hydrogen peroxide or urea peroxide is generally used. The bleaching agent has two functions, that is, a decoloring function to decompose a coloring matter deposited on teeth and a function to attain whiteness by roughening the surfaces of teeth for causing diffuse reflection of light. Owing to these two functions, the teeth can be made to look white. Although the bleaching treatment is effective for improving the aesthetic property, plaque, protein, a coloring matter and the like tend to adhere to the teeth after the bleaching treatment because the surfaces of the teeth are roughened. Therefore, for a while after the bleaching treatment, particularly for a couple of days after the bleaching, it is necessary to refrain from ingesting coffee, curry and citrus fruit juice and smoking, which can be a cause of stain. Even when the ingestion and smoking are thus restricted, however, the teeth may be stained in a short period of time. Also, plaque, protein, a coloring matter and the like are gradually accumulated on the teeth, or the surfaces of the teeth having been roughened through the bleaching treatment are gradually naturally restored due to remineralization caused by saliva in the oral cavity, and therefore, the bleached color is frequently returned to the former color prior to the bleaching treatment in approximately a half or two years after the bleaching. In order to suppress the stain and the color return of teeth occurring after the bleaching, application of a finishing coating composition to teeth after the bleaching treatment is conventionally proposed. As such a finishing coating composition, for example, a composition including 10 wt % through 80 wt % of a polyfunctional acrylate monomer, 20 wt % through 80 wt % of a low-boiling solvent and 0.4 wt % through 5 wt % of a visible light-initiated polymerization initiator is proposed in Japanese Laid-Open Patent Publication No. 2001-271009, and a composition including 10 wt % through 80 wt % of a polyfunctional acrylate monomer, 20 wt % through 80 wt % of a low-boiling solvent, 0.4 wt % through 5 wt % of a visible light-initiated polymerization initiator and 0.5 wt % through 10 wt % of a white inorganic impalpable powder is proposed in Japanese Laid-Open Patent Publication No. 2002-3327. Both of these compositions are, however, poor at adhesiveness to teeth. As a countermeasure against this disadvantage, addition of 0.1 wt % through 5 wt % of a phosphoric ester adhesive monomer to each composition is proposed (see Japanese Laid-Open Patent Publication No. 2001-271009, claim 8, [0030] and [0031]; and Japanese Laid-Open Patent Publication No. 2002-3327, claim 10, [0039] and [0040]). The present inventors have, however, found the following: Even when a given amount of phosphoric ester adhesive monomer is added, the adhesiveness to teeth is not largely improved but the surface curing property is largely degraded. Therefore, it is difficult to thus obtain a practically usable coating composition. The present invention was devised to overcome the aforementioned problem, and an object is providing a dental coating kit that is good at adhesiveness to teeth and is useful for preventing stain and color change of teeth. DISCLOSURE OF INVENTION In order to achieve the object, the dental coating kit (hereinafter sometimes referred to as the “first kit”) of this invention includes a primer composition including an acidic group-containing polymeric monomer (a), water (b) and a water-soluble solvent (c); and a surface smoothing composition including a polyfunctional polymeric monomer (f), a volatile solvent (g) and a photopolymerization initiator (h). The primer composition used in this invention is one generally designated as a self-etching type primer, and permeates into teeth while etching them so as to exhibit high adhesiveness. In particular, it deeply permeates into roughened teeth obtained after bleaching so as to exhibit very high adhesiveness. Since the adhesiveness to teeth is secured by the primer composition, there is no need to add a phosphoric ester adhesive monomer to the surface smoothing composition applied after the application of the primer composition. In the case where a phosphoric ester adhesive monomer is not added to the surface smoothing composition, a kit good not only at adhesiveness to teeth owing to the primer composition but also at surface curing property is obtained. The primer composition used in the invention includes an acidic group-containing polymeric monomer (a), water (b) and a water-soluble solvent (c). The acidic group-containing polymeric monomer (a) secures the adhesiveness to teeth. The acidic group-containing polymeric monomer (a) is a polymeric monomer that has an acidic group such as a phosphoric group, a pyrophosphoric group, a thiophosphoric group, a carboxylic group or a sulfonic group and also has a polymerizable unsaturated group such as an acryloyl group, a methacryloyl group, a vinyl group or a vinylbenzyl group. In particular, a polymeric monomer having an acryloyl group or a methacryloyl group as the unsaturated group is preferred. Also, in the acidic group-containing polymeric monomer (a), the solubility of its calcium salt in water at 25° C. is preferably 10 wt % or less, more preferably 1 wt % or less and most preferably 0.1 wt % or less because such a polymeric monomer is good at adhesiveness and acid resistance. Specific examples of the acidic group-containing polymeric monomer (a) are described below. Hereinafter, methacryl and acryl are sometimes comprehensively mentioned as (meth)acryl and methacryloyl and acryloyl are sometimes comprehensively mentioned as (meth)acryloyl. Examples of a phosphoric group-containing polymeric monomer are 2-(meth)acryloyloxyethyl dihydrogenphosphate, 3-(meth)acryloyloxypropyl dihydrogenphosphate, 4-(meth)acryloyloxybutyl dihydrogenphosphate, 5-(meth)acryloyloxypentyl dihydrogenphosphate, 6-(meth)acryloylhexyl dihydrogenphosphate, 7-(meth)acryloyloxyheptyl dihydrogenphosphate, 8-(meth)acryloyloxyoctyl dihydrogenphosphate, 9-(meth)acryloyloxynonyl dihydrogenphosphate, 10-(meth)acryloyloxydecyl dihydrogenphosphate, 11-(meth)acryloyloxyundecyl dihydrogenphosphate, 12-(meth)acryloyloxydodecyl dihydrogenphosphate, 16-(meth)acryloyloxyhexadecyl dihydrogenphosphate, 20-(meth)acryloyloxyeicosyl dihydrogenphosphate, 4-[2-(meth)acryloyloxyethyl]cyclohexyloxy dihydrogenphosphate, di[2-(meth)acryloyloxyethyl]hydrogenphosphate, di[3-(meth)acryloyloxypropyl]hydrogenphosphate, di[4-(meth)acryloyloxybutyl]hydrogenphosphate, di[5-(meth)acryloyloxypentyl]hydrogenphosphate, di[6-(meth)acryloyloxyhexyl]hydrogenphosphate, di[7-(meth)acryloyloxyheptyl]hydrogenphosphate, di[8-(meth)acryloyloxyoctyl]hydrogenphosphate, di[9-(meth)acryloyloxynonyl]hydrogenphosphate, di[10-(meth)acryloyloxydecyl hydrogenphosphate, 2-(meth)acryloyloxyethyl phenyl hydrogenphosphate, 2-(meth)acryloyloxyethyl hexyl hydrogenphosphate, 2-(meth)acryloyloxyethyl 2′-bromooctyl hydrogenphosphate, 2-(meth)acryloyloxyethyl octyl hydrogenphosphate, 2-(meth)acryloyloxyethyl nonyl hydrogenphosphate, 2-(meth)acryloyloxyethyl decyl hydrogenphosphate, 2-(meth)acryloyloxybutyl decyl hydrogenphosphate, (meth)acryloyloxyethyl phenyl phosphonate; (8-methacryloxy)octyl-3-phosphonopropionate, (9-methacryloxy)nonyl-3-phosphonopropionate, (10-methacryloxy)decyl-3-phosphonopropionate, (6-methacryloxy)octyl-3-phosphonoacetate, (10-methacryloxy)decyl-3-phosphonoacetate; 2-methacryloyloxyethyl (4-methoxyphenyl) hydrogenphosphate, 2-methacryloyloxypropyl (4-methoxyphenyl) hydrogenphosphate, and phosphoric group-containing hydrophobic polymeric monomers and their acid chlorides described in Japanese Laid-Open Patent Publication No. Sho 52-113089, Japanese Laid-Open Patent Publication No. Sho 53-67740, Japanese Laid-Open Patent Publication No. Sho 53-69494, Japanese Laid-Open Patent Publication No. Sho 53-144939, Japanese Laid-Open Patent Publication No. Sho 58-128393 and Japanese Laid-Open Patent Publication No. Sho 58-192891. In addition, the examples are alkali metal salts (such as sodium salt, potassium salt and lithium salt) and an ammonium salt of each of the aforementioned phosphoric group-containing polymeric monomers. Examples of a pyrophosphoric group-containing polymeric monomer are di[2-(meth)acryloyloxyethyl]pyrophosphate, di[3-(meth)acryloyloxypropyl]pyrophosphate, di[4-(meth)acryloyloxybutyl]pyrophosphate, di[5-(meth)acryloyloxypentyl]pyrophosphate, di[6-(meth)acryloyloxyhexyl]pyrophosphate, di[7-(meth)acryloyloxyheptyl]pyrophosphate, di[8-(meth)acryloyloxyoctyl]pyrophosphate, di[9-(meth)acryloyloxynonyl]pyrophosphate, di[10-(meth)acryloyloxydecyl]pyrophosphate, di[12-(meth)acryloyloxydodecyl]pyrophosphate, and their acid chlorides, alkali metal salts and ammonium salts. Examples of a thiophosphoric group-containing polymeric monomer are 2-(meth)acryloyloxyethyl dihydrogendithiophosphate, 3-(meth)acryloyloxypropyl dihydrogendithiophosphate, 4-(meth)acryloyloxybutyl dihydrogendithiophosphate, 5-(meth)acryloyloxypentyl dihydrogendithiophosphate, 6-(meth)acryloyloxyhexyl dihydrogendithiophosphate, 7-(meth)acryloyloxyheptyl dihydrogendithiophosphate, 8-(meth)acryloyloxyoctyl dihydrogendithiophosphate, 9-(meth)acryloyloxynonyl dihydrogendithiophosphate, 10-(meth)acryloyloxydecyl dihydrogenthiophosphate, and their acid chlorides, alkali metal salts and ammonium salts. Examples of a carboxylic group-containing polymeric monomer are 4-(meth)acryloyloxyethyloxycarbonylphthalic acid, 4-(meth)acryloyloxybutyloxycarbonylphthalic acid, 4-(meth)acryloyloxyoctyloxycarbonylphthalic acid, 4-(meth)acryloyloxydecyloxycarbonylphthalic acid, and their acid anhydrides, 6-(meth)acryloylaminohexylcarboxylic acid, 8-(meth)acryloylaminooctylcarboxylic acid, 9-(meth)acryloyloxy-1,1-nonanedicarboxylic acid, 10-(meth)acryloyloxy-1,1-decanedicarboxylic acid, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, (meth)acrylic acid, maleic acid, and their acid chlorides, alkali metal salts and ammonium salts. Examples of a sulfonic group-containing polymeric monomer are compounds having a sulfonic group such as 2-(meth)acrylamidoethyl sulfonic acid, 3-(meth)acrylamidopropyl sulfonic acid, 4-(meth)acrylamidobutyl sulfonic acid, 6-(meth)acrylamidohexyl sulfonic acid, 8-(meth)acrylamidooctyl sulfonic acid, 10-(meth)acrylamidodecyl sulfonic acid and styrene sulfonic acid, and their acid chlorides, alkali metal salts and ammonium salts. As the acidic group-containing polymeric monomer (a), the phosphoric group-containing polymeric monomers are preferably used because of their high adhesiveness. In particular, a phosphoric group-containing polymeric monomer having an alkylene group with a carbon number of 6 through 25 and a phosphoric group-containing polymeric monomer having an alkyl group and/or a phenyl group are more preferably used, and a phosphoric group-containing polymeric monomer having an alkylene group with a carbon number of 6 through 12 is most preferably used. One of these acidic group-containing polymeric monomers (a) may be singly used, or two or more of them may be used together if necessary. The adhesive strength to teeth may be lowered when the acidic group-containing polymeric monomer (a) is deficiently or excessively included. The mixing ratio of the acidic group-containing polymeric monomer (a) is generally 1 wt % through 90 wt %, preferably 5 wt % through 70 wt % and more preferably 10 wt % through 50 wt % based on a total weight of the primer composition. The water (b) increases the demineralization against teeth of the acidic group-containing polymeric monomer (a). It is necessary to use water that includes substantially no impurity harmfully affecting the adhesiveness. Distilled water or ion-exchanged water is preferably used. The adhesive strength to teeth may be lowered when the water (b) is deficiently or excessively included. The mixing ratio of the water (b) is generally 0.1 wt % through 90 wt %, preferably 1 wt % through 70 wt % and more preferably 5 wt % through 50 wt % based on the total weight of the primer composition. The water-soluble solvent (c) improves the permeability to teeth. A solvent that can dissolve the acidic group-containing polymeric monomer (a) and that can be dissolved in water at 25° C. at solubility of 5 wt % or more, preferably 30 wt % or more and more preferably in an arbitrary ratio is used. Examples of the water-soluble solvent (c) are a water-soluble volatile solvent (c-1) having a boiling point at normal pressure of 150° C. or less and preferably 100° C. or less, a water-soluble solvent (c-2) having a boiling point higher than 150° C. at normal pressure, and a water-soluble solvent (c-3) having a polymerizable unsaturated group and solubility in water at 25° C. of 10 wt % or more (hereinafter sometimes referred to as the “hydrophilic polymeric monomer (c-3)”). Examples of the water-soluble volatile solvent (c-1) are ethanol, methanol, 1-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, 1,2-diethoxyethane and tetrahydrofuran. Examples of the water-soluble solvent (c-2) are dimethyl sulfoxide, ethylene glycol and polyethylene glycol. Examples of the hydrophilic polymeric monomer (c-3) are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-trimethylammoniumethyl (meth)acryl chloride, (meth)acrylamide, 2-hydroxyethyl (meth)acrylamide and polyethylene glycol di(meth)acrylate (having nine or more oxyethylene groups). Among the aforementioned water-soluble solvents (c), the water-soluble volatile solvent (c-1) and the hydrophilic polymeric monomer (c-3) are preferred. The water-soluble volatile solvent (c-1) is preferred because it can be easily perspired with a dental air syringe. Also, the hydrophilic polymeric monomer (c-3) is preferred because it can be cured simultaneously with the acidic group-containing polymeric monomer (a). Among the aforementioned examples of the hydrophilic polymeric monomer (c-3), 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate and polyethylene glycol di(meth)acrylate (having nine oxyethylene groups) are particularly preferred. One of the water-soluble solvents (c) may be singly used, or two or more of them may be used together if necessary. The permeability to teeth and the adhesive strength may be lowered when the water-soluble solvent (c) is deficiently or excessively included. The mixing ratio of the water-soluble solvent (c) is generally 1 wt % through 98 wt %, preferably 5 wt % through 90 wt % and more preferably 10 wt % through 60 wt % based on the total weight of the primer composition. In order to improve the adhesiveness, the mechanical strength and the coating property of the primer composition, a hydrophobic polymeric monomer with solubility in water at 25° C. of less than 10 wt % and preferably of 1 wt % or less may be included apart from the acidic group-containing polymeric monomer (a) and the hydrophilic polymeric monomer (c-3). Examples of such a hydrophobic polymeric monomer are esters such as α-cyanoacrylic ester, (meth)acrylic ester, α-halogenoacrylic acid ester, crotonic ester, cinnamic ester, sorbic ester, maleic ester and itaconic ester, a (meth)acrylamide derivative, vinyl esters, vinyl ethers, a mono-N-vinyl derivative and a styrene derivative. Among these monomers, (meth)acrylic ester is preferred. Now, specific examples of the (meth)acrylic ester will be described. A monomer having n (wherein n=1, 2, 3, etc.) olefin double bonds is expressed as an n-functional monomer, and the examples are divided into three groups of mono-functional monomers, bifunctional monomers, and monomers of trifunctional or higher functionality. Mono-functional monomers: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, 3-methacryloyloxypropyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane Bifunctional monomers: ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, bisphenol A diglycidyl (meth)acrylate, 2,2-bis[4-(meth)acryloyloxyethoxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxypolyethoxyphenyl]propane, 2,2-bis[4-[3- (meth)acryloyloxy-2-hydroxypropoxy]phenyl]propane, 1,2-bis [3-(meth)acryloyloxy-2-hydroxypropoxy]ethane, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, [2,2,4-trimethylhexamethylene bis(2-carbamoyloxyethyl)]dimethacrylate Monomers of trifunctional or higher functionality: trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, N,N′-(2,2,4-trimethylhexamethylene) bis[2-(aminocarboxy)propane-1,3-diol]tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate One of these hydrophobic polymeric monomers may be singly used, or two or more of them may be used together if necessary. When the hydrophobic polymeric monomer is excessively included, the permeability to teeth and the adhesive strength may be lowered. The mixing ratio of the hydrophobic polymeric monomer is generally 70 wt % or less, preferably 50 wt % or less and more preferably 30 wt % or less based on the total weight of the primer composition. In order to improve the adhesiveness, the primer composition may include a photopolymerization initiator and/or a chemical polymerization initiator. Examples of the photopolymerization initiator are α-diketones, ketals, thioxanthones, acylphosphine oxides and α-aminoacetophenones. Examples of the α-diketones are camphorquionone, benzyl and 2,3-pentanedione. Examples of the ketals are benzyl dimethyl ketal and benzyl diethyl ketal. Examples of the thioxanthones are 2-chlorothioxanthone and 2,4-diethylthioxanthone. Examples of the acylphosphine oxides are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(benzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, tris(2,4-dimethylbenzoyl)phosphine oxide, tris(2-methoxybenzoyl)phosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi-(2,6-dimethylphenyl) phosphonate, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, and a water-soluble acylphosphine oxide compound disclosed in Japanese Patent Publication No. Hei 3-57916. Examples of the α-aminoacetophenones are 2-benzyl-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-1,2-benzyl-dimethylamino-1-(4-morpholinophenyl)-propanone-1,2-benzyl-diethylamino- 1-(4-morpholinophenyl)-propanone-1,2-benzyl-dimethylamino-1-(4-morpholinophenyl)-pentanone-1, and 2-benzyl-diethylamino-1-(4-morpholinophenyl)-pentanone-1. One of these photopolymerization initiators may be singly used, or two or more of them may be used together if necessary. The mixing ratio of the photopolymerization initiator is preferably 0.01 wt % through 10 wt %, more preferably 0.05 wt % through 7 wt % and most preferably 0.1 wt % through 5 wt % based on the total weight of the polymeric monomer(s) included in the primer composition. The photopolymerization initiator may be used by itself or used together with a polymerization promoter such as a tertiary amine, an aldehyde or a compound having a thiol group for accelerating the photo-curing property. Examples of the tertiary amine are 2-dimethylaminoethyl (meth)acrylate, N,N-bis[(meth)acryloyloxyethyl]-N-methylamine, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, butoxyethyl 4-dimethylaminobenzoate, N-methyldiethanolamine, 4-dimethylaminobenzophenone and N,N-di(2-hydroxyethyl)-p-toluidine. Examples of the aldehyde are dimethylaminobenzaldehyde and terephthalaldehyde. Examples of the compound having a thiol group are 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane and thiobenzoic acid. One of these polymerization promoters may be singly used, or two or more of them may be used together if necessary. The mixing ratio of the polymerization promoter is preferably 0.01 wt % through 10 wt %, more preferably 0.05 wt % through 7 wt % and most preferably 0.1 wt % through 5 wt % based on the total weight of the polymeric monomer(s) included in the primer composition. As the chemical polymerization initiator, a redox type polymerization initiator composed of an oxidizing agent and a reducing agent is preferably used. When the redox type polymerization initiator is used, it is necessary to divide packaging of the primer composition into two or more sections so that the oxidizing agent and the reducing agent can be spaced from each other. Examples of the oxidizing agent are organic peroxides such as diacyl peroxides, peroxy esters, dialkyl peroxides, peroxy ketals, ketone peroxides and hydroperoxides. Specific examples of the diacyl peroxides are benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m-toluoyl peroxide. Specific examples of the peroxy esters are t-butyl peroxybenzoate, bis-t-butyl peroxyisophthalate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butyl peroxy-2-ethylhexanoate and t-butylperoxy isopropyl carbonate. Specific examples of the dialkyl peroxides are dicumyl peroxide, di-t-butyl peroxide and lauroyl peroxide. A specific example of the peroxy ketals is 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane. Specific examples of the ketone peroxides are methyl ethyl ketone peroxide, cyclohexanone peroxide and methyl acetoacetate peroxide. Specific examples of the hydroperoxides are t-butyl hydroperoxide, cumene hydroperoxide and p-diisopropylbenzene peroxide. As the reducing agent, an aromatic tertiary amine, an aliphatic tertiary amine, a sulfinic acid or its salt is preferably used. Examples of the aromatic tertiary amine are N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, N,N-dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-isopropylaniline, N,N-dimethyl-4-t-butylaniline, N,N-dimethyl-3,5-di-t-butylaniline, N,N-bis(2-hydroxyethyl)-3, 5-dimethylaniline, N,N-di(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-isopropylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)- 3,5-di-isopropylaniline, N,N-bis(2-hydroxyethyl)-3,5-dibutylaniline, ethyl 4-dimethylaminobenzoate, n-butoxyethyl 4-dimethylaminobenzoate and (2-methacryloyloxy)ethyl 4-dimethylaminobenzoate. Examples of the aliphatic tertiary amine are trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-n-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, (2-dimethylamino)ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate and triethanolamine trimethacrylate. Examples of the sulfinic acid and its salt are benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, calcium benzenesulfinate, lithium benzenesulfinate, toluenesulfinic acid, sodium toluenesulfinate, potassium toluenesulfinate, calcium toluenesulfinate, lithium toluenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate and calcium 2,4,6-triisopropylbenzenesulfinate. One of these oxidizing agents or these reducing agents may be singly used, or two or more of them may be used together if necessary. The mixing ratio of each of the oxidizing agent and the reducing agent is preferably 0.01 wt % through 10 wt %, more preferably 0.05 wt % through 7 wt % and most preferably 0.1 wt % through 5 wt % based on the total weight of the polymeric monomer(s) included in the primer composition. In order to adjust the coating property and the flowability of the primer composition, it may include a filler. As the filler, an inorganic filler, an organic filler or an organo-mineral complex filler may be used. As the inorganic filler, silica, a mineral including, as a matrix, silica such as kaoline, clay, isinglass or mica, and ceramics and glass including silica as a matrix and further including Al2O3, B2O3, TiO2, ZrO2, BaO, La2O3, SrO2, CaO, P2O5 or the like are preferably used. Specific examples of such glass are lanthanum glass, barium glass, strontium glass, soda glass, lithium borosilicate glass, zinc glass, fluoroalumino silicate glass, borosilicate glass and bioglass. Apart from them, crystalline quartz, hydroxyl-apatite, alumina, titanium oxide, yttrium oxide, zirconia, calcium phosphate, barium sulfate, aluminum hydroxide, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride or ytterbium fluoride is also preferably used. Examples of the organic filler are polymethyl methacrylate, polymethyl methacrylate, a polymer of polyfunctional methacrylate, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber and styrene-butadiene rubber. Examples of the organo-mineral complex filler are a filler obtained by dispersing an inorganic filler in an organic filler and an inorganic filler coated with any of various polymeric monomers. In order to adjust the flowability of the primer composition or to improve the coating property thereof, the filler may be subjected to surface-treating with a known surface-treatment agent such as a silane coupling agent before adding to the primer composition. Examples of the surface-treatment agent used in this case are vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and γ-aminopropyltriethoxysilane. One of these fillers may be singly used, or two or more of them may be used together if necessary. The mixing ratio of the filler is generally 50 wt % or less and preferably 30 wt % or less based on the total weight of the primer composition. When the mixing ratio exceeds 50 wt %, the permeability to teeth and the adhesiveness may be lowered. Furthermore, in order to improve the demineralization of the primer composition against teeth, an acid that has smaller pKa than the acidic group-containing polymeric monomer (a) and does not have a polymeric group may be included in the primer composition. Examples of such an acid are inorganic acids such as phosphoric acid, nitric acid and sulfuric acid, and organic acids such as acetic acid, citric acid, trichloroacetic acid and p-toluenesulfonic acid. When such an acid having no polymeric group is excessively included, however, the acid may damage the dentine or be eluted after the application so as to lower the adhesiveness to teeth of the primer composition. Accordingly, in general, the mixing ratio of the acid is preferably 10 wt % or less and more preferably 5 wt % or less based on the total weight of the primer composition. The primer composition may include a polymerization inhibitor, a coloring agent, a fluorescent agent, a ultraviolet absorbing agent and the like. Also, in order to provide antibacterial activity, an antibacterial substance such as cetylpyridinium chloride, benzalkonium chloride, (meth)acryloyloxydodecylpyridinium bromide, (meth)acryloyloxyhexadecylpyridinium chloride, (meth)acryloyloxydecylammonium chloride or Triclosan may be included in the primer composition. The surface smoothing composition used in this invention includes a polyfunctional polymeric monomer (f), a volatile solvent (g) and a photopolymerization initiator (h). As the polyfunctional polymeric monomer (i), a hydrophobic polymeric monomer having two or more olefin double bonds is used. As such a hydrophobic polymeric monomer, any of the aforementioned bifunctional polymeric monomers and the polymeric monomers of trifunctional or higher functionality of (meth)acrylic ester to be included in the primer composition as an arbitrary component can be used. From the viewpoint of the surface curing property, a polymeric monomer having three or more olefin double bonds, such as pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate or dipentaerythritol hexa(meth)acrylate, is preferred, and a polymeric monomer having five or more olefin double bonds, such as dipentaerythritol penta(meth)acrylate or dipentaerythritol hexa(meth)acrylate, is particularly preferred. The polyfunctional polymeric monomer (f) includes a polymeric monomer having three or more olefin double bonds in a ratio of preferably 70 wt % or more and more preferably 80 wt % or more based on the total weight of the polyfunctional polymeric monomer (f). The mixing ratio of the polyfunctional polymeric monomer (f) is preferably 40 wt % through 98 wt % and more preferably 80 wt % through 95 wt % based on the total weight of the surface smoothing composition. When the mixing ratio is smaller than 40 wt %, the coating property and the operability of the surface smoothing composition may be lowered. The volatile solvent (g) dilutes the polyfunctional polymeric monomer (f) and improves the coating property and the operability of the surface smoothing composition. As the volatile solvent (g), one having a boiling point at normal pressure of 150° C. or less is preferably used and one having a boiling point of 100° C. or less is more preferably used. When a volatile solvent having a boiling point higher than 150° at normal pressure is used as the volatile solvent (g), the surface curing property of the surface smoothing composition may be lowered. Examples of the volatile solvent (g) are alcohols such as ethanol, methanol, 1-propanol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone and diethyl ketone, ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane and tetrahydrofuran, esters such as methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate and butyl acetate, and (meth)acrylic esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate and isopropyl (meth)acrylate. Among these solvents, the (meth)acrylic esters are preferred because they can be cured simultaneously with the polyfunctional polymeric monomer (f), and methyl methacrylate is particularly preferred because it has low toxicity and a low boiling point. One of these volatile solvents (g) may be singly used, or two or more of them may be used together if necessary. From the viewpoint of the coating property and the operability, the mixing ratio of the volatile solvent (g) is preferably 1 wt % through 59 wt %, more preferably 5 wt % through 50 wt % and most preferably 10 wt % through 40 wt % based on the total weight of the surface smoothing composition. When the mixing ratio exceeds 59 wt %, the surface smoothing composition tends to have so high flowability that the operability and the coating property are degraded or to emit a strong odor in curing. As the photopolymerization initiator (h), any of the aforementioned photopolymerization initiators to be included in the primer composition as an arbitrary component can be used. Among them, α-diketones and acylphosphine oxides are preferred. More preferably, 2,4,6-trimethylbenzoyldiphenylphosphine oxide is used because it is less colored and is less yellowed after curing. One of these photopolymerization initiators (h) may be singly used, or two or more of them may be used together if necessary. The mixing ratio of the photopolymerization initiator (h) is preferably 0.01 wt % through 10 wt % and more preferably 1 wt % through 5 wt % based on the total weight of the polymeric monomer(s) included in the surface smoothing composition. The photopolymerization initiator (h) may be used by itself or used together with a polymerization promoter for accelerating the curing property. As such a polymerization promoter, any of the aforementioned polymerization promoters to be included in the primer composition as an arbitrary component can be used. The mixing ratio of the polymerization promoter is preferably 0.01 wt % through 10 wt %, more preferably 0.05 wt % through 7 wt % and most preferably 0.1 wt % through 5 wt % based on the total weight of the polymeric monomer(s) included in the surface smoothing composition. The surface smoothing composition may include a pigment if necessary. When a pigment is included, the color tone of a resultant coating layer can be adjusted. Examples of such a pigment are blood red, phthalocyanine blue, various azo pigments and titanium oxide. For example, when the surface smoothing composition includes titanium oxide, the resultant composition attains an opaque property so as to cover the aesthetic property of the teeth. One of these pigments may be singly used, or two or more of them may be used together if necessary. The mixing ratio of the pigment is appropriately adjusted in consideration of the color tone of the coating layer and the aesthetic property. The surface smoothing composition may include a filler if necessary. As the filler, any of the aforementioned fillers to be included in the primer composition as an arbitrary component can be used. One of these fillers may be singly used, or two or more of them may be used together if necessary. The mixing ratio of the filler is preferably 40 wt % or less and more preferably 20 wt % or less based on the total weight of the surface smoothing composition. When the mixing ratio exceeds 40 wt %, the coating property and the operability of the surface smoothing composition may be lowered. Also, as the filler, one with an average particle diameter of 0.01 μm through 50 μm is generally used, and when the surface smoothing composition includes a pigment, a ultrafine filler with a particle diameter of 0.001 μm through 0.1 μm is preferably used for effectively suppressing precipitation of the pigment. As such a ultrafine filler, colloidal silica (for example, trade name “Aerosil” manufactured by Japan Aerosil) is preferred. The surface smoothing composition may further include a polymerization inhibitor, a fluorescent agent, a ultraviolet absorbing agent and the like if necessary. In the preparation of the surface smoothing composition, the respective components are preferably appropriately selected and blended so as to attain appropriate viscosity. From the viewpoint of the coating property and the operability, the viscosity of the surface smoothing composition at 30° C. is preferably 30 cP through 3,000 cP, more preferably 50 cP through 1,000 cP and most preferably 80 cP through 500 cP. When the viscosity is lower than 30 cP, the flowability is so high that the composition may permeate into a space between adjacent teeth in the application to the teeth, and when it exceeds 3,000 cP, the coating property may be lowered. The first kit is useful particularly for preventing the stain and the color return of bleached teeth. Therefore, a method for using the first kit will now be described by exemplifying the case where bleached teeth are coated. First, the primer composition is applied on the surfaces of the bleached teeth, and the thus coated layer is dried by using a dental air syringe if necessary until the primer composition loses its flowability, or in the case where the primer composition includes a polymerization initiator (a photopolymerization initiator and/or a chemical polymerization initiator), the coated layer is polymerically cured. Thus, a primer layer is formed (step 1). Next, the surface smoothing composition is applied on the primer layer, and the applied surface smoothing composition is polymerically cured through light irradiation, so as to form a surface layer on the surfaces of the bleached teeth (step 2). In the case where the primer composition includes a photopolymerization initiator, the primer composition and the surface smoothing composition may be simultaneously polymerically cured through the light irradiation. The thickness of the applied surface smoothing composition is preferably 0.005 mm through 0.5 mm and more preferably 0.01 mm through 0.3 mm. A preferable light source used for the light irradiation is, for example, a xenone lamp, a halogen lamp, a mercury lamp or a light emitting diode. The time of the light irradiation depends upon the wavelength and the amount of the light. When a dental irradiator is used, the composition can be cured in approximately 3 seconds through 3 minutes. After forming the coating layer on the bleached teeth, if a part or the whole of the coating layer is peeled off from the surfaces of the teeth or if any defect occurs owing to stain or the like, the defective portion is peeled off by using a dental instrument such as a scaler, and then the composition is applied on the teeth again. When the treatment is thus repeated, the stain and the color return of the teeth otherwise occurring after the bleaching can be effectively prevented. The first kit can be used on teeth a part of which is restored with a restorative dental material such as a metal, porcelain, ceramics or a composite curing substance. Also, the first kit may be used by itself or may be used in combination with a commercially available dental metal primer, a primer for adhering porcelain or a tooth plane cleaning agent such as a sodium hypochlorite solution. As described above, when the first kit is used, the adhesiveness to teeth can be secured owing to the primer composition, and therefore, a coating layer with high adhesiveness to teeth can be formed. The first kit has, however, a problem to be solved that chipping (that is, a phenomenon that a small part of the coating layer is chipped and peeled off) and peeling off are easily caused in the coating layer by stress applied in biting because the layer (surface layer) made of the surface smoothing composition is hard and crumbly. Another dental coating kit according to this invention (hereinafter sometimes referred to as the “second kit”) overcomes the above-described disadvantage of the first kit. Specifically, the second kit includes a primer composition composed of an acidic group-containing polymeric monomer (a), water (b) and a water-soluble solvent (c), a coating composition composed of a polymeric monomer (d) and a photopolymerization initiator (e), and a surface smoothing composition composed of a polyfunctional polymeric monomer (f), a volatile solvent (g) and a photopolymerization initiator (h). The primer composition and the surface smoothing composition of the second kit are the same as those of the first kit described above. Therefore, hereinafter, the coating composition included in the second kit alone will be described. The coating composition is a composition used for forming an intermediate layer between a layer made of the primer composition (a primer layer) and a layer made of the surface smoothing composition (a surface layer). This intermediate layer functions as a buffer layer for preventing the chipping and peeling off of the uppermost layer made of the surface smoothing composition. The coating composition includes a polymeric monomer (d) and a photopolymerization initiator (e). The polymeric monomer (d) is not particularly specified as far as it can form the intermediate layer on the primer layer. The polymeric monomer (d) is appropriately selected in consideration of the viscosity and the polymerizing property of the resultant coating composition and the strength of the resultant coating layer. When the content of the polymeric monomer (d) is excessive, the coating property, the flowability, the operability and the like of the coating composition (II) may be lowered. Therefore, the content is preferably 40 through 99.99 wt % and more preferably 60 through 99.95 wt % based on the total weight of the coating composition. One of polymeric monomers (d) may be singly used, or two or more of them may be used together if necessary. In particular, when a combination of a hydrophilic polymeric monomer and a hydrophobic polymeric monomer is used, a coating layer effectively usable as a buffer layer that is good at wettability and permeability to teeth and attains high tenacity after polymerically curing the composition can be obtained. The hydrophilic polymeric monomer not only improves the wettability and the permeability to teeth but also increases the tenacity of the resultant coating layer. The tenacity is increased by using the hydrophilic polymeric monomer because a polymerically cured coating layer including the hydrophilic polymeric monomer absorbs water and swells in a humid environment in an oral cavity. The hydrophilic polymeric monomer herein means a polymeric monomer with solubility in water at 25° C. of 10 wt % or more. As the hydrophilic polymeric monomer, a polymeric monomer with the solubility of 30 wt % or more is preferably used. Specific examples of the hydrophilic polymeric monomer are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl-1,3-di(meth)acrylate, 3-hydroxypropyl-1,2-di(meth)acrylate, pentaerythritol di(meth)acrylate, 2-trimethylammonium ethyl (meth)acryl chloride, (meth)acrylamide, 2-hydroxyethyl (meth)acrylamide and polyethylene glycol di(meth)acrylate (having nine or more oxyethylene groups). In particular, 2-hydroxyethyl methacrylate is preferred. One of these hydrophilic polymeric monomers may be singly used, or two or more of them may be used together if necessary. The mixing ratio of the hydrophilic polymeric monomer is preferably 5 wt % through 50 wt % based on the total weight of the coating composition. When the mixing ratio is smaller than 5 wt %, the wettability of the coating composition or the tenacity of the resultant cured substance tend to be lowered, and when it exceeds 50 wt %, the strength of the resultant cured substance may be lowered. The mixing ratio is more preferably 5 wt % through 40 wt % and most preferably 10 wt % through 35 wt %. The hydrophobic polymeric monomer improves the adhesiveness, the mechanical strength and the coating property. The hydrophobic polymeric monomer herein means a polymeric monomer with solubility in water at 25° C. of 10 wt % or less. As the hydrophobic polymeric monomer, a polymeric monomer with the solubility of 1 wt % or less is preferably used. Specific examples of the hydrophobic polymeric monomer are esters such as (meth)acrylic ester, α-cyanoacrylic ester, α-acrylic acid ester halide, crotonic ester, cinnamic ester, sorbic ester, maleic ester and itaconic ester, and a compound having a polymerizable unsaturated group such as a (meth)acrylamide derivative, a vinyl ester, a vinyl ether, a mono-N-vinyl derivative or a styrene derivative. In particular, (meth)acrylic ester is preferred. As the (meth)acrylic ester, any of the aforementioned (meth)acrylic esters to be included in the primer composition as an arbitrary component can be used. The kind of hydrophobic polymeric monomer is appropriately selected in consideration of the viscosity, the polymerizing property and the like of the coating composition. One of the hydrophobic polymeric monomers may be singly used, or two or more of them may be used together if necessary. From the viewpoint of the polymerizing property, a monomer of a bifunctional or higher functionality is preferably used. When the hydrophobic polymeric monomer is deficiently included, the coating property, the flowability and the operability of the coating composition may be lowered. The mixing ratio of the hydrophobic polymeric monomer is preferably 20 wt % through 90 wt % and more preferably 40 wt % through 80 wt % based on the total weight of the coating composition. When a polymeric monomer (an acidic group-containing polymeric monomer) that has one or more acidic groups such as a phosphoric group, a pyrophosphoric group, a thiophosphoric group, a carboxylic group and a sulfonic group and also has a polymerizable unsaturated group such as an acryloyl group, a methacryloyl group, a vinyl group or a styrene group is included as the polymeric monomer (d) in addition to the hydrophilic polymeric monomer and the hydrophobic polymeric monomer, the adhesiveness to teeth can be further improved. From the viewpoint of the adhesiveness, the acidic group-containing polymeric monomer has solubility in water at 25° C. of preferably 10 wt % or less, more preferably 1 wt % or less and most preferably 0.1 wt % or less. As the acidic group-containing polymeric monomer, any of the aforementioned acidic group-containing polymeric monomers (a) to be included in the primer composition as an essential component can be used. As the acidic group-containing polymeric monomer, a phosphoric group-containing polymeric monomer is preferably used because of its high adhesiveness. In particular, a phosphoric group-containing polymeric monomer having an alkylene group with a carbon number of 6 through 25, an alkyl group and/or a phenyl group is more preferred, and a phosphoric group-containing polymeric monomer having an alkylene group with a carbon number of 6 through 12 is most preferred. One of the acidic group-containing polymeric monomers may be singly used, or two or more of them may be used together if necessary. When the acidic group-containing polymeric monomer is excessively included, the polymerizing property (surface curing property) of the coating composition may be lowered. Therefore, the mixing ratio of the acidic group-containing polymeric monomer is preferably 0.1 wt % through 30 wt % and more preferably 0.1 wt % through 20 wt % based on the total weight of the coating composition. As the photopolymerization initiator (e) included in the coating composition, any of known photopolymerization initiators can be used. For example, any of the aforementioned photopolymerization initiators to be included in the primer composition as an arbitrary component can be used as the photopolymerization initiator (e). One of the photopolymerization initiators may be singly used, or two or more of them may be used together if necessary. The mixing ratio of the photopolymerization initiator (e) is preferably 0.01 wt % through 10 wt %, more preferably 0.05 wt % through 7 wt % and most preferably 0.1 wt % through 5 wt % based on the polymeric monomer (d). In order to accelerate the photo-setting property, the photopolymerization initiator (e) may be used together with a polymerization promoter. As the polymerization promoter, for example, any of the aforementioned tertiary amines, aldehydes and compounds having thiol to be included in the primer composition as an arbitrary component can be used. One of these compounds may be singly used, or two or more of them may be used together if necessary. The content of the polymerization promoter is preferably 0.01 wt % through 10 wt %, more preferably 0.05 wt % through 7 wt % and most preferably 0.1 wt % through 5 wt % based on the total weight of the coating composition. If necessary, the photopolymerization initiator (e) may be used together with a chemical polymerization initiator. When the chemical polymerization initiator is used together, the polymerizing property in an inside portion of the coating layer, which is difficult to photopolymerize because light minimally reaches it, can be improved. As such a chemical polymerization initiator, a redox type chemical polymerization initiator composed of an oxidizing agent and a reducing agent is preferably used. When the redox type chemical polymerization initiator is used, it is necessary to divide packaging of the coating composition into two or more sections so that the oxidizing agent and the reducing agent can be spaced from each other as described above. As each of the oxidizing agent and the reducing agent, any of the aforementioned oxidizing agents and reducing agents to be included in the primer composition as arbitrary components can be used. One of these oxidizing agents or these reducing agents may be singly used, or two or more of them may be used together if necessary. The mixing ratio of each of the oxidizing agent and the reducing agent is preferably 0.01 wt % through 10 wt %, more preferably 0.05 wt % through 7 wt % and most preferably 0.1 wt % through 5 wt % based on the total weight of the polymeric monomer(s) included in the coating composition. The coating composition may include an inorganic filler with a refractive index of 1.9 or more. The refractive index herein means a refractive index measured with light of a wavelength of 589.3 nm at 20° C. The inorganic filler with a refractive index of 1.9 or more is very useful not only in improving the surface curing property of the coating layer by reducing the thickness of a surface unpolymerized layer formed after polymerically curing the composition but also in improving the aesthetic property because it increases opaque property against color-changed teeth and increases the brightness of the coating layer. From the viewpoint of the surface curing property and the improvement of the aesthetic property, an inorganic filler with a refractive index of 2.1 or more is preferably used. When the refractive index is lower than 1.9, the surface curing property may be lowered. Examples of the inorganic filler with a refractive index of 1.9 or more are titanium oxide (with a refractive index of 2.49 through 2.90), zirconium oxide (with a refractive index of 2.13 through 2.19) and zinc oxide (with a refractive index of 2.00 through 2.02). Also, the inorganic filler with a refractive index of 1.9 or more has an average particle diameter of preferably 0.1 Ξm through 100 μm and more preferably 0.1 μm through 80 μm. Although the reason why the surface unpolymerized layer formed after polymerically curing the composition is reduced in the thickness is not clearly found but the present inventors presume the reason as follows: In general, when a polymeric monomer is polymerized by using a photopolymerization initiator, oxygen present in the air works as a polymerization inhibitor, and as a result, an unpolymerized layer with a thickness in micron unit is formed in a surface portion of the coating layer in contact with the air. When the coating layer includes a small amount of opaque inorganic filler (corresponding to a pigment) with a refractive index of 1.9 or more, the inorganic filler causes diffuse reflection of light (light emitted in starting the polymerization) entering the coating layer, and owing to the scattering effect of the light, the polymerizing property in the surface portion is improved. As a result, the unpolymerized layer formed in the surface portion after the polymerically curing the composition has a small thickness. One of inorganic fillers with a refractive index of 1.9 or more may be singly used, or two or more of them may be used together if necessary. The mixing ratio of the inorganic filler with a refractive index of 1.9 or more is preferably 0.1 wt % through 50 wt % based on the total weight of the coating composition. When the mixing ratio is smaller than 0.1 wt %, the surface curing property tends to be lowered, and when the mixing ratio exceeds 50 wt %, the curing depth attained by a photopolymerization catalyst alone tends to be too small to sufficiently cure the inside portion of the layer. The mixing ratio is more preferably 0.1 wt % through 10 wt % and most preferably 0.1 wt % through 5 wt %. In order to suppress precipitation of the inorganic filler with a refractive index of 1.9 or more or to improve the mechanical strength, the coating property, easiness in taking out of a vessel and the operability, another filler may be used together. Examples of the filler to be used together with the inorganic filler with a refractive index of 1.9 or more are an inorganic filler, an organic filler and an organo-mineral composite filler all having a refractive index less than 1.9. As the inorganic filler, the organic filler and the organo-mineral composite filler, any of the aforementioned inorganic fillers, organic fillers and organo-mineral fillers to be included in the primer composition as an arbitrary component can be used. As the filler to be used together with the inorganic filler with a refractive index of 1.9 or more, one of the aforementioned fillers may be singly used, or two or more of them may be used together if necessary. The mixing ratio of the filler to be used together with the inorganic filler with a refractive index of 1.9 or more is preferably 60 wt % or less and more preferably 40 wt % or less based on the total weight of the coating composition. The filler to be used together with the inorganic filler with a refractive index of 1.9 or more preferably has an average particle diameter of 0.001 μm through 50 μm. In order to suppress the precipitation of the filler with a refractive index of 1.9 or more and to improve the coating property and the operability, colloidal silica with an average particle diameter of 0.001 μm through 0.1 μm is used in a ratio of preferably 1 wt % through 40 wt %, more preferably 3 wt % through 35 wt % and most preferably 5 wt % through 30 wt % based on the total weight of the coating composition. Examples of such colloidal silica are silica with a small particle diameter obtained by spray pyrolysis (for example, one manufactured by Japan Aerosil, trade name “Aerosil”), silica sol obtained by a wet method and monodisperse silica obtained by a sol-gel process. The inorganic filler with a refractive index of 1.9 or more and the filler to be used together may be previously subjected to the coupling with a known coupling agent such as a silane coupling agent in order to improve the mechanical strength, the coating property, the operability and the flowability of the coating composition. As the coupling agent, any of the aforementioned coupling agents used for the filler to be included in the primer composition as an arbitrary component can be used. The coating composition may include a pigment. When a pigment is included, the color tone of the resultant coating layer can be adjusted. Examples of the pigment are blood red, phthalocyanine blue and various azo pigments. One of these pigments may be singly used, or two or more of them may be used together if necessary. The mixing ratio of the pigment is not particularly specified, and the pigment is appropriately included in consideration of the color tone of the coating composition and the aesthetic property. The coating composition may include a fluorine ion emitting substance. When the fluorine ion emitting substance is included, acid resistance can be given to the surfaces of the teeth. Examples of the fluorine ion emitting substance are fluorine glass such as fluoroaminosilicate glass, metal fluoride such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride or ytterbium fluoride, a fluorine ion emitting polymer such as a copolymer of methyl methacrylate and methacrylic fluoride disclosed in Japanese Laid-Open Patent Publication No. 5-85912 and cetylamine hydrofluoride. The coating composition may include a polymerization inhibitor, a fluorescent agent and a ultraviolet absorbing agent. Also, in order to provide antibacterial activity, an antibacterial substance such as cetyl pyridinium chloride, benzalkonium chloride, (meth)acryloyloxydodecyl pyridinium bromide, (meth)acryloyloxyhexadecyl pyridinium chloride, (meth)acryloyloxydecyl ammonium chloride or 2-4-4′-trichloro-2′-hydroxydiphenyl ether may be included. In the preparation of the coating composition, the respective components are preferably appropriately selected so as to attain appropriate viscosity. From the viewpoint of the coating property on teeth and the operability, the viscosity of the coating composition at 30° C. is preferably 300 cP through 50,000 cP, more preferably 500 cP through 30,000 cP and most preferably 1,000 cP through 20,000 cP. When the viscosity is lower than 300 cP, the flowability is so high that the operability may be lowered, and when it exceeds 50,000 cP, the coating property may be lowered so as to degrade uniformity in the color tone of the coating layer. Next, a method for using the second kit, namely, a coating method using the second kit, will be described. First, the primer composition is applied on the surfaces of teeth, and the applied primer composition is dried by using a dental air syringe if necessary until the primer composition loses its flowability, or in the case where the primer composition includes a polymerization initiator (a photopolymerization initiator and/or a chemical polymerization initiator), the thus coated layer is polymerically cured. Thus, a primer layer is formed (step 1). Next, the coating composition is applied on the primer layer, and the thus coated layer is polymerically cured through light irradiation, so as to form an intermediate layer (step 2). In the case where the primer composition includes a photopolymerization initiator, the primer composition and the coating composition may be simultaneously polymerically cured through the light irradiation. Ultimately, the surface smoothing composition is applied on the intermediate layer, and the thus coated layer is polymerically cured through light irradiation, so as to form a surface layer. Thus, a coating layer with a three-layered structure is formed on the teeth (step 3). If a large amount of unpolymerized layer is present in a surface portion of the intermediate layer after step 2, the surface curing property of the surface layer obtained after step 3 may be insufficient. In order to prevent this, the unpolymerized layer is preferably wiped out with, for example, a sponge or the like after step 2. The thickness of the coating composition applied in step 2 is preferably 0.005 mm through 1 mm, more preferably 0.01 mm through 0.7 mm and most preferably 0.1 mm through 0.5 mm. When the layer of the applied coating composition is polymerically cured through the light irradiation, a light source of a xenone lamp, a halogen lamp, a mercury lamp, a light emitting diode or the like is suitably used. The time of the light irradiation depends upon the wavelength or the amount of the light. When a dental irradiator is used, the composition can be cured in approximately 3 seconds through 3 minutes. Also the second kit is applicable not only to teeth not bleached but also to bleached teeth similarly to the first kit. The bleaching of teeth is recently spreading as means for making teeth white, and it is known that the surfaces of teeth are roughened by the bleaching. The second kit is also suitably used for such roughened teeth similarly to the first kit, so as to complement the effect of the bleaching and prevent the phenomenon of the color return otherwise occurring after the bleaching. The second kit can be also used not only on teeth but also on a restorative dental material such as a metal, porcelain, ceramics or a composite curing substance similarly to the first kit. Also, the second kit may be used in combination with a commercially available dental metal primer, a primer for adhering porcelain or a tooth plane cleaning agent such as a sodium hypochlorite solution similarly to the first kit. EMBODIMENTS The present invention will now be described in detail on the basis of preferred embodiments thereof, and it is noted that the invention is not limited to the following embodiments. First, embodiments of the first kit will be described, and in Embodiments 1 through 12 (the embodiments of the first kit) and Comparative Examples 1 through 4 described below, teeth were all bleached by the following method: [Bleaching Method for Teeth]A gel bleaching agent was prepared by adding 3.5 ml of 35% hydrogen peroxide to one package of a bleaching agent (manufactured by Kerativ, trade name “Power Gel”) and sufficiently mixing the resultant. This gel bleaching agent was applied, in a thickness of approximately 1 mm, on the labial surface of an extracted human central incisor, which was previously cleaned with a brush (manufactured by Nihon Shika Kogyosha Co., Ltd., trade name “brush-corn”). The labial surface of the central incisor coated with the gel bleaching agent was irradiated with light for 30 seconds by using a dental visible light irradiator (manufactured by AIR TECHNIQUES, trade name “Arc Light”) and was allowed to stand for 5 minutes, and then, the labial surface of the central incisor was cleaned with running water. This operation from the application of the gel bleaching agent to the cleaning with running water was repeated by three times, and the bleaching was completed. Abbreviations used in description below stand for the following: [Acidic group-containing polymeric monomer (a)] MDP: 10-(meth)acryloyloxydecyl dihydrogenphosphate [Water-soluble solvent (c)] HEMA: 2-hydroxyethyl methacrylate [Polyfunctional polymeric monomer (f)] DPHA: dipentaerythritol hexaacrylate DPPA: dipentaerythritol pentaacrylate PTA: pentaerythritol triacrylate [Volatile solvent (g)] MMA: methyl methacrylate [Photopolymerization initiator (h)] TMDPO: 2,4,6-trimethylbenzoyl diphenylphosphine oxide CQ: camphorquinone [Polymerization promoter] DMABE: 4-dimethylaminobenzoate [Phosphoric ester adhesive monomer] PMEAP: phenyl(2-methacryloxyethyl) acid phosphate DPMEP: diphenyl(methacryloxyethyl) phosphate Embodiment 1 A primer composition composed of MDP (20 wt %), distilled water (25 wt %) and HEMA (55 wt %) was prepared. Also, a surface smoothing composition composed of DPHA (93 wt %), MMA (5 wt %) and TMDPO (2 wt %) was prepared. With respect to a coating kit including the primer composition and the surface smoothing composition, the viscosity of the surface smoothing composition was obtained by a method described in a paragraph (1) below. Also, the operability, the odor and the surface curing property were checked by methods described in paragraphs (2) through (4) below. The results are shown in Table 1. It is noted that the viscosity, the operability, the odor and the surface curing property obtained in embodiments and comparative examples described below were also obtained by the methods of the paragraphs (1) through (4). (1) Viscosity The viscosity at 30° C. of 0.6 cc of the surface smoothing composition collected from the kit was measured with a corn-plate-type viscometer (manufactured by Toki Sangyo Co., Ltd.). (2) Operability The primer composition prepared in Embodiment 1 was applied on a bleached human central incisor, the resultant was allowed to stand for 30 seconds, and a volatile component was perspired with a dental air syringe until the primer composition lost its flowability. Subsequently, the central incisor was fixed in parallel to the ground with the labial surface thereof facing upward, and the surface smoothing composition prepared in Embodiment 1 was applied on the labial surface from the cutting edge to the cervical line with a small brush. Thus, run of the composition to a space between adjacent teeth or to a radicular surface and pool of the composition in the vicinity of the cutting edge were visually evaluated. A kit in which neither run nor pool was found was evaluated as ◯, a kit in which the run and the pool were slightly found was evaluated as Δ, and a kit in which they were conspicuously found was evaluated as ×. (3) Odor The surface coated with the surface smoothing composition in the paragraph (2) was irradiated with light for 60 seconds by using a dental irradiator (manufactured by Gunma Ushio Electric Inc., trade code “LIGHTEL II”), so as to cure the surface smoothing composition. At the time of curing, the nostril of a panelist was fixed in a position 3 cm above the coated surface so as to evaluate the odor of the surface smoothing composition. Seven panelists were employed, a panelist that did not feel the odor gave 3 marks, a panelist that felt the odor but was not uncomfortable gave 2 marks, and a panelist that felt the odor uncomfortable gave 1 mark. A kit in which the average marks of the seven panelists were 2 marks or more was evaluated as ◯ and a kit in which the average marks were less than 2 marks was evaluated as ×. (4) Surface Curing Property The surface of the cured surface layer obtained in the paragraph (3) was strongly scraped with a wiper (manufactured by Crecia Corporation, trade code “JK wiper”), so as to visually evaluate the surface curing property. A kit in which the surface layer was sufficiently cured with no flaw found on the surface was evaluated as ◯ and a kit in which the surface layer was insufficiently cured with flaws found on the surface was evaluated as ×. Embodiments 2 through 7 Six kinds of surface smoothing compositions were prepared by mixing DPHA, DPPA, PTA, MMA, ethanol, TMDPO, CQ and DMABE in weight ratios listed in Table 1. With respect to coating kits each including each of these surface smoothing compositions and the primer composition prepared in Embodiment 1, the viscosity of the surface smoothing composition was obtained and the operability, the odor and the surface curing property were checked. The results are shown in Table 1. TABLE 1 Mixing ratios in each composition (wt %) Emb. 1 Emb. 2 Emb. 3 Emb. 4 Emb. 5 Emb. 6 Emb. 7 Primer composition Acidic group-containing polymeric monomer (a): MDP 20 20 20 20 20 20 20 Water (b): Distilled water 25 25 25 25 25 25 25 Water-soluble solvent (c): HEMA 55 55 55 55 55 55 55 Surface smoothing Polyfunctional composition polymeric monomer (f): DPHA 93 88 88 88 — — 83 DPPA — — — — 88 — — PTA — — — — — 88 — Volatile solvent (g): MMA 5 10 10 — 10 10 15 Ethanol — — — 10 — — — Photopolymerization initiator (h): TMDPO 2 2 — 2 2 2 2 CQ — — 2 — — — — Polymerization promoter: DMABE — — 2 — — — — Viscosity of surface 310 205 204 198 201 185 124 smoothing composition (cP) Operability ο ο ο ο ο ο ο Odor ο ο ο ο ο ο ο Surface curing property ο ο ο ο ο ο ο It is understood from Table 1 that the first kits according to Embodiments 1 through 7 emit less uncomfortable odor and are good at operability. Also, since the first kits according to Embodiments 1 through 7 do not include a phosphoric ester adhesive monomer in the surface smoothing compositions, they are good at surface curing property. EMBODIMENT 8 A primer composition including MDP (10 wt %), distilled water (30 wt %) and HEMA (60 wt %) was prepared. A coating kit including this primer composition and the surface smoothing composition prepared in Embodiment 1 was used for forming a surface layer by a method described in a paragraph (1) below, and the surface curing property thereof was evaluated. Also, the adhesive strength to a bleached tooth of the surface layer was obtained by a method described in a paragraph (2) below. The adhesive strengths obtained in Embodiments 9 through 12 and Comparative Examples 1 through 4 below were also obtained by the method described below. The results are shown in Table 2. (1) Formation of Surface Layer A tape with a thickness of 150 μm having a hole with a diameter of 3 mm was adhered on the center of a bleached human central incisor, and the primer composition prepared in Embodiment 8 was applied on the inside of the hole of the tape. After allowing it to stand for 30 seconds, a volatile component was perspired with a dental air syringe until the primer composition lost its flowability, so as to form a primer layer. Subsequently, the surface smoothing composition prepared in Embodiment 1 was applied on the primer layer so as to fill the hole. The thus coated surface was irradiated with a dental irradiator (manufactured by Gunma Ushio Electric Inc., trade code “LIGHTEL II”) for 60 seconds for polymerically curing the composition, so as to form a surface layer. (2) Adhesive Strength A stainless steel cylindrical bar (with a diameter of 5mm and a length of 1.5 cm) was adhered to the surface layer with an end face (circular face) of the bar used as an adhesive surface by using a commercially available resin cement (manufactured by Kuraray Co., Ltd., trade code “Panavia 21”). After thirty minutes, the thus obtained test piece was immersed in water at 37° C., and the adhesive strength was measured one day after. The adhesive strength was measured by pulling the stainless steel bar downward with the tooth fixed by using several metal plates each with a thickness of 0.5 mm so that the stainless steel cylindrical bar extend within a range of ±5° or less against the axis of the pulling direction. The adhesive strength was measured by using a tensile testing apparatus (manufactured by Shimadzu Corporation, trade name “Autograph”) with a cross head speed set to 2 mm/min. The adhesive strength was obtained as an average value of values measured in eight test pieces. Embodiments 9 through 12 Four kinds of primer compositions were prepared by mixing MDP, distilled water, HEMA, ethanol, CQ and DMABE in weight ratios listed in Table 2. With respect to coating kits each including each of these primer compositions and the surface smoothing composition prepared in Embodiment 1, the surface curing property of the surface layer was evaluated. Also, the adhesive strength to a bleached tooth was obtained. The results are shown in Table 2. COMPARATIVE EXAMPLE 1 A tape with a thickness of 150 μm having a hole with a diameter of 3 mm was adhered on the center of a bleached human central incisor, and the surface smoothing composition prepared in Embodiment 1 was applied on the inside of the hole of the tape. With the surface smoothing composition filled in the hole of the tape, the thus coated surface was irradiated with a dental irradiator (manufactured by Gunma Ushio Electric Inc., trade code “LIGHTEL II”) for 60 seconds so as to form a coating layer on the bleached tooth. With respect to this coating layer, the surface curing property was evaluated and the adhesive strength to the bleached tooth was obtained. The results are shown in Table 2. COMPARATIVE EXAMPLES 2 THROUGH 4 Four kinds of surface smoothing compositions were prepared by mixing DPHA, MMA, CQ, DMABE and a phosphoric ester adhesive monomer (phenyl(2-methacryloylethy) acid phosphate or diphenyl(methacryloxyethyl) phosphate) in weight ratios listed in Table 2. Each of these surface smoothing compositions was directly applied on the labial surface of a bleached human central incisor so as to form a coating layer. With respect to this coating layer, the surface curing property was evaluated and the adhesive strength to the bleached tooth was obtained. The results are shown in Table 2. TABLE 2 Mixing ratios in each composition (wt %) Emb. Emb. Emb. Emb. Emb. Com. Com. Com. Com. 8 9 10 11 12 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Primer composition Acidic group-containing polymeric monomer (a): MDP 10 30 50 20 20 — — — — Water (b): Distilled water 30 20 15 25 25 — — — — Water-soluble solvent (c): HEMA 60 50 35 — 53 — — — — Ethanol — — — 55 — — — — — Photo- polymerization initiator: CQ — — — — 1 — — — — Polymerization promoter: DMABE — — — — 1 — — — — Surface smoothing Polyfunctional composition polymeric monomer (f): DPHA 88 88 88 88 88 88 56 54 54 Volatile solvent (g): MMA 10 10 10 10 10 10 40 40 40 Photo- polymerization initiator (h): TMDPO 2 2 2 2 2 2 — — — CQ — — — — — — 2 2 2 Polymerization promoter: DMABE — — — — — — 2 2 2 Phosphoric ester adhesive monomer: PMEAP — — — — — — — 2 — DPMEP — — — — — — — — 2 Surface curing ο ο ο ο ο ο ο X X property Adhesive strength 15.3 14.8 15.6 15.2 15.9 1.5 1.3 3.7 3.9 (MPa) It is understood from Table 2 that very high adhesive strength can be obtained when a primer layer and a surface layer are successively formed on a bleached tooth by using the first kit according to any of Embodiments 8 through 12. Also, since the first kit of any of Embodiments 8 through 12 does not include a phosphoric ester adhesive monomer in its surface smoothing composition, it is good at the surface curing property. On the contrary, in the case where a surface smoothing composition is directly applied on a bleached tooth without forming a primer layer (Comparative Examples 1 and 2), although the surface curing property is high, the adhesive strength is very low. Alternatively, in the case where a composition including a phosphoric ester adhesive monomer is directly applied on a bleached tooth without forming a primer layer, although the adhesiveness to the bleached tooth is slightly improved, the surface curing property is poor (Comparative Examples 3 and 4). Although the first kit is used for coating a bleached tooth in each of the aforementioned embodiments, the first kit is suitably used for a tooth not having been bleached. Next, preferred embodiments of the second kit will be described. Abbreviations used in description below stand for the following: MDP: 10-(meth)acryloyloxydecyl dihydrogenphosphate HEMA: 2-hydroxyethyl methacrylate UDMA: [2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)]dimethacrylate U-4TH: N,N′-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate Bis-GMA: bisphenol A diglycidyl methacrylate 3G: triethylene glycol dimethacrylate DPHA: dipentaerythritol hexaacrylate DPPA: dipentaerythritol pentaacrylate MMA: methyl methacrylate CQ: camphorquionone DMABE: 4-dimethylaminobenzoate TMDPO: 2,4,6-trimethylbenzoyl diphenylphosphine oxide Embodiment 13 A primer composition including MDP (20 wt %), distilled water (40 wt %) and HEMA (40 wt %), a coating composition including UDMA (50 wt %), U-4TH (20 wt %), 3G (29 wt %), CQ (0.5 wt %) and DMABE (0.5 wt %) and a surface smoothing composition including DPHA (73 wt %), MMA (25 wt %) and TMDPO (2 wt %) were respectively prepared. With respect to a coating kit (second kit) including these primer composition, coating composition and surface smoothing composition, the adhesive strength to a tooth was measured by an adhesiveness testing method A1 described below. Also, the chipping resistance was evaluated by a chipping resistance testing method B1 described below. The results are shown in Table 3. [Adhesiveness Testing Method A1] (1) After cleaning the enamel surface on the labial surface of an extracted human central incisor with a brush (manufactured by Nihon Shika Kogyo Co., Ltd., trade name “brush-corn”), a tape with a thickness of 150 μm having a hole with a diameter of 3 mm was adhered to the center of a flat portion of the enamel surface, and the primer composition prepared in Embodiment 13 was applied on the inside of the hole of the tape. After allowing it to stand for 30 seconds, a volatile component was perspired with a dental air syringe until the primer composition lost its flowability, so as to form a primer layer. The coating composition prepared in Embodiment 13 was applied on the primer layer so as to fill the hole. The thus coated surface was irradiated with a dental irradiator (manufactured by Gunma Ushio Electric Inc., trade code “LIGHTEL II”) for 30 seconds for curing, so as to form an intermediate layer. Furthermore, the surface smoothing composition prepared in Embodiment 13 was applied on the intermediate layer with a small brush, and the resultant was irradiated with the aforementioned dental irradiator for 60 seconds, so as to form a surface layer. (2) A stainless steel cylindrical bar (with a diameter of 5mm and a length of 1.5 cm) was adhered to the surface layer with an end face (circular face) of the bar used as an adhesive surface by using a commercially available resin cement (manufactured by Kuraray Co., Ltd., trade code “Panavia 21”). After thirty minutes, the thus obtained test piece was immersed in water at 37° C., and the adhesive strength was measured one day after. The adhesive strength was measured by pulling the stainless steel bar downward with the tooth fixed by using several metal plates each with a thickness of 0.5 mm so that the stainless steel cylindrical bar extend within a range of ±5° or less against the axis of the pulling direction. The adhesive strength was measured by using a tensile testing apparatus (manufactured by Shimadzu Corporation, trade name “Autograph”) with a cross head speed set to 2 mm/min. The adhesive strength was obtained as an average value of values measured in eight test pieces. [Chipping resistance testing method B1] (1) The lingual surface of an extracted human anterior tooth was planed off to be parallel to a flat portion of the enamel surface on the labial surface, and thus, the tooth was processed into a tabular shape with a thickness of 2 mm. After cleaning the enamel surface on the labial surface of the thus processed tooth with a brush (manufactured by Nihon Shika Kogyo Co., Ltd., trade name “brush-corn”), a tape with a thickness of 150 μm having a hole with a diameter of 5 mm was adhered to the center of the flat portion of the enamel surface, and the primer composition prepared in Embodiment 13 was applied. After allowing it to stand for 30 seconds, a volatile component was perspired with a dental air syringe until the primer composition lost its flowability, so as to form a primer layer. The coating composition prepared in Embodiment 13 was applied on the primer layer so as to fill the hole. The thus coated surface was irradiated with a dental irradiator (manufactured by Gunma Ushio Electric Inc., trade code “LIGHTEL II”) for 30 seconds for curing, so as to form an intermediate layer. Furthermore, the surface smoothing composition prepared in Embodiment 13 was applied on the intermediate layer with a small brush, and the resultant was irradiated with the aforementioned dental irradiator for 60 seconds. Thereafter, the tape was peeled off, resulting in obtaining a tabular tooth having a surface layer with a diameter of 5 mm formed on the enamel surface. The tabular tooth having the surface layer was placed on the center of a mold with a length of 3 cm, a width of 2 cm and a thickness of 2 mm with the circular surface layer facing upward, the tooth was fixed by filling the periphery with a dental composite resin, and in this state, the dental composite resin was polymerically cured, so as to obtain a test piece. The test piece was fixed on the bottom of a water bath filled with water, the brush tip of a toothbrush (manufactured by Lion Corporation, trade name “Between”; hardness: medium) was vertically brought to contact with the surface of the surface layer, and the toothbrush was reciprocated by a swing range of 10 cm under a load of 250 g. (2) After repeating the reciprocation by 10000 times, 20000 times and 40000 times, the test piece was taken out, the peripheral portion of the circular surface layer was observed with a light microscope (of 10 magnifications). Thus, occurrence of chipping with a major axis of 0.1 mm or more was checked, and the chipping resistance was evaluated in accordance with the following evaluation criterion: (Evaluation Criterion) No chipping was found: ◯ Any chipping was found: × Embodiments 14 through 17 Four kinds of dental coating kits (second kits) were fabricated by preparing primer compositions, coating compositions and surface smoothing compositions respectively having compositions listed in Table 3. With respect to each of these dental coating kits, the adhesive strength was obtained by the aforementioned adhesiveness testing method A1 and the chipping resistance was evaluated by the aforementioned chipping resistance testing method B1. The results are shown in Table 3. COMPARATIVE EXAMPLES 5 AND 6 With respect to each of the surface smoothing composition prepared in Embodiment 13 (as Comparative Example 5) and the surface smoothing composition prepared in Comparative Example 1 (as Comparative Example 6), the adhesive strength was obtained by an adhesiveness testing method A2 described below and the chipping resistance was evaluated by a chipping resistance testing method B2 described below. The results are shown in Table 3. However, although a test piece was to be taken out for evaluating the chipping resistance after 10000 reciprocations, the coating layers of both Comparative Example 5 and Comparative Example 6 were dropped off from the teeth before the 10000 reciprocations for the chipping resistance test, and therefore, the chipping resistance could not be evaluated. [Adhesiveness Testing Method A2] (1) After cleaning the enamel surface on the labial surface of an extracted human central incisor with a brush (manufactured by Nihon Shika Kogyo Co., Ltd., trade name “brush-corn”), a tape with a thickness of 150 μm having a hole with a diameter of 3 mm was adhered to the center of a flat portion of the enamel surface, and the surface smoothing composition prepared in Embodiment 13 or Comparative Example 1 was applied on the inside of the hole of the tape. The thus coated surface was irradiated with a dental irradiator (manufactured by Gunma Ushio Electric Inc., trade code “LIGHTEL II”) for 60 seconds for curing, so as to form a coating layer. (2) The adhesive strength to the tooth of the coating layer formed by the method described in the paragraph (1) was measured by the aforementioned adhesiveness testing method Al (2). [Chipping resistance testing method B2] (1) The lingual surface of an extracted human anterior tooth was planed off to be parallel to a flat portion of the enamel surface on the labial surface, and thus, the tooth was processed into a tabular shape with a thickness of 2 mm. After cleaning the enamel surface on the labial surface of the thus processed tooth with a brush (manufactured by Nihon Shika Kogyo Co., Ltd., trade name “brush-corn”), a tape with a thickness of 150 μm having a hole with a diameter of 5 mm was adhered to the center of the flat portion of the enamel surface, and the surface smoothing composition prepared in Embodiment 13 or Comparative Example 1 was applied. The thus coated surface was irradiated with the aforementioned dental irradiator for 60 seconds for curing, and the tape was peeled off, resulting in obtaining a tabular tooth having a coating layer with a diameter of 5 mm formed on the enamel surface. (2) The chipping resistance of the coating layer formed in the method described in the paragraph (1) was evaluated by the chipping resistance testing method B1 (2). TABLE 3 Mixing ratios in each composition (wt %) Emb. 13 Emb. 14 Emb. 15 Emb. 16 Emb. 17 Com. Ex. 5 Com. Ex. 6 Primer composition Acidic group-containing polymeric monomer (a): MDP 20 20 20 20 20 — — Water (b): Distilled water 40 40 40 40 40 — — Water-soluble solvent (c): HEMA 40 — 40 40 40 — — Ethanol — 40 — — — — — Coating composition Polymeric monomer (d): UDMA 50 50 — 50 — — — U-4TH 20 20 — 20 — — — Bis-GMA — — 60 — 60 — — 3G 29 29 39 — — — — HEMA — — — 29 39 — — Photo- polymerization initiator (e): CQ 0.5 0.5 0.5 0.5 0.5 — — Polymerization promoter: DMABE 0.5 0.5 0.5 0.5 0.5 — — Surface smoothing Polyfunctional composition polymeric monomer (f): DPHA 73 73 73 73 73 73 88 Volatile solvent (g): MMA 25 25 25 25 25 25 10 Photo- polymerization initiator (h): TMDPO 2 2 2 2 2 2 2 Adhesive strength (MPa) 15.4 14.6 14.7 15.7 15.5 0.3 1.5 Chipping 10000 ο ο ο ο ο — — resistance reciprocations 20000 ο ο ο ο ο — — reciprocations 40000 ο ο ο ο ο — — reciprocations Embodiments 18 through 22 Five kinds of dental coating kits (second kits) were fabricated by preparing primer compositions, coating compositions and surface smoothing compositions respectively having compositions listed in Table 4. With respect to each of these dental coating kits, the adhesive strength was obtained by the aforementioned adhesiveness testing method A1 and the chipping resistance was evaluated by the aforementioned chipping resistance testing method B1. The results are shown in Table 4. TABLE 4 Mixing ratios in each composition (wt %) Emb. 18 Emb. 19 Emb. 20 Emb. 21 Emb. 22 Primer composition Acidic group-containing polymeric monomer (a): MDP 20 20 20 20 20 Water (b): Distilled water 40 40 40 40 40 Water-soluble solvent (c): HEMA 40 40 40 40 40 Coating composition Polymeric monomer (d): UDMA 50 50 50 50 50 U-4TH 20 20 20 20 20 3G 29 29 29 29 29 Photopolymerization initiator (e): CQ 0.5 0.5 0.5 0.5 0.5 Polymerization promoter: DMABE 0.5 0.5 0.5 0.5 0.5 Surface smoothing Polyfunctional composition polymeric monomer (f): DPHA 83 — 73 85 70 DPPA — 73 — — — Volatile solvent (g): MMA 15 25 — 10 25 Ethanol 25 Photopolymerization initiator (h): TMDPO 2 2 2 — — CQ — — — 2.5 2.5 Polymerization promoter: DMABE — — — 2.5 2.5 Adhesive strength (MPa) 15.6 14.9 15.3 15.8 14.6 Chipping 10000 ο ο ο ο ο resistance reciprocations 20000 ο ο ο ο ο reciprocations 40000 ο ο ο ο ο reciprocations Embodiments 23 through 37 Seven kinds of dental coating kits (according to Embodiments 23 through 29; second kits) were fabricated by preparing primer compositions, coating compositions and surface smoothing compositions respectively having compositions listed in Table 5. Also, eight kinds of dental coating kits (according to Embodiments 30 through 37; first kits) were fabricated by preparing primer compositions and surface smoothing compositions respectively having compositions listed in Table 6. The kit of Embodiment 32 is the same as the kit of Embodiment 7, the kit of Embodiment 33 is the same as the kit of Embodiment 2, the kit of Embodiment 34 is the same as the kit of Embodiment 1, the kit of Embodiment 35 is the same as the kit of Embodiment 8, the kit of Embodiment 36 is the same as the kit of Embodiment 9, and the kit of Embodiment 37 is the same as the kit of Embodiment 10. With each of these dental coating kits, the adhesive strength was obtained by the aforementioned adhesiveness testing method A1 and the chipping resistance was evaluated by the aforementioned chipping resistance testing method B1. Furthermore, change of the brightness of a tooth caused by the coating was measured by a measurement method for brightness change described below. The results are shown in Table 5 and Table 6. [Measurement Method for Brightness Change] (1) The lingual surface of an extracted human anterior tooth was planed off to be parallel to a flat portion of the enamel surface on the labial surface, and thus, the tooth was processed into a tabular shape with a thickness of 2 mm. After cleaning the enamel surface on the labial surface of the thus processed tooth with a brush (manufactured by Nihon Shika Kogyo Co., Ltd., trade name “brush-corn”), a tape with a thickness of 150 μm having a hole with a diameter of 7 mm was adhered to the center of the flat portion of the enamel surface, and the brightness index of the hole portion was measured (L*0). The brightness index (L*) was measured by using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., Σ90 type, with a light source of a D65 light source, a view angle of 2 degrees and a color measuring range of 5 mmφ) with a standard white board placed behind. The L* described herein corresponds to a brightness index in a L*a*b* color system according to JIS-Z8729. (2) Subsequently, the primer composition prepared in any of Embodiments 23 through 37 was applied on the inside of the hole of the tape. After allowing it to stand for 30 seconds, a volatile component was perspired with a dental air syringe until the flowability was lost, so as to form a primer layer. (3) Subsequently, the coating composition prepared in any of Embodiments 23 through 29 was applied on the primer layer so as to fill the hole. The thus coated surface was irradiated with the aforementioned dental irradiator for 30 seconds for polymerically curing the composition, so as to form an intermediate layer. With respect to the kits of Embodiments 30 through 37 including no coating composition, this step (3) was omitted and the process proceeded to step (4) below. (4) The surface smoothing composition prepared in any of Embodiments 23 through 37 was applied on the intermediate layer (on the primer layer in Embodiments 30 through 37) with a small brush, and the resultant was irradiated by using the aforementioned dental irradiator for 60 seconds, and then the tape was peeled off. Thus, a tabular tooth having a coating layer with a diameter of 7 mm on the enamel surface was obtained. (5) Subsequently, the brightness index of the coating portion of the tabular tooth was measured in the same manner as in step (1) above (L*1). Change of the brightness caused by the coating was calculated in accordance with the following formula: Change of brightness (ΔL*)=L*1−L*0 TABLE 5 Mixing ratios in each composition (wt %) Emb. 23 Emb. 24 Emb. 25 Emb. 26 Emb. 27 Emb. 28 Emb. 29 Primer composition Acidic group-containing polymeric monomer (a): MDP 20 20 20 20 20 20 20 Water (b): Distilled water 40 40 40 40 40 40 40 Water-soluble solvent (c): HEMA 40 40 40 40 40 40 40 Coating composition Polymeric monomer (d): UDMA 50 50 50 50 80.9 65.9 50.9 U-4TH 20 20 20 20 — — — 3G 21.3 20.9 20.5 18.5 — — — HEMA 10 25 40 Photo- polymerization initiator (e): CQ 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Polymerization promoter: DMABE 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Inorganic filler (i): Titanium oxide 0.2 0.6 1.0 3.0 0.6 0.6 0.6 powder (*1) Colloidal silica (j): Aerosil 130 (*2) 7.5 7.5 7.5 7.5 7.5 7.5 7.5 Surface smoothing Polyfunctional composition polymeric monomer (f): DPHA 73 73 73 73 83 83 83 Volatile solvent (g): MMA 25 25 25 25 15 15 15 Photo- polymerization initiator (h): TMDPO 2 2 2 2 2 2 2 Adhesive strength (MPa) 16.0 15.1 15.7 14.9 18.5 17.8 18.2 Chipping 10000 ο ο ο ο ο ο ο resistance reciprocations 20000 ο ο ο ο ο ο ο reciprocations 40000 ο ο ο ο ο ο ο reciprocations Change of brightness (ΔL*) 8.1 17.1 19.5 22.5 17.4 17.3 17.0 (*1) titanium oxide powder having been subjected to silane treatment with γ-methacryloxypropyl trimethoxysilane (*2) manufactured by Japan Aerosil (trade name) TABLE 6 Mixing ratios in each composition (wt %) Emb. Emb. Emb. Emb. Emb. Emb. Emb. Emb. 30 31 32 33 34 35 36 37 Primer composition Acetic group-containing polymeric monomer (a): MDP 20 20 20 20 20 10 30 50 Water (b): Distilled water 40 25 25 25 25 30 20 15 Water-soluble solvent (c): HEMA 40 55 55 55 55 60 50 35 Surface smoothing Polyfunctional composition polymeric monomer (f): DPHA 73 73 83 88 93 88 88 88 Volatile solvent (g): MMA 25 25 15 10 5 10 10 10 Photopolymerization initiator (h): TMDPO 2 2 2 2 2 2 2 2 Adhesive strength (MPa) 11.2 12.5 13.7 14.2 13.9 15.3 14.8 15.6 Chipping 10000 reciprocations ο ο ο ο ο ο ο ο resistance 20000 reciprocations ο ο ο ο ο ο ο ο 40000 reciprocations X X X X X X X X As shown in Tables 3 through 5, in the case where a coating layer with a three-layered structure was formed by using a second kit including a primer composition, a coating composition and a surface smoothing composition, the resultant coating layer exhibited high adhesive strength to teeth, and in addition, was good at chipping resistance (Embodiments 13 through 29). On the contrary, as shown in Table 3, in the case where a single-layered coating layer was formed by directly applying a surface smoothing composition on a tooth without applying a primer composition and a coating composition, the adhesiveness to the tooth of the resultant coating layer was poor (Comparative Examples 5 and 6). Also, as shown in Table 6, in the case where a coating layer with a two-layered structure was formed by applying a primer composition and a surface smoothing composition in this order on a tooth without applying a coating composition, although the adhesive strength was high, the chipping resistance was poor (Embodiments 30 through 37). Also, as shown in Table 5, in the case where a coating layer with a three-layered structure was formed on a tooth by using a second kit including a coating composition containing an inorganic filler with a refractive index of 1.9 or more, the brightness of the tooth was improved through the coating, and the aesthetic property was improved (Embodiments 23 through 29). INDUSTRIAL APPLICABILITY The dental coating kit according to this invention is particularly useful as a kit for preventing stain and color return of bleached teeth.
<SOH> BACKGROUND ART <EOH>Teeth are stained or changed in color due to deposit of a colored substance included in a cigarette, coffee and the like, or breeding of chromogenic bacteria. In general, women wish to make their teeth look white and beautiful by preventing the stain and color change of the teeth more strongly than men. This is the reason why the number of women, and particularly young women, that receive a bleaching treatment for teeth described below is recently rapidly increasing. The bleaching treatment for teeth is carried out not only as a part of beauty culture for making teeth look white and beautiful but also as means for restoring stained or color-changed teeth to former natural teeth. In the bleaching treatment, a bleaching agent including, as a principal component, hydrogen peroxide or urea peroxide is generally used. The bleaching agent has two functions, that is, a decoloring function to decompose a coloring matter deposited on teeth and a function to attain whiteness by roughening the surfaces of teeth for causing diffuse reflection of light. Owing to these two functions, the teeth can be made to look white. Although the bleaching treatment is effective for improving the aesthetic property, plaque, protein, a coloring matter and the like tend to adhere to the teeth after the bleaching treatment because the surfaces of the teeth are roughened. Therefore, for a while after the bleaching treatment, particularly for a couple of days after the bleaching, it is necessary to refrain from ingesting coffee, curry and citrus fruit juice and smoking, which can be a cause of stain. Even when the ingestion and smoking are thus restricted, however, the teeth may be stained in a short period of time. Also, plaque, protein, a coloring matter and the like are gradually accumulated on the teeth, or the surfaces of the teeth having been roughened through the bleaching treatment are gradually naturally restored due to remineralization caused by saliva in the oral cavity, and therefore, the bleached color is frequently returned to the former color prior to the bleaching treatment in approximately a half or two years after the bleaching. In order to suppress the stain and the color return of teeth occurring after the bleaching, application of a finishing coating composition to teeth after the bleaching treatment is conventionally proposed. As such a finishing coating composition, for example, a composition including 10 wt % through 80 wt % of a polyfunctional acrylate monomer, 20 wt % through 80 wt % of a low-boiling solvent and 0.4 wt % through 5 wt % of a visible light-initiated polymerization initiator is proposed in Japanese Laid-Open Patent Publication No. 2001-271009, and a composition including 10 wt % through 80 wt % of a polyfunctional acrylate monomer, 20 wt % through 80 wt % of a low-boiling solvent, 0.4 wt % through 5 wt % of a visible light-initiated polymerization initiator and 0.5 wt % through 10 wt % of a white inorganic impalpable powder is proposed in Japanese Laid-Open Patent Publication No. 2002-3327. Both of these compositions are, however, poor at adhesiveness to teeth. As a countermeasure against this disadvantage, addition of 0.1 wt % through 5 wt % of a phosphoric ester adhesive monomer to each composition is proposed (see Japanese Laid-Open Patent Publication No. 2001-271009, claim 8, [0030] and [0031]; and Japanese Laid-Open Patent Publication No. 2002-3327, claim 10, [0039] and [0040]). The present inventors have, however, found the following: Even when a given amount of phosphoric ester adhesive monomer is added, the adhesiveness to teeth is not largely improved but the surface curing property is largely degraded. Therefore, it is difficult to thus obtain a practically usable coating composition. The present invention was devised to overcome the aforementioned problem, and an object is providing a dental coating kit that is good at adhesiveness to teeth and is useful for preventing stain and color change of teeth.
20050407
20101019
20060413
97863.0
A61K881
0
ROBERTS, LEZAH
DENTAL COATING KIT
UNDISCOUNTED
0
ACCEPTED
A61K
2,005
10,530,583
ACCEPTED
System and method for providing advanced reservations in a compute environment
A system and method are disclosed for dynamically reserving resources within a duster environment. The method embodiment of the invention comprises receiving a request for resources in the duster environment, monitoring events after receiving the request for resources and based on the monitored events, dynamically modifying at least one of the request for resources and the cluster environment.
1. A method of dynamically modifying resources within a compute environment, the method comprising: receiving a request for resources in the compute environment; monitoring events after receiving the request for resources; and based on the monitored events, dynamically modifying at least one of the request for resources and the compute environment. 2. The method of claim 1, wherein the compute environment is one of a compute farm, a duster environment and a grid environment. 3. The method of claim 1, wherein the request for resources is a request for consumption resources. 4. The method of claim 1, wherein the request for resources is a request for provisioning services. 5. The method of claim 1, wherein the request for resources is a request to process a batch job. 6. The method of claim 1, wherein the request for resources is a request for direct volume access. 7. The method of claim 1, wherein the request for resources is a request for a virtual private cluster. 8. The method of claim 1, wherein monitoring events after receiving the request for resources further comprises monitoring the compute environment. 9. The method of claim 1, wherein monitoring events after receiving the request for resources further comprises monitoring to determine if a party submitting the request has submitted a job for processing once resources in the compute environment are reserved for the job. 10. The method of claim 9, wherein if the party submitting the request for resources has not submitted a job for processing after a predetermined amount of time, then dynamically modifying the request for resources further comprises canceling the request for resources. 11. The method of claim 10, wherein a job comprises one of a reservation, an object that monitors policy, an object that monitors credentials, an object that monitors node states and an object that monitors the compute environment. 12. The method of claim 11, wherein based on the monitored events in the compute environment, modifying the compute environment further comprises dynamically modifying the compute environment to satisfy the request for resources. 13. The method of claim 12, wherein dynamically modifying the compute environment further comprises at least one of: modifying at least one node, modifying at least one operating system, installing end user applications, dynamically partitioning node resources and adjusting network configuration. 14. The method of claim 1, wherein the request for resources is a request for a reservation of resources in the compute environment. 15. The method of claim 14, wherein monitoring events after receiving the request for a reservation further comprises monitoring compute resources associated with the reservation. 16. The method of claim 15, further comprising dynamically modifying the compute environment to more adequately process jobs submitted within the reservation. 17. The method of claim 1, wherein modifying the request for resources comprises migrating a reservation to be associated with new resources. 18. The method of claim 17, wherein migrating the reservation is one of a migration in space and a migration in time to the new resources. 19. The method of claim 17, wherein the new resources better meet needs associated with the request for resources. 20. The method of claim 18, wherein the migration in time seeks to create a reservation at the earliest time possible. 21. The method of claim 18, wherein the migration in time seeks to create a reservation based on availability of resources in the compute environment. 22. The method of claim 18, wherein the migration in space comprises migrating the reservation to resources that will provide better performance of the compute environment for the request for resources. 23. The method of claim 18, wherein the migration in space comprises migrating the reservation to resources according to a failure or projected failure of resources. 24. The method of claim 1, wherein monitoring events after receiving the request for resources further comprises monitoring a job submitted within a reservation based on the request. 25. The method of claim 24, wherein if the job submitted within the reservation will extend beyond the reservation, the method further comprises canceling the job. 26. The method of claim 25, wherein prior to canceling the job, the method further comprises presenting to the entity that submitted the job an option of extending the reservation to accommodate the job. 27. The method of claim 26, wherein the option of extending the reservation to accommodate the job is subject to pre-established policies. 28. The method of claim 27, further comprising presenting to the entity, with the option of extending the reservation, a pricing option to extend the reservation. 29. The method of claim 1, wherein the request for resources in a compute environment comprises a reservation of resources for a window of time in which at least one user can submit personal reservations. 30. The method of claim 29, wherein personal reservations are one of a non-administrator reservation and an administrator reservation. 31. The method of claim 29, wherein the reservation of compute resources for a window of time is a request for cluster resources for a periodic window of time. 32. The method of claim 31, wherein the periodic window of time may be daily, weekly, monthly, quarterly or yearly. 33. The method of claim 29, further comprising: receiving a personal reservation for the use of compute resources within the window of time; and providing access to the reserved compute resources for the personal reservation to process jobs. 34. The method of claim 33, wherein if a received consumption job associated with the personal reservation will exceed the window of time for the reservation of compute resources, then the method comprises canceling and locking out the personal reservation from access to the compute resources. 35. The method of claim 33, wherein if a received consumption job associated with the personal reservation will exceed the window of time, then the method comprises never starting the consumption job. 36. The method of claim 34, further comprising, before canceling and locking out the personal reservation, the step of: presenting to a user who submitted the personal reservation an option of allowing the jobs running within the personal reservation to complete although it is beyond the window of time for their reservation of compute resources. 37. The method of claim 34, further comprising, if the job submitted under a personal reservation would exceed the personal reservation, extending the personal reservation to meet the needs of the job. 38. A method of managing resources within a compute environment, the method comprising: receiving a request for resources in the compute environment; reserving resources in the compute environment according to the request; and charging the requestor based on the reservation of resources. 39. The method of claim 38, wherein charging the requestor further comprises charging a specific rate for the reserved resources whether the reserved resources are used or not. 40. The method of claim 38, wherein charging the requestor further comprises charging a first rate for reserved resources that are used and a second rate for reserved resources that are not used. 41. The method of claim 40, wherein a used resources is consumed by a job run within the reservation. 42. The method of claim 1, further comprising: creating a reservation for resources within the compute environment based on the request for resource; and dynamically customizing resources within the reservation to meet workload submitted within the reservation. 43. The method of claim 42, wherein the reservation is associated with one of an individual or a group. 44. A computer-readable medium storing instructions for controlling a computing device to dynamically manage resources within a compute environment, the instructions comprising: receiving a request for resources in the compute environment; monitoring events after receiving the request for resources; and based on the monitored events, dynamically modifying at least one of the request for resources and the compute environment. 45. A system for dynamically managing resources within a compute environment, the system comprising: means for receiving a request for resources in the compute environment; means for monitoring events after receiving the request for resources; and based on the monitored events, means for dynamically modifying at least one of the request for resources and the compute environment. 46. A system for dynamically managing resources within a compute environment, the system comprising: a module configured to receive a request for resources in the compute environment; a module configured to monitor events after receiving the request for resources; and a module configured to dynamically modify at least one of the request for resources and the compute environment based on the monitored events. 47. A compute environment comprising a plurality of computing devices, the compute environment having resources which are dynamically managed according to a method comprising: receiving a request for resources in the compute; monitoring events after receiving the request for resources; and based on the monitored events, dynamically modifying at least one of the request for resources and the compute environment.
PRIORITY CLAIM The present application claims priority to U.S. Provisional Application No. 60/552,653 filed Mar. 13, 2004, the contents of which are incorporated herein by reference. The present application also cites priority to U.S. Provisional Application No. 60/581,257 filed Jun. 18, 2004, the contents of which are incorporated herein by reference. RELATED APPLICATIONS The present application is related to Attorney Docket Numbers 010-0011A, 010-0011B, 010-0011C, 010-0013, 010-0019, 010-0026, 010-0028 and 010-0030 filed on the same day as the present application. The content of each of these cases is incorporated herein by reference. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to reservations in a compute environment and more specifically to a system and method of providing advanced reservations to resources within a compute environment such as a cluster. 2. Introduction There are challenges in the complex process of managing the consumption of resources within a compute environment such as a grid, compute farm or cluster of computers. Grid computing may be defined as coordinated resource sharing and problem solving in dynamic, multi-institutional collaborations. Many computing projects require much more computational power and resources than a single computer may provide. Networked computers with peripheral resources such as printers, scanners, I/O devices, storage disks, scientific devices and instruments, etc. may need to be coordinated and utilized to complete a task. The term compute resource generally refers to computer processors, network bandwidth, and any of these peripheral resources as well. A compute farm may comprise a plurality of computers coordinated for such purposes of handling Internet traffic. The web search website Google® had a compute farm used to process its network traffic and Internet searches. Grid/cluster resource management generally describes the process of identifying requirements, matching resources to applications, allocating those resources, and scheduling and monitoring grid resources over time in order to run grid applications or jobs submitted to the compute environment as efficiently as possible. Each project or job will utilize a different set of resources and thus is typically unique. For example, a job may utilize computer processors and disk space, while another job may require a large amount of network bandwidth and a particular operating system. In addition to the challenge of allocating resources for a particular job or a request for resources, administrators also have difficulty obtaining a dear understanding of the resources available, the current status of the compute environment and available resources, and real-time competing needs of various users. One aspect of this process is the ability to reserve resources for a job. A cluster manager will seek to reserve a set of resources to enable the cluster to process a job at a promised quality of service. General background information on clusters and grids may be found in several publications. See, e.g., Grid Resource Management, State of the Art and Future Trends, Jarek Nabrzyski, Jennifer M. Schopf, and Jan Weglarz, Kluwer Academic Publishers, 2004; and Beowulf Cluster Computing with Linux, edited by William Gropp, Ewing Lusk, and Thomas Sterling, Massachusetts Institute of Technology, 2003. It is generally understood herein that the terms grid and cluster are interchangeable, although they have different connotations. For example, when a grid is referred to as receiving a request for resources and the request is processed in a particular way, the same method may also apply to other compute environments such as a cluster or a compute farm. A cluster is generally defined as a collection of compute nodes organized for accomplishing a task or a set of tasks. In general, a grid will comprise a plurality of clusters as will be shown in FIG. 1A. Several general challenges exist when attempting to maximize resources in a grid. First, there are typically multiple layers of grid and cluster schedulers. A grid 100 generally comprises a group of clusters or a group of networked computers. The definition of a grid is very flexible and may mean a number of different configurations of computers. The introduction here is meant to be general given the variety of configurations that are possible. A grid scheduler 102 communicates with a plurality of duster schedulers 104A, 104B and 104C. Each of these cluster schedulers communicates with a respective resource manager 106A, 106B or 106C. Each resource manager communicates with a respective series of compute resources shown as nodes 108A, 108B, 108C in cluster 110, nodes 108D, 108E, 108F in cluster 112 and nodes 108G, 108H, 108I in cluster 114. Local schedulers (which may refer to either the cluster schedulers 104 or the resource managers 106) are doser to the specific resources 108 and may not allow grid schedulers 102 direct access to the resources. The grid level scheduler 102 typically does not own or control the actual resources. Therefore, jobs are submitted from the high level grid-scheduler 102 to a local set of resources with no more permissions that then user would have. This reduces efficiencies and can render the reservation process more difficult. The heterogeneous nature of the shared compute resources also causes a reduction in efficiency. Without dedicated access to a resource, the grid level scheduler 102 is challenged with the high degree of variance and unpredictability in the capacity of the resources available for use. Most resources are shared among users and projects and each project varies from the other. The performance goals for projects differ. Grid resources are used to improve performance of an application but the resource owners and users have different performance goals: from optimizing the performance for a single application to getting the best system throughput or minimizing response time. Local policies may also play a role in performance. Within a given cluster, there is only a concept of resource management in space. An administrator can partition a cluster and identify a set of resources to be dedicated to a particular purpose and another set of resources can be dedicated to another purpose. In this regard, the resources are reserved in advance to process the job. There is currently no ability to identify a set of resources over a time frame for a purpose. By being constrained in space, the nodes 108A, 108B, 108C, if they need maintenance or for administrators to perform work or provisioning on the nodes, have to be taken out of the system, fragmented permanently or partitioned permanently for special purposes or policies. If the administrator wants to dedicate them to particular users, organizations or groups, the prior art method of resource management in space causes too much management overhead requiring a constant adjustment the configuration of the cluster environment and also losses in efficiency with the fragmentation associated with meeting particular policies. To manage the jobs submissions or requests for resources within a cluster, a cluster scheduler will employ reservations to insure that jobs will have the resources necessary for processing. FIG. 1B illustrates a cluster/node diagram for a cluster 124 with nodes 120. Time is along the X axis. An access control list 114 (ACL) to the cluster is static, meaning that the ACL is based on the credentials of the person, group, account, class or quality of service making the request or job submission to the cluster. The ACL 114 determines what jobs get assigned to the cluster 110 via a reservation 112 shown as spanning into two nodes of the cluster. Either the job can be allocated to the cluster or it can't and the decision is determined based on who submits the job at submission time. The deficiency with this approach is that there are situations in which organizations would like to make resources available but only in such a way as to balance or meet certain performance goals. Particularly, groups may want to establish a constant expansion factor and make that available to all users or they may want to make a certain subset of users that are key people in an organization and want to give them special services but only when their response time drops below a certain threshold. Given the prior art model, companies are unable to have the flexibility over their cluster resources. To improve the management of compute resources, what is needed in the art is a method for a scheduler, such as a grid scheduler, a cluster scheduler or cluster workload management system to manage resources more efficiently. Furthermore, given the complexity of the cluster environment, what is needed is more power and flexibility in the reservations process. SUMMARY OF THE INVENTION Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The features and advantages of the invention may be realized and obtained by means of the instruments and combinations particularly pointed out in the appended claims. These and other features of the present invention will become more fully apparent from the following description and appended claims, or may be learned by the practice of the invention as set forth herein. The invention relates to systems, methods and computer-readable media for dynamically modifying either compute resources or a reservation for compute resources within a compute environment such as a grid or a cluster. In one aspect of the invention, a method of dynamically modifying resources within a compute environment comprises receiving a request for resources in the compute environment, monitoring events after receiving the request for resources and based on the monitored events, dynamically modifying at least one of the request for resources and the compute environment. The invention enables an improved matching between a reservation and jobs submitted for processing in the compute environment. A benefit of the present invention is that the compute environment and the reservation or jobs submitted under the reservation will achieve a better fit. The closer the fit between jobs, reservations and the compute resources provides increased efficiency of the resources. BRIEF DESCRIPTION OF THE DRAWINGS In order to describe the manner in which the above-recited and other advantages and features of the invention can be obtained, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. Understanding that these drawings depict only typical embodiments of the invention and are not therefore to be considered to be limiting of its scope, the invention will be described and explained with additional specificity and detail through the use of the accompanying drawings in which: FIG. 1A illustrates generally a grid scheduler, cluster scheduler, and resource managers interacting with compute nodes within plurality of clusters; FIG. 1B illustrates an access control list which provides access to resources within a compute environment; FIG. 2A illustrates a plurality of reservations made for compute resources; FIG. 2B illustrates a plurality of reservations and jobs submitted within those reservations; FIG. 3 illustrates a dynamic access control list; FIG. 4 illustrates a reservation creation window; FIG. 5 illustrates a dynamic reservation migration process; FIG. 6 illustrates a method embodiment of the invention; and FIG. 7 illustrates another method aspect of the invention. DETAILED DESCRIPTION OF THE INVENTION Various embodiments of the invention are discussed in detail below. While specific implementations are discussed, it should be understood that this is done for illustration purposes only. A person skilled in the relevant art will recognize that other components and configurations may be used without parting from the spirit and scope of the invention. The present invention relates to reservations of resources within the context of a compute environment. One example of a compute environment is a cluster. The cluster may be, for example, a group of computing devices operated by a hosting facility, a hosting center, a virtual hosting center, a data center, grid and/or utility-based computing environments. Every reservation consists of three major components: a set of resources, a timeframe, and an access control list (ACL). Additionally, a reservation may also have a number of optional attributes controlling its behavior and interaction with other aspects of scheduling. A reservation's ACL specifies which jobs can use the reservation. Only jobs which meet one or more of a reservation's access criteria are allowed to use the reserved resources during the reservation timeframe. The reservation access criteria comprises, in one example, at least following: users, groups, accounts, classes, quality of service (QOS) and job duration. A job may be any venue or end of consumption of resource for any broad purpose, whether it be for a batch system, direct volume access or other service provisioning. A workload manager, or scheduler, will govern access to the compute environment by receiving requests for reservations of resources and creating reservations for processing jobs. A workload manager functions by manipulating five primary, elementary objects. These are jobs, nodes, reservations, QOS structures, and policies. In addition to these, multiple minor elementary objects and composite objects are also utilized. These objects are also defined in a scheduling dictionary. A workload manager may operate on a single computing device or multiple computing devices to manage the workload of a compute environment The “system” embodiment of the invention may comprise a computing device that includes the necessary hardware and software components to enable a workload manager or a software module performing the steps of the invention. Such a computing device may include such known hardware elements as one or more central processors, random access memory (RAM), read-only memory (ROM), storage devices such as hard disks, communication means such as a modem or a card to enable networking with other computing devices, a bus that provides data transmission between various hardware components, a keyboard, a display, an operating system and so forth. There is no restriction that the particular system embodiment of the invention have any specific hardware components and any known or future developed hardware configurations are contemplated as within the scope of the invention when the computing device operates as is claimed. Job information is provided to the workload manager scheduler from a resource manager such as Loadleveler, the Portable Batch System (PBS), Wiki or Platform's LSF products. Those of skill in the art will be familiar with each of these software products and their variations. Job attributes include ownership of the job, job state, amount and type of resources required by the job, required criteria (I need this job finished in 1 hour), preferred criteria (I would like this job to complete in ½ hour) and a wallclock limit, indicating how long the resources are required. A job consists of one or more requirements each of which requests a number of resources of a given type. For example, a job may consist of two requirements, the first asking for ‘1 IBM node with at least 512 MB of RAM’ and the second asking for ‘24 IBM nodes with at least 128 MB of RAM’. Each requirement consists of one or more tasks where a task is defined as the minimal independent unit of resources. A task is a collection of elementary resources which must be allocated together within a single node. For example, a task may consist of one processor, 512 MB or memory, and 2 GB of local disk. A task may also be just a single processor. In symmetric multiprocessor (SMP) environments, however, users may wish to tie one or more processors together with a certain amount of memory and/or other resources. A key aspect of a task is that the resources associated with the task must be allocated as an atomic unit, without spanning node boundaries. A task requesting 2 processors cannot be satisfied by allocating 2 uni-processor nodes, nor can a task requesting 1 processor and 1 GB of memory be satisfied by allocating 1 processor on one node and memory on another. A job requirement (or req) consists of a request for a single type of resources. Each requirement consists of the following components: (1) a task definition is a specification of the elementary resources which compose an individual task; (2) resource constraints provide a specification of conditions which must be met in order for resource matching to occur. Only resources from nodes which meet all resource constraints may be allocated to the job requirement; (3) a task count relates to the number of task instances required by the requirement; (4) a task List is a list of nodes on which the task instances have been located; and (5) requirement statistics are statistics tracking resource utilization. As far as the workload manager is concerned, a node is a collection of resources with a particular set of associated attributes. In most cases, it fits nicely with the canonical world view of a node such as a PC cluster node or an SP node. In these cases, a node is defined as one or more CPU's, memory, and possibly other compute resources such as local disk, swap, network adapters, software licenses, etc. Additionally, this node will described by various attributes such as an architecture type or operating system. Nodes range in size from small uni-processor PC's to large SMP systems where a single node may consist of hundreds of CPU's and massive amounts of memory. Information about nodes is provided to the scheduler chiefly by the resource manager. Attributes include node state, configured and available resources (i.e., processors, memory, swap, etc.), run classes supported, etc. Policies are generally specified via a configuration file and serve to control how and when jobs start. Policies include, but are not limited to, job prioritization, fairness policies, fairshare configuration policies, and scheduling policies. Jobs, nodes, and reservations all deal with the abstract concept of a resource. A resource in the workload manager world is one of the following: (1) processors which are specified with a simple count value; (2) memory such as real memory or ‘RAM’ is specified in megabytes (MB); (3) swap which is virtual memory or ‘swap’ is specified in megabytes (MB); and (4) disk space such as a local disk is specified in megabytes (MB) or gigabytes (GB). In addition to these elementary resource types, there are two higher level resource concepts used within workload manager. These are the task and the processor equivalent (PE). In a workload manager, jobs or reservations that request resources make such a request in terms of tasks typically using a task count and a task definition. By default, a task maps directly to a single processor within a job and maps to a fill node within reservations. In all cases, this default definition can be overridden by specifying a new task definition. Within both jobs and reservations, depending on task definition, it is possible to have multiple tasks from the same job mapped to the same node. For example, a job requesting 4 tasks using the default task definition of 1 processor per task, can be satisfied by two dual processor nodes. The concept of the PE arose out of the need to translate multi-resource consumption requests into a scalar value. It is not an elementary resource, but rather, a derived resource metric. It is a measure of the actual impact of a set of requested resources by a job on the total resources available system wide. It is calculated as: PE = MAX(ProcsRequestedByJob/TotalConfiguredProcs, MemoryRequestedByJob/TotalConfiguredMemory, DiskRequestedByJob/TotalConfiguredDisk, SwapRequestedByJob/TotalConfiguredSwap) * TotalConfiguredProcs For example, say a job requested 20% of the total processors and 50% of the total memory of a 128 processor MPP system. Only two such jobs could be supported by this system. The job is essentially using 50% of all available resources since the system can only be scheduled to its most constrained resource, in this case memory. The processor equivalents for this job should be 50% of the PE=64. A further example will be instructive. Assume a homogeneous 100 node system with 4 processors and 1 GB of memory per node. A job is submitted requesting 2 processors and 768 MB of memory. The PE for this job would be calculated as: PE=MAX(2/(100*4), 768/(100*1024))*(100*4)=3. This result makes sense since the job would be consuming ¾ of the memory on a 4 processor node. The calculation works equally well on homogeneous or heterogeneous systems, uni-processor or large way SMP systems. A class (or queue) is a logical container object which can be used to implicitly or explicitly apply policies to jobs. In most cases, a class is defined and configured within the resource manager and associated with one or more of the attributes or constraints shown in Table 1 below. TABLE 1 Attributes of a Class Attribute Description Default Job A queue may be associated with a default job duration, Attributes default size, or default resource requirements Host A queue may constrain job execution to a Constraints particular set of hosts Job A queue may constrain the attributes of jobs which may Constraints submitted including setting limits such as max wallclock time, minimum number of processors, etc. Access List A queue may constrain who may submit jobs into it based on user lists, group lists, etc. Special A queue may associate special privileges with jobs Access including adjusted job priority. As stated previously, most resource managers allow full class configuration within the resource manager. Where additional class configuration is required, the CLASSCFG parameter may be used. The workload manager tracks class usage as a consumable resource allowing sites to limit the number of jobs using a particular class. This is done by monitoring class initiators which may be considered to be a ticket to run in a particular class. Any compute node may simultaneously support several types of classes and any number of initiators of each type. By default, nodes will have a one-to-one mapping between class initiators and configured processors. For every job task run on the node, one class initiator of the appropriate type is consumed. For example, a three processor job submitted to the class batch will consume three batch class initiators on the nodes where it is run. Using queues as consumable resources allows sites to specify various policies by adjusting the class initiator to node mapping. For example, a site running serial jobs may want to allow a particular 8 processor node to run any combination of batch and special jobs subject to the following constraints: only 8 jobs of any type allowed simultaneously no more than 4 special jobs allowed simultaneously To enable this policy, the site may set the node's MAXJOB policy to 8 and configure the node with 4 special class initiators and 8 batch class initiators. Note that in virtually all cases jobs have a one-to-one correspondence between processors requested and class initiators required. However, this is not a requirement and, with special configuration sites may choose to associate job tasks with arbitrary combinations of class initiator requirements. In displaying class initiator status, workload manager signifies the type and number of class initiators available using the format [<CLASSNAME>:<CLASSCOUNT>]. This is most commonly seen in the output of node status commands indicating the number of configured and available class initiators, or in job status commands when displaying class initiator requirements. Nodes can also be configured to support various arbitrary resources. Information about such resources can be specified using the NODECFG parameter. For example, a node may be configured to have “256 MB RAM, 4 processors, 1 GB Swap, and 2 tape drives”. We next turn to the concept of reservations. There are several types of reservations which sites typically deal with. The first, administrative reservations, are typically one-time reservations created for special purposes and projects. These reservations are created using a command that sets a reservation. These reservations provide an integrated mechanism to allow graceful management of unexpected system maintenance, temporary projects, and time critical demonstrations. This command allows an administrator to select a particular set of resources or just specify the quantity of resources needed. For example, an administrator could use a regular expression to request a reservation be created on the nodes ‘blue0[1-9]’ or could simply request that the reservation locate the needed resources by specifying a quantity based request such as ‘TASKS==20’. Another type of reservation is called a standing reservation. This is shown in FIG. 2A. A standing reservation is useful for recurring needs for a particular type of resource distribution. For example, a site could use a standing reservation to reserve a subset of its compute resources for quick turnaround jobs during business hours on Monday thru Friday. Standing reservations are created and configured by specifying parameters in a configuration file. As shown in FIG. 2A, the compute environment 202 includes standing reservations shown as 204A, 204B and 204C. These reservations show resources allocated and reserved on a periodic basis. These are, for example, consuming reservations meaning that cluster resources will be consumed by the reservation. These reservations are specific to a user or a group of users and allow the reserved resources to be also customized specific to the workload submitted by these users or groups. For example, one aspect of the invention is that a user may have access to reservation 204A and not only submit jobs to the reserved resources but request, perhaps for optimization or to meet preferred criteria as opposed to required criteria, that the resources within the reservation be modified by virtual partitioning or some other means to accommodate the particular submitted job. In this regard, this embodiment of the invention enables the user to submit and perhaps request modification or optimization within the reserved resources for that particular job. There may be an extra charge or debit of an account of credits for the modification of the reserved resources. The modification of resources within the reservation according to the particular job may also be performed based on a number of factors discussed herein, such as criteria, class, quality of service, policies etc. Standing reservations build upon the capabilities of advance reservations to enable a site to enforce advanced usage policies in an efficient manner. Standing reservations provide a superset of the capabilities typically found in a batch queuing system's class or queue architecture. For example, queues can be used to allow only particular types of jobs access to certain compute resources. Also, some batch systems allow these queues to be configured so that they only allow this access during certain times of the day or week. Standing reservations allow these same capabilities but with greater flexibility and efficiency than is typically found in a normal queue management system. Standing Reservations provide a mechanism by which a site can dedicate a particular block of resources for a special use on a regular daily or weekly basis. For example, node X could be dedicated to running jobs only from users in the accounting group every Friday from 4 to 10 PM. A standing reservation is a powerful means of controlling access to resources and controlling turnaround of jobs. Another embodiment of reservation is something called a reservation mask, which allows a site to create “sandboxes” in which other guarantees can be made. The most common aspects of this reservation are for grid environments and personal reservation environments. In a grid environment, a remote entity will be requesting resources and will want to use these resources on an autonomous cluster for the autonomous duster to participate. In many cases it will want to constrain when and where the entities can reserve or utilize resources. One way of doing that is via the reservation mask. FIG. 2B illustrates the reservation mask shown as creating sandboxes 206A, 206B, 206C in compute environment 210 and allows the autonomous cluster to state that only a specific subset of resources can be used by these remote requesters during a specific subset of times. When a requester asks for resources, the scheduler will only report and return resources available within this reservation, after which point the remote entity desires it, it can actually make a consumption reservation and that reservation is guaranteed to be within the reservation mask space. The consumption reservations 212A, 212B, 212C, 212D are shown within the reservation masks. Another concept related to reservations is the personal reservation and/or the personal reservation mask. In compute environment 210, the reservation masks operate differently from consuming reservations in that they are enabled to allow personal reservations to be created within the space that is reserved. ACL's are independent inside of a sandbox reservation or a reservation mask in that you can also exclude other requesters out of those spaces so they're dedicated for these particular users. One benefit of the personal reservation approach includes preventing local job starvation, and providing a high level of control to the cluster manager in that he or she can determine exactly when, where, how much and who can use these resources even though he doesn't necessarily know who the requesters are or the combination or quantity of resources they will request. The administrator can determine when, how and where requestors will participate in these clusters or grids. A valuable use is in the space of personal reservations which typically involves a local user given the authority to reserve a block of resources for a rigid time frame. Again, with a personal reservation mask, the requests are limited to only allow resource reservation within the mask time frame and mask resource set, providing again the administrator the ability to constrain exactly when and exactly where and exactly how much of resources individual users can reserve for a rigid time frame. The individual user is not known ahead of time but it is known to the system, it is a standard local cluster user. The reservation masks 206A, 206B and 206C define periodic, personal reservation masks where other reservations in the compute environment 210 may be created, i.e., outside the defined boxes. These are provisioning or policy-based reservations in contrast to consuming reservations. In this regard, the resources in this type of reservation are not specifically allocated but the time and space defined by the reservation mask cannot be reserved for other jobs. Reservation masks enable the system to be able to control the fact that resources are available for specific purposes, during specific time frames. The time frames may be either single time frames or repeating time frames to dedicate the resources to meet project needs, policies, guarantees of service, administrative needs, demonstration needs, etc. This type of reservation insures that reservations are managed and scheduled in time as well as space. Boxes 208A, 208B, 208C and 208D represent non-personal reservation masks. They have the freedom to be placed anywhere in duster including overlapping some or all of the reservation masks 206A, 206B, 206C. Overlapping is allowed when the personal reservation mask was setup with a global ACL. To prevent the possibility of an overlap of a reservation mask by a non-personal reservation, the administrator can set an ACL to constrain it is so that only personal consumption reservations are inside. These personal consumption reservations are shown as boxes 212B, 212A, 212C, 212D which are constrained to be within the personal reservation masks 206A, 206B, 206C. The 208A, 208B, 208C and 208D reservations, if allowed, can go anywhere within the cluster 210 including overlapping the other personal reservation masks. The result is the creation of a “sandbox” where only personal reservations can go without in any way constraining the behavior of the scheduler to schedule other requests. All reservations possess a start and an end time which define the reservation's active time. During this active time, the resources within the reservation may only be used as specified by the reservation ACL. This active time may be specified as either a start/end pair or a start/duration pair. Reservations exist and are visible from the time they are created until the active time ends at which point they are automatically removed. For a reservation to be useful, it must be able to limit who or what can access the resources it has reserved. This is handled by way of an access control list, or ACL. With reservations, ACL's can be based on credentials, resources requested, or performance metrics. In particular, with a standing reservation, the attributes userlist, grouplist, accountlist, classlist, qoslist, jobattrlist, proclimit, timelimit and others may be specified. FIG. 3 illustrates an aspect of the present invention that allows the ACL 306 for the reservation 304 to have a dynamic aspect instead of simply being based on who the requester is. The ACL decision-making process is based at least in part on the current level of service or response time that is being delivered to the requester. To illustrate the operation of the ACL 306, assume that a user 308 submits a job 314 to a queue 310 and that the ACL 306 reports that the only job that can access these resources 302 are those that have a queue time that currently exceeds two hours. The resources 302 are shown with resources N on the y axis and time on the x axis. If the job 314 has sat in the queue 310 for two hours it will then access the additional resources to prevent the queue time for the user 308 from increasing significantly beyond this time frame. The decision to allocate these additional resources can be keyed off of utilization of an expansion factor and other performance metrics of the job. For example, the reservation 304 may be expanded or contracted or migrated to cover a new set of resources. Whether or not an ACL 306 is satisfied is typically and preferably determined the scheduler 104A. However, there is no restriction in the principle of the invention regarding where or on what node in the network the process of making these allocation of resource decisions occurs. The scheduler 104A is able to monitor all aspects of the request by looking at the current job 314 inside the queue 310 and how long it has sat there and what the response time target is and the scheduler itself determines whether all requirements of the ACL 306 are satisfied. If requirements are satisfied, it releases the resources that are available to the job 314. A job 314 that is located in the queue and the scheduler communicating with the scheduler 104A. If resources are allocated, the job 314 is taken from the queue 310 and inserted into the reservation 314 in the duster 302. An example benefit of this model is that it makes it significantly easier for a site to balance or provide guaranteed levels of service or constant levels of service for key players or the general populace. By setting aside certain resources and only making them available to the jobs which threaten to violate their quality of service targets, the system increases the probability of satisfying targets. When specifying which resources to reserve, the administrator has a number of options. These options allow control over how many resources are reserved and where they are reserved at. The following reservation attributes allow the administrator to define resources. An important aspect of reservations is the idea of a task. The scheduler uses the task concept extensively for its job and reservation management. A task is simply an atomic collection of resources, such as processors, memory, or local disk, which must be found on the same node. For example, if a task requires 4 processors and 2 GB of memory, the scheduler must find all processors AND memory on the same node; it cannot allocate 3 processors and 1 GB on one node and 1 processor and 1 GB of memory on another node to satisfy this task. Tasks constrain how the scheduler must collect resources for use in a standing reservation, however, they do not constrain the way in which the scheduler makes these cumulative resources available to jobs. A job can use the resources covered by an accessible reservation in whatever way it needs. If reservation X allocated 6 tasks with 2 processors and 512 MB of memory each, it could support job Y which requires 10 tasks of 1 processor and 128 MB of memory or job Z which requires 2 tasks of 4 processors and 1 GB of memory each. The task constraints used to acquire a reservation's resources are completely transparent to a job requesting use of these resources. Using the task description, the taskcount attribute defines how many tasks must be allocated to satisfy the reservation request. To create a reservation, a taskcount and/or a hostlist may be specified. A hostlist constrains the set of resource which are available to a reservation. If no taskcount is specified, the reservation will attempt to reserve one task on each of the listed resources. If a taskcount is specified which requests fewer resources than listed in the hostlist, the scheduler will reserve only the number of tasks from the hostlist specified by the taskcount attribute. If a taskcount is specified which requests more resources than listed in the hostlist, the scheduler will reserve the hostlist nodes first and then seek additional resources outside of this list. Reservation flags allow specification of special reservation attributes or behaviors. Supported flags are listed in table 2 below. TABLE 2 Flag Name Description BESTEFFORT N/A BYNAME reservation will only allow access to jobs which meet reservation ACL's and explicitly request the resources of this reservation using the job ADVRES flag IGNRSV request will ignore existing resource reservations allowing the reservation to be forced onto available resources even if this conflicts with other reservations. OWNERPREEMPT job's by the reservation owner are allowed to preempt non-owner jobs using reservation resources PREEMPTEE Preempts a job or other object SINGLEUSE reservation is automatically removed after completion of the first job to use the reserved resources SPACEFLEX reservation is allowed to adjust resources allocated over time in an attempt to optimize resource utilization TIMEFLEX reservation is allowed to adjust the reserved timeframe in an attempt to optimize resource utilization Reservations must explicitly request the ability to float for optimization purposes by using a flag such as the SPACEFLEX flag. The reservations may be established and then identified as self-optimizing in either space or time. If the reservation is flagged as such, then after the reservation is created, conditions within the compute environment may be monitored to provide feedback on where optimization may occur. If so justified, a reservation may migrate to a new time or migrate to a new set of resources that are more optimal than the original reservation. FIG. 4 illustrates a reservation creation window 400 that includes the use of the flags in Table 2. A user Scott input reservation information in a variety of fields 402 for name, partition, node features and floating reservation. Each of these input fields includes a drop-down menu to enable the selection of options easy. An access control list input field 404 allows the user to input an account, class/queue, user, group and QoS information. Resources may be assigned and searched and tasks created 406 and reservation flags set 408, such as best effort, single use, preemptee, time flex, by name, owner preempt, space flex, exclusive and force. These flags set parameters that may cause the reservation to be optimized such as in time or space where it migrates to a new time or over new resources based on monitored events or other feedback. A reservation time-frame 410 may also be input such as one, daily, weekly, with start and end times for the reservation. Menu drop down calendars and docks are available for easily enabling the user to view and graphically input and select the various timeframe parameters. Event triggers may also be input wherein the user can create one or more triggers associated with the reservation. As generally shown in FIG. 4, the use of a graphical interface simplifies the reservation-creation process for the administrator or user. FIG. 5 illustrates a particular instance where the user has identified the time-flex and space-flex flags within the reservation. A window 500 identifies three reservations 502 for 96 nodes, 504 for 128 nodes and 506 for 256 nodes. The height of each of these reservations generally relates to resources reserved, such as a number of processors reserved or processors and disk space. The X-axis represents time. Reservation 508 represents a reservation in the future that will in a position to receive submitted jobs. Assume that reservation 506 which was scheduled to end at time T2 has finished early at time T1. Also assume that reservation 508 is flagged for time flex and space flex. In this case, based on the monitored event that reservation 506 has ended early, the system would cause reservation 508 to migrate in time (and space in this example) to position 510. This represents a movement of the reservation to a new time and a new set of resources. If reservation 504 ends early, and reservation 508 migrates to position 520, that would represent a migration in time (to an earlier time) but not in space. This would be enabled by the time-flex flag being set wherein the migration would seek to create a new reservation at the earliest time possible and/or according to available resources. The new time may be based on criteria to minimize the time for the reservation or to maximize usage of the overall resources or better performance of the compute environment. Next, assume that reservation 508 is for 128 processors and reservation 506 is for 256 processors and reservation 508 is flagged for space flex. If reservation 506 ends are time T1 instead of time T2, then reservation 508 may migrate to position 512 to a reservation of 256 processors. The time frame of the starting and ending time may be the same but the reservation has migrated in space and thus been optimized. In another aspect of reservation migration, assume that reservation 508 is set but that a node or a group of nodes that are part of the reservation go down or are projected to fail as represented by 518. In this regard, reservation 508 may be enabled to migrate as shown by 516 and 508 to cover new resources but to accommodate for the nodes that are no longer available. Standing reservations allow resources to be dedicated for particular uses. This dedication can be configured to be permanent or periodic, recurring at a regular time of day and/or time of week. There is extensive applicability of standing reservations for everything from daily dedicated job runs to improved use of resources on weekends. All standing reservation attributes are specified via a parameter using available attributes In addition to standing and administrative reservations, a workload manager according to the invention can also create priority reservations. These reservations are used to allow the benefits of out-of-order execution (such as is available with a backfill feature) without the side effect of job starvation. Starvation can occur in any system where the potential exists for a job to be overlooked by the scheduler for an indefinite period. In the case of backfill, small jobs may continue to be run on available resources as they become available while a large job sits in the queue never able to find enough nodes available simultaneously to run on. To avoid such situations, priority reservations are created for high priority jobs which cannot run immediately. When making these reservations, the scheduler determines the earliest time the job could start, and then reserves these resources for use by this job at that future time. By default, only the highest priority job will receive a priority reservation. However, this behavior is configurable via a reservation depth policy. The workload manager's default behavior of only reserving the highest priority job allows backfill to be used in a form known as liberal backfill. This liberal backfill tends to maximize system utilization and minimize overall average job turnaround time. However, it does lead to the potential of some lower priority jobs being indirectly delayed and may lead to greater variance in job turnaround time. A reservation depth parameter can be set to a very large value, essentially enabling what is called conservative backfill where every job which cannot run is given a reservation. Most sites prefer the liberal backfill approach associated with the default reservation depth 1 or select a slightly higher value. It is important to note that to prevent starvation in conjunction with reservations, monotonically increasing priority factors such as queuetime or job x-factor should be enabled. Another important consequence of backfill and reservation depth is its affect on job priority. In the workload manager, all jobs are preferably prioritized. Backfill allows jobs to be run out of order and thus, to some extent, job priority to be ignored. This effect, known as ‘priority dilution’ can cause many site policies implemented via workload manager prioritization policies to be ineffective. Setting the reservation depth parameter to a higher value will give job priority ‘more teeth’ at the cost of slightly lower system utilization. This lower utilization results from the constraints of these additional reservations, decreasing the scheduler's freedom and its ability to find additional optimizing schedules. Anecdotal evidence indicates that these utilization losses are fairly minor, rarely exceeding 8%. In addition to the reservation depth parameter, sites also have the ability to control how reservations are maintained. The workload manager's dynamic job prioritization allows sites to prioritize jobs so that their priority order can change over time. It is possible that one job can be at the top of the priority queue for a time, and then get bypassed by another job submitted later. A reservation policy parameter allows a site to determine what how existing reservations should be handled when new reservations are made. The value “highest” will cause that all jobs which have ever received a priority reservation will maintain that reservation until they run even if other jobs later bypass them in priority value. The value of the parameter “current highest” will cause that only the current top <RESERVATIONDEPTH> priority jobs will receive reservations. If a job had a reservation but has been bypassed in priority by another job so that it no longer qualifies as being among the top <RESERVATIONDEPTH> jobs, it will lose its reservation. Finally, the value “never” indicates that no priority reservations will be made. QOS-based reservation depths can be enabled via the reservation QOS list parameter. This parameter allows varying reservation depths to be associated with different sets of job QoS's. For example, the following configuration will create two reservation depth groupings: - - - - RESERVATIONDEPTH[0] 8 RESERVATIONQOSLIST[0] highprio interactive debug RESERVATIONDEPTH[1] 2 RESERVATIONQOSLIST[1] batch - - - - This example will cause that the top 8 jobs belonging to the aggregate group of highprio, interactive, and debug QoS jobs will receive priority reservations. Additionally, the top 2 batch QoS jobs will also receive priority reservations. Use of this feature allows sites to maintain high throughput for important jobs by guaranteeing a significant proportion of these jobs are making progress toward starting through use of the priority reservation. The following are example default values for some of these parameters: RESERVATIONDEPTH[DEFAULT] =1; RESERVATIONQOSLIST[DEFAULT] =ALL. This allows one job with the highest priority to get a reservation. These values can be overwritten by modifying the default policy. A final reservation policy is in place to handle a number of real-world issues. Occasionally when a reservation becomes active and a job attempts to start, various resource manager race conditions or corrupt state situations will prevent the job from starting. By default, the workload manager assumes the resource manager is corrupt, releases the reservation, and attempts to re-create the reservation after a short timeout. However, in the interval between the reservation release and the re-creation timeout, other priority reservations may allocate the newly available resources, reserving them before the original reservation gets an opportunity to reallocate them. Thus, when the original job reservation is re-established, its original resource may be unavailable and the resulting new reservation may be delayed several hours from the earlier start time. The parameter reservation retry time allows a site that is experiencing frequent resource manager race conditions and/or corruption situations to tell the workload manager to hold on to the reserved resource for a period of time in an attempt to allow the resource manager to correct its state. Next we discuss the use of partitions. Partitions are a logical construct which divide available resources and any single resource (i.e., compute node) may only belong to a single partition. Often, natural hardware or resource manager bounds delimit partitions such as in the case of disjoint networks and diverse processor configurations within a cluster. For example, a cluster may consist of 256 nodes containing four 64 port switches. This cluster may receive excellent interprocess communication speeds for parallel job tasks located within the same switch but sub-stellar performance for tasks which span switches. To handle this, the site may choose to create four partitions, allowing jobs to run within any of the four partitions but not span them. While partitions do have value, it is important to note that within the workload manager, the standing reservation facility provides significantly improved flexibility and should be used in the vast majority of politically motivated cases where partitions may be required under other resource management systems. Standing reservations provide time flexibility, improved access control features, and more extended resource specification options. Also, another workload manager facility called node sets allows intelligent aggregation of resources to improve per job node allocation decisions. In cases where system partitioning is considered for such reasons, node sets may be able to provide a better solution. An important aspect of partitions over standing reservations and node sets is the ability to specify partition specific policies, limits, priorities, and scheduling algorithms although this feature is rarely required. An example of this need may be a cluster consisting of 48 nodes owned by the Astronomy Department and 16 nodes owned by the Mathematics Department. Each department may be willing to allow sharing of resources but wants to specify how their partition will be used. As mentioned earlier, many of the workload manager's scheduling policies may be specified on a per partition basis allowing each department to control the scheduling goals within their partition. The partition associated with each node should be specified as indicated in the node location section. With this done, partition access lists may be specified on a per job or per QOS basis to constrain which resources a job may have access to. By default, QOS's and jobs allow global partition access. Note that by default, a job may only utilize resources within a single partition. If no partition is specified, the workload manager creates one partition per resource manager into which all resources corresponding to that resource manager are placed. This partition may be given the same name as the resource manager. A partition preferably does not span multiple resource managers. In addition to these resource manager partitions, a pseudo-partition named [ALL] is created which contains the aggregate resources of all partitions. While the resource manager partitions are real partitions containing resources not explicitly assigned to other partitions, the [ALL] partition is only a convenience object and is not a real partition; thus it cannot be requested by jobs or included in configuration ACL's. Node-to-partition mappings are established using a node configuration parameter as shown in this example: NODECFG[node001] PARTITION=astronomy NODECFG[node002] PARTITION=astronomy . . . NODECFG[node049] PARTITION=math . . . By default, the workload manager only allows the creation of 4 partitions total. Two of these partitions, DEFAULT, and [ALL], are used internally, leaving only two additional partition definition slots available. If more partitions will be needed, the maximum partition count should be adjusted. Increasing the maximum number of partitions can be managed. Determining who can use which partition is specified using *CFG parameters (for example, these parameters may be defined as: usercfg, groupcfg, accountcfg, quoscfg, classcfg and systemcfg). These parameters allow both a partition access list and default partition to be selected on a credential or system wide basis using the PLIST and PDEF keywords. By default, the access associated with any given job is the logical or of all partition access lists assigned to the job's credentials. Assume a site with two partitions: general and test. The site management would like everybody to use the general partition by default. However, one user, Steve, needs to perform the majority of his work on the test partition. Two special groups, staff and mgmt will also need access to use the test partition from time to time but will perform most of their work in the general partition. The example configuration below will enable the needed user and group access and defaults for this site. SYSCFG[base] PLIST= USERCFG[DEFAULT] PLIST=general USERCFG[steve] PLIST=general:test PDEF=test GROUPCFG[staff] PLIST=general:test PDEF=general GROUPCFG[mgmt] PLIST=general:test PDEF=general By default, the system partition access list allows global access to all partitions. If using logically or based partition access lists, the system partition list should be explicitly constrained using the SYSCFG parameter. While using a logical or approach allows sites to add access to certain jobs, some sites prefer to work the other way around. In these cases, access is granted by default and certain credentials are then restricted from access various partitions. To use this model, a system partition list must be specified. See the example below: SYSCFG[base] PLIST=general,test& USERCFG[demo] PLIST=test& GROUP[staff] PLIST=general& In the above example, note the ampersand (‘&’). This character, which can be located anywhere in the PLIST line, indicates that the specified partition list should be logically AND'd with other partition access lists. In this case, the configuration will limit jobs from user demo to running in partition test and jobs from group staff to running in partition general. All other jobs will be allowed to run in either partition. When using and based partition access lists, the base system access list must be specified with SYSCFG. Users may request to use any partition they have access to on a per job basis. This is accomplished using the resource manager extensions, since most native batch systems do not support the partition concept. For example, on a PBS system, a job submitted by a member of the group staff could request that the job run in the test partition by adding the line ‘#PBS-W×=PARTITION:test’ to the command file. Special jobs may be allowed to span the resources of multiple partitions if desired by associating the job with a QOS which has the flag ‘SPAN’ set. The disclosure now continues to discuss reservations further. An advance reservation is the mechanism by which the present invention guarantees the availability of a set of resources at a particular time. With an advanced reservation a site now has an ability to actually specify how the scheduler should manage resources in both space and time. Every reservation consists of three major components, a list of resources, a timeframe (a start and an end time during which it is active), and the ACL. These elements are subject to a set of rules. The ACL acts as a doorway determining who or what can actually utilize the resources of the cluster. It is the job of the cluster scheduler to make certain that the ACL is not violated during the reservation's lifetime (i.e., its timeframe) on the resources listed. The ACL governs access by the various users to the resources. The ACL does this by determining which of the jobs, various groups, accounts, jobs with special service levels, jobs with requests for specific resource types or attributes and many different aspects of requests can actually come in and utilize the resources. With the ability to say that these resources are reserved, the scheduler can then enforce true guarantees and can enforce policies and enable dynamic administrative tasks to occur. The system greatly increases in efficiency because there is no need to partition the resources as was previously necessary and the administrative overhead is reduced it terms of staff time because things can be automated and scheduled ahead of time and reserved. As an example of a reservation, a reservation may specify that node 002 is reserved for user John Doe on Friday. The scheduler will thus be constrained to make certain that only John Doe's jobs can use node 002 at any time on Friday. Advance reservation technology enables many features including backfill, deadline based scheduling, QOS support, and meta scheduling. There are several reservation concepts that will be introduced as aspects of the invention. These include dynamic reservations, co-allocating reservation resources of different types, reservations that self-optimize in time, reservations that self-optimization in space, reservations rollbacks and reservation masks. The present invention relates to a system and method of providing dynamic reservations in a compute environment. Dynamic reservations are reservations that are able to be modified once they are created. The workload manager allows dynamic modification of most scheduling parameters allowing new scheduling policies, algorithms, constraints, and permissions to be set at any time. For example, a reservation may be expanded or contracted after a job is submitted to more closely match the reservation to the workload. Changes made via client commands are preferably temporary and will be overridden by values specified in a config files the next time the workload manager is shutdown and restarted. Various commands may be used manually or automatically to control reservations. Examples of such commands and their function are illustrated in Table 3: TABLE 3 mdiag -r display summarized reservation information and any unexpected state mrsvctl reservation control mrsvctl -r remove reservations mrsvctl -c create an administrative reservation showres display information regarding location and state of reservations FIG. 6 illustrates a method of dynamically modifying a request, a reservation or the compute environment. Attributes of a reservation may change based on a feedback mechanism that adds intelligence as to ideal characteristics of the reservation and how it should be applied as the context of its environment or an entities needs change. One example of a dynamic reservation is a reservation that provides for a guarantee of resources for a request unless no jobs that consume resources are submitted under the request or if the user is not using the reserved resources. In other words, if no jobs are submitted on reserved resources or the job that is submitted does not need all of the reserved resources. The example method in FIG. 6 can relate to the scenario where a job has or has not yet been submitted to reserved compute resources. The method comprises receiving a request for resources within the compute environment (602) and monitoring events after receiving the request for resources (604). Based on the monitored events, the method comprises dynamically modifying at least one of the request for resources, a reservation and the compute environment (606). The compute environment may be a computer farm, a cluster, a grid, an on-demand computing center and the like. The request for resources may be a request for consumption of resources such as processor time and network bandwidth. The request may also be for provisioning resources such as available licenses for particular software or operating systems. The request may also be for such things as a request to process a batch job or for direct volume access, or a request for a virtual private cluster. The monitored events may further mean monitoring events related to the compute environment. Events that may be identified include, but are not limited to, new resources that become available because other jobs finish early, compute nodes that go down and are unavailable, other jobs submitted to the compute environment. In this regard, the monitoring may include jobs submitted by an administrator, other users or the requestor. For example, if the requestor never submits a job within a reservation made according to the request, then the method may modify the reservation by shrinking the reservation or reduce the reserved amount of resources for efficiency. The request or the reservation may also be canceled if no jobs are submitted or based on other criteria. A job submitted may also be one of a reservation, an object that monitors policy, an object that monitors credentials, an object that monitors node states and an object that monitors the compute environment. If the compute environment is dynamically modified according to the monitored events, the modification may be performed to satisfy the request for resources or preferences within the request. The modifications to the compute environment may also be constrained within the reservation space. Examples of modifications that may be done to the compute environment include but are not limited to modifying a node or nodes, modifying at least one operating system or other software, installing end-user applications, dynamically partitioning node resources and adjusting network configurations. Once a job has been submitted, the compute resources may be dynamically modified to more adequately process the job or more efficiently process the job. For example, if it is foreseen that the job will end early, the system may shorten the reservation of time for the resources to free-up migration of other reservations in that time and space. Another example may exist where if a reservation is partly consumed by a job, but based on monitored events, the remaining reserved resources, say 128 nodes, could be expanded to 256 nodes such that the job may finish early. In that case, the reservation from the current time would be dynamically modified to include additional resources. These changes may be based on The modifications to a request, a reservation or a compute environment may be based on a policy. For example, a dynamic reservation policy may apply which says that if the project does not use more than 25% of what it is guaranteed by the time that 50% of its time has expired, then, based on the feedback, the system dynamically modifies the reservation of resources to more closely match the job (606). In other words, the reservation dynamically adjust itself to reserve X % fewer resources for this project, thus freeing up unused resource for others to use. If the party submitting the request for resources has not submitted a job for processing after a predetermined amount of time, then the request for resources or the job submitted to the reservation may be cancelled. This is illustrated more with reference to FIG. 7 which illustrates this reservation. A self-terminating reservation is a reservation that can cancel itself if certain criteria take place. A reservation of compute resources is created (702) and the system monitors events associated with the reservation (704). The system determines whether the monitored events justifies canceling the reservation or jobs submitted according to the reservation (706). If no, there is no justification to terminate, then the system continues to monitor events in step (704). If, however, conditions justify terminating one of the reservation or a job, then the reservation terminates itself or a job is cancelled (708). An example of a self-terminating reservation is a reservation that uses an event policy to check that if after 30 minutes no jobs have been submitted against the reservation, or if utilization of the assigned resources is below x % then the reservation will cancel itself, thus making those resources available to be used by others. Another example is if a job is submitted to the reserved cluster resources, but to process the job would require the use of compute resources beyond the reservation time or the reserved duster resources, then the job may be canceled and notification provided to the submitted regarding the reasons for the cancellation. Options may then be provided to the submitter for modifying the reservation, or modifying the job and so forth to enable the job to be resubmitted under modified circumstances that may enable the job to be processed. Based on the monitored events in the cluster environment, modifying the request for resources may involve dynamically modifying the compute environment or modifying the compute environment to more adequately process jobs submitted within the reservation. Preferably, the option of extending the reservation to accommodate the job is subject to pre-established policies that are either required or preferred. One example of presenting these types of offers includes presenting the submitter the option of extending the reservation according to a pricing plan that would meet the preferred policies. This pricing plan may include options to pay for extended time, extended or modified resources, licenses, other provisioning options and so forth. Any combination of job or resource modification is envisioned. In this regard, the reservation of resources could migrate to “cover” a new set of resources that may meet a preferred criteria, an increased payment plan, or some other threshold. The migration of a reservation may be in both space (compute resources) and time (such as, for example, to move the start time of the reservation to as soon as possible). The migration in space may be for the purpose of increasing the performance for the overall compute environment or may be for optimizing the time of completion for a job or jobs. The migration may be for any other reason such as to modify the resources used because of a node failure or a projected maintenance of other failure of a resource. The system may also present a user with the option of allowing jobs running within a personal reservation to complete although the job is projected to run beyond the window of time for the reservation of resources. As mentioned above, the option of extending or modifying a reservation may be based on pre-established policies that govern whether a reservation may be modified and to what extent it may be modified. There are preferably thresholds established in time and space governing the modifications. The request for resources in a compute environment may include a request for a reservation of resources for a window of time in which at least one user can submit personal reservations. A personal reservation is a non-administrator reservation submitted by an individual user or a group of users that are not considered administrators. The personal reservation may be submitted by an administrator but is of a non-administrative nature. The window of time may also be a request for cluster resources for a periodic window of time, such as daily, weekly, monthly, quarterly and so on. Then, if the system receives a personal reservation for the use of compute resources within the window of time, the system provides access to the reserved cluster resources for the personal reservation to process submitted jobs. If the processing personal reservation exceeds the window of time for the reservation of compute resources, then the system may cancel and lock out the personal reservation from access to the cluster resources. Before canceling and locking out the personal reservation, the system may present to a user who submitted the personal reservation an option of allowing the personal reservation to complete although it is beyond the window of time for their reservation of compute resources. If a job submitted under the personal reservation would exceed the personal reservation, then the system may extend the personal reservation to meet the needs of the job or perform some other modification. A consumption job submitted may exceed the window of time allowed for the reservation and thus the system may never start the consumption job in the first place. Charging for resource use and reservation is also an aspect of the present invention. The system may also charge the requestor a specific rate for reserved resources and a different rate for consumed resources. Yet a different rate may be charged for reserved resources that are never used. The user/requestor may be charged for use of the resources in the duster environment in a variety of ways. For example, the user may be charged for reserved resources at one rate, and another rate for reserved and consumed resources. Within a reservation, the system may provide a modification of the compute resources within the reservation space. For example, the system may optimize the use of resources within that reservation to meet needs and preferences of particular jobs submitted under that reservation. Another dynamic reservation may perform the following step: if usage of resources provided by a reservation is above 90% with fewer than 10 minutes left in the reservation then the reservation will attempt to add 10% more time to the end of the reservation to help ensure the project is able to complete. In summary, it is the ability for a reservation to receive manual or automatic feedback to an existing reservation in order to have it more accurately match any given needs, whether those be of the submitting entity, the community of users, administrators, etc. The dynamic reservation improves the state of the art by allowing the ACL to the reservation to have a dynamic aspect instead of simply being based on who the requestor is. The reservation can be based on a current level of service or response time being delivered to the requestor. The ACL and scheduler are able to monitor all aspects of the request by looking at the current job inside the queue and how long it has sat there and what the response time target is. It is preferable, although not required, that the scheduler itself determines whether all requirements of the ACL are satisfied. If the requirements are satisfied, the scheduler releases the resources that are available to the job. The benefits of this model is it makes it significantly easier for a site to balance or provide guaranteed levels of service or constant levels of service for key players or the general populace. By setting aside certain resources and only making them available to the jobs which threaten to violate their quality of service targets it increases the probability of satisfying it. As can be appreciated, the methods described above for managing a compute environment provide marked improvements in how resources are reserved and how those reservations are managed in connection with the compute environment to maximize efficiency for both the user and the compute environment. Embodiments within the scope of the present invention may also include computer-readable media for carrying or having computer-executable instructions or data structures stored thereon. Such computer-readable media can be any available media that can be accessed by a general purpose or special purpose computer. By way of example, and not limitation, such computer-readable media can comprise RAM, ROM, EEPROM, CD-ROM or other optical disk storage, magnetic disk storage or other magnetic storage devices, or any other medium which can be used to carry or store desired program code means in the form of computer-executable instructions or data structures. When information is transferred or provided over a network or another communications connection (either hardwired, wireless, or combination thereof) to a computer, the computer properly views the connection as a computer-readable medium. Thus, any such connection is properly termed a computer-readable medium. Combinations of the above should also be included within the scope of the computer-readable media. Computer-executable instructions include, for example, instructions and data which cause a general purpose computer, special purpose computer, or special purpose processing device to perform a certain function or group of functions. Computer-executable instructions also include program modules that are executed by computers in stand-alone or network environments. Generally, program modules include routines, programs, objects, components, and data structures, etc. that perform particular tasks or implement particular abstract data types. Computer-executable instructions, associated data structures, and program modules represent examples of the program code means for executing steps of the methods disclosed herein. The particular sequence of such executable instructions or associated data structures represents examples of corresponding acts for implementing the functions described in such steps. Those of skill in the art will appreciate that other embodiments of the invention may be practiced in network computing environments with many types of computer system configurations, including personal computers, hand-held devices, multi-processor systems, microprocessor-based or programmable consumer electronics, network PCs, minicomputers, mainframe computers, and the like. Embodiments may also be practiced in distributed computing environments where tasks are performed by local and remote processing devices that are linked (either by hardwired links, wireless links, or by a combination thereof) through a communications network. In a distributed computing environment, program modules may be located in both local and remote memory storage devices. Although the above description may contain specific details, they should not be construed as limiting the claims in any way. Other configurations of the described embodiments of the invention are part of the scope of this invention. Accordingly, the appended claims and their legal equivalents should only define the invention, rather than any specific examples given.
<SOH> BACKGROUND OF THE INVENTION <EOH>1. Field of the Invention The present invention relates to reservations in a compute environment and more specifically to a system and method of providing advanced reservations to resources within a compute environment such as a cluster. 2. Introduction There are challenges in the complex process of managing the consumption of resources within a compute environment such as a grid, compute farm or cluster of computers. Grid computing may be defined as coordinated resource sharing and problem solving in dynamic, multi-institutional collaborations. Many computing projects require much more computational power and resources than a single computer may provide. Networked computers with peripheral resources such as printers, scanners, I/O devices, storage disks, scientific devices and instruments, etc. may need to be coordinated and utilized to complete a task. The term compute resource generally refers to computer processors, network bandwidth, and any of these peripheral resources as well. A compute farm may comprise a plurality of computers coordinated for such purposes of handling Internet traffic. The web search website Google® had a compute farm used to process its network traffic and Internet searches. Grid/cluster resource management generally describes the process of identifying requirements, matching resources to applications, allocating those resources, and scheduling and monitoring grid resources over time in order to run grid applications or jobs submitted to the compute environment as efficiently as possible. Each project or job will utilize a different set of resources and thus is typically unique. For example, a job may utilize computer processors and disk space, while another job may require a large amount of network bandwidth and a particular operating system. In addition to the challenge of allocating resources for a particular job or a request for resources, administrators also have difficulty obtaining a dear understanding of the resources available, the current status of the compute environment and available resources, and real-time competing needs of various users. One aspect of this process is the ability to reserve resources for a job. A cluster manager will seek to reserve a set of resources to enable the cluster to process a job at a promised quality of service. General background information on clusters and grids may be found in several publications. See, e.g., Grid Resource Management, State of the Art and Future Trends , Jarek Nabrzyski, Jennifer M. Schopf, and Jan Weglarz, Kluwer Academic Publishers, 2004; and Beowulf Cluster Computing with Linux , edited by William Gropp, Ewing Lusk, and Thomas Sterling, Massachusetts Institute of Technology, 2003. It is generally understood herein that the terms grid and cluster are interchangeable, although they have different connotations. For example, when a grid is referred to as receiving a request for resources and the request is processed in a particular way, the same method may also apply to other compute environments such as a cluster or a compute farm. A cluster is generally defined as a collection of compute nodes organized for accomplishing a task or a set of tasks. In general, a grid will comprise a plurality of clusters as will be shown in FIG. 1A . Several general challenges exist when attempting to maximize resources in a grid. First, there are typically multiple layers of grid and cluster schedulers. A grid 100 generally comprises a group of clusters or a group of networked computers. The definition of a grid is very flexible and may mean a number of different configurations of computers. The introduction here is meant to be general given the variety of configurations that are possible. A grid scheduler 102 communicates with a plurality of duster schedulers 104 A, 104 B and 104 C. Each of these cluster schedulers communicates with a respective resource manager 106 A, 106 B or 106 C. Each resource manager communicates with a respective series of compute resources shown as nodes 108 A, 108 B, 108 C in cluster 110 , nodes 108 D, 108 E, 108 F in cluster 112 and nodes 108 G, 108 H, 108 I in cluster 114 . Local schedulers (which may refer to either the cluster schedulers 104 or the resource managers 106 ) are doser to the specific resources 108 and may not allow grid schedulers 102 direct access to the resources. The grid level scheduler 102 typically does not own or control the actual resources. Therefore, jobs are submitted from the high level grid-scheduler 102 to a local set of resources with no more permissions that then user would have. This reduces efficiencies and can render the reservation process more difficult. The heterogeneous nature of the shared compute resources also causes a reduction in efficiency. Without dedicated access to a resource, the grid level scheduler 102 is challenged with the high degree of variance and unpredictability in the capacity of the resources available for use. Most resources are shared among users and projects and each project varies from the other. The performance goals for projects differ. Grid resources are used to improve performance of an application but the resource owners and users have different performance goals: from optimizing the performance for a single application to getting the best system throughput or minimizing response time. Local policies may also play a role in performance. Within a given cluster, there is only a concept of resource management in space. An administrator can partition a cluster and identify a set of resources to be dedicated to a particular purpose and another set of resources can be dedicated to another purpose. In this regard, the resources are reserved in advance to process the job. There is currently no ability to identify a set of resources over a time frame for a purpose. By being constrained in space, the nodes 108 A, 108 B, 108 C, if they need maintenance or for administrators to perform work or provisioning on the nodes, have to be taken out of the system, fragmented permanently or partitioned permanently for special purposes or policies. If the administrator wants to dedicate them to particular users, organizations or groups, the prior art method of resource management in space causes too much management overhead requiring a constant adjustment the configuration of the cluster environment and also losses in efficiency with the fragmentation associated with meeting particular policies. To manage the jobs submissions or requests for resources within a cluster, a cluster scheduler will employ reservations to insure that jobs will have the resources necessary for processing. FIG. 1B illustrates a cluster/node diagram for a cluster 124 with nodes 120 . Time is along the X axis. An access control list 114 (ACL) to the cluster is static, meaning that the ACL is based on the credentials of the person, group, account, class or quality of service making the request or job submission to the cluster. The ACL 114 determines what jobs get assigned to the cluster 110 via a reservation 112 shown as spanning into two nodes of the cluster. Either the job can be allocated to the cluster or it can't and the decision is determined based on who submits the job at submission time. The deficiency with this approach is that there are situations in which organizations would like to make resources available but only in such a way as to balance or meet certain performance goals. Particularly, groups may want to establish a constant expansion factor and make that available to all users or they may want to make a certain subset of users that are key people in an organization and want to give them special services but only when their response time drops below a certain threshold. Given the prior art model, companies are unable to have the flexibility over their cluster resources. To improve the management of compute resources, what is needed in the art is a method for a scheduler, such as a grid scheduler, a cluster scheduler or cluster workload management system to manage resources more efficiently. Furthermore, given the complexity of the cluster environment, what is needed is more power and flexibility in the reservations process.
<SOH> SUMMARY OF THE INVENTION <EOH>Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The features and advantages of the invention may be realized and obtained by means of the instruments and combinations particularly pointed out in the appended claims. These and other features of the present invention will become more fully apparent from the following description and appended claims, or may be learned by the practice of the invention as set forth herein. The invention relates to systems, methods and computer-readable media for dynamically modifying either compute resources or a reservation for compute resources within a compute environment such as a grid or a cluster. In one aspect of the invention, a method of dynamically modifying resources within a compute environment comprises receiving a request for resources in the compute environment, monitoring events after receiving the request for resources and based on the monitored events, dynamically modifying at least one of the request for resources and the compute environment. The invention enables an improved matching between a reservation and jobs submitted for processing in the compute environment. A benefit of the present invention is that the compute environment and the reservation or jobs submitted under the reservation will achieve a better fit. The closer the fit between jobs, reservations and the compute resources provides increased efficiency of the resources.
20050407
20091117
20070125
59439.0
G06F946
1
PATEL, HARESH N
SYSTEM AND METHOD FOR PROVIDING ADVANCED RESERVATIONS IN A COMPUTE ENVIRONMENT
UNDISCOUNTED
0
ACCEPTED
G06F
2,005
10,531,069
ACCEPTED
Controlled release preparation
A controlled release preparation wherein the release of active ingredient is controlled, which releases an active ingredient for an extended period of time by staying or slowly migrating in the gastrointestinal tract, is provided by means such as capsulating a tablet, granule or fine granule wherein the release of active ingredient is controlled and a gel-forming polymer. Said tablet, granule or fine granule has a release-controlled coating-layer formed on a core particle containing an active ingredient.
1. A capsule comprising a tablet, granule or fine granule wherein the release of active ingredient is controlled and a gel-forming polymer. 2. The capsule according to claim 1, wherein the release of active ingredient is controlled by a release-controlled coating-layer formed on a core particle containing an active ingredient. 3. The capsule according to claim 2, wherein the release-controlled coating-layer contains a pH-dependently soluble polymer. 4. The capsule according to claim 2, wherein the release-controlled coating-layer is a diffusion-controlled layer. 5. The capsule according to claim 1, wherein the release of active ingredient is controlled by dispersing an active ingredient into a release-controlled matrix composing tablet, granule or fine granule. 6. The capsule according to claim 2, wherein the tablet, granule or fine granule in which the release of active ingredient is controlled has a disintegrant layer containing disintegrant formed on the core particle containing an active ingredient and a release-controlled coating-layer formed on said disintegrant layer, and the release of active ingredient is initiated after a certain lag time. 7. The capsule according to claim 1, wherein the tablet, granule or fine granule in which the release of active ingredient is controlled is coated with a gel-forming polymer. 8. The capsule according to claim 7 which further contains a gel-forming polymer. 9. The capsule according to claim 1, which comprises two kinds of tablet, granule or fine granule having different release properties of active ingredient. 10. The capsule according to claim 9, which comprises a tablet, granule or fine granule having an enteric coat that releases an active ingredient at the pH of about 5.5 and a tablet, granule or fine granule having a release-controlled coating-layer that releases an active ingredient at the pH of about 6.0 or above. 11. The capsule according to claim 1, 7 or 8, wherein the gel-forming polymer is a polymer whose viscosity of 5% aqueous solution is about 3,000 mPa·s or more at 25° C. 12. The capsule according to claim 1, 7 or 8, wherein the gel-forming polymer is a polymer having molecular weight of 400,000 to 10,000,000. 13. The capsule according to any one of claims 2 to 4 or 6, wherein the release-controlled coating-layer is a layer containing one or more kinds of polymeric substances selected from the group consisting of hydroxypropylmethyl cellulose phthalate, cellulose acetate phthalate, carboxymethylethyl cellulose, methyl methacrylate-methacrylic acid copolymer, methacrylic acid-ethyl acrylate copolymer, ethyl acrylate-methyl methacrylate-trimethylammoniumethyl methacrylate chloride copolymer, methyl methacrylate-ethyl acrylate copolymer, methacrylic acid-methyl acrylate-methyl methacrylate copolymer, hydroxypropyl cellulose acetate succinate and polyvinyl acetate phthalate. 14. The capsule according to claim 13, wherein the release-controlled coating-layer is comprised of 2 or more kinds of layers. 15. The capsule according to claim 1, wherein the release-controlled granule or fine granule has a particle size of about 100-1,500 μm. 16. The capsule according to claim 1, wherein the active ingredient is a proton pump inhibitor (PPI). 17. The capsule according to claim 16, wherein the PPI is an imidazole compound represented by the formula (I′): wherein ring C′ is an optionally substituted benzene ring or an optionally substituted aromatic monocyclic heterocyclic ring, R0 is a hydrogen atom, an optionally substituted aralkyl group, acyl group or acyloxy group, R1, R2 and R3 are the same or different and are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted amino group, and Y represents a nitrogen atom or CH; or a salt thereof or an optically active isomer thereof. 18. The capsule according to claim 17, wherein the imidazole compound is lansoprazole. 19. The capsule according to claim 17, wherein PPI is an optically active R-isomer of lansoprazole. 20. The capsule according to any one of claim 1, 7 or 8, wherein the gel-forming polymer is one or more kinds of substances selected from the group consisting of polyethylene oxide (PEO, molecular weight: 400,000-10,000,000), hydroxypropylmethyl cellulose (HPMC), carboxymethyl cellulose (CMC-Na), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose and carboxyvinyl polymer. 21. The capsule according to any one of claim 1, 7 or 8, wherein the gel-forming polymer is polyethylene oxide (molecular weight: 400,000-10,000,000). 22. The capsule according to claim 1, wherein the gel-forming polymer is added as a powder, fine granule or granule. 23. The capsule according to claim 3, wherein the pH-dependently soluble polymer is methyl methacrylate-methacrylic acid copolymer. 24. A tablet, granule or fine granule wherein the release of active ingredient is controlled, said tablet, granule or fine granule comprising a core particle containing an imidazole compound represented by the formula (I′): wherein ring C′ is an optionally substituted benzene ring or an optionally substituted aromatic monocyclic heterocyclic ring, R0 is a hydrogen atom, an optionally substituted aralkyl group, acyl group or acyloxy group, R1, R2 and R3 are the same or different and are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted amino group, and Y represents a nitrogen atom or CH; or a salt thereof or an optically active isomer thereof as an active ingredient, and a pH-dependently soluble release-controlled coating-layer which comprises one kind of polymeric substance or a mixture of two or more kinds of polymeric substances having different release properties selected from the group consisting of hydroxypropylmethyl cellulose phthalate, cellulose acetate phthalate, carboxymethylethyl cellulose, methyl methacrylate-methacrylic acid copolymer, methacrylic acid-ethyl acrylate copolymer, methacrylic acid-methyl acrylate-methyl methacrylate copolymer, hydroxypropyl cellulose acetate succinate, polyvinyl acetate phthalate and shellac, and said polymeric substance is soluble in the pH range of 6.0 to 7.5. 25. The tablet, granule or fine granule according to claim 24, wherein the pH-dependently soluble release-controlled coating-layer is formed on an intermediate layer which is formed on a core particle. 26. The capsule comprising the tablet, granule or fine granule according to claim 24. 27. The capsule comprising the tablet, granule or fine granule according to claim 24 and an enteric-coated tablet, granule or fine granule containing a compound represented by the formula (I′). 28. The tablet, granule or fine granule according to claim 24, wherein the active ingredient is lansoprazole. 29. The tablet, granule or fine granule according to claim 24, wherein the active ingredient is an optically active R-isomer of lansoprazole. 30. The tablet, granule or fine granule according to claim 24, wherein the active ingredient is an optically active S-isomer of lansoprazole. 31. The tablet, granule or fine granule according to claim 24, wherein the active ingredient is a derivative of lansoprazole. 32. The tablet, granule or fine granule according to claim 24, wherein the active ingredient is a derivative of optically active R-isomer of lansoprazole. 33. The tablet, granule or fine granule according to claim 24, 25 or 28 to 32, comprising having an enteric coat on the core particle containing an active ingredient, a disintegrant layer containing disintegrant on said enteric coat and a release-controlled coating-layer on said disintegrant layer. 34. The tablet, granule or fine granule according to any one of claim 24, 25, or 28 to 32, which is coated with a gel-forming polymer. 35. An extended release capsule comprising the tablet, granule or fine granule according to any one of claim 28 to 32 and a gel-forming polymer. 36. A tablet, granule or fine granule according to claim 24 wherein the release of active ingredient is controlled by two or more kinds of release-controlled coating-layers, and the outermost release-controlled coating-layer is soluble at higher pH than the inner release-controlled coating-layer. 37. The tablet, granule or fine granule according to claim 36, wherein the inner release-controlled coating-layer is soluble in the pH range of 6.0-7.0 and the outermost release-controlled coating-layer is soluble at the pH of 7.0 or above. 38. The tablet, granule or fine granule according to claim 36, wherein the inner release-controlled coating-layer is soluble in the pH range of 6.5-7.0 and the outermost release-controlled coating-layer is soluble at the pH of 7.0 or above. 39. The tablet, granule or fine granule according to claim 36, wherein the thickness of the outermost release-controlled coating-layer is 100 μm or less. 40. The granule or fine granule according to claim 36, wherein the release-controlled granule or fine granule has a particle size of about 100-1,500 μm. 41. A capsule comprising (i) a tablet, granule or fine granule in which the release of active ingredient is controlled; said tablet, granule or fine granule comprises a core particle containing an imidazole compound represented by the formula (I′): wherein ring C′ is an optionally substituted benzene ring or an optionally substituted aromatic monocyclic heterocyclic ring, R0 is a hydrogen atom, an optionally substituted aralkyl group, acyl group or acyloxy group, R1, R2 and R3 are the same or different and are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted amino group, and Y represents a nitrogen atom or CH; or a salt thereof or an optically active isomer thereof as an active ingredient, and a pH-dependently soluble release-controlled coating-layer which comprises one kind of polymeric substance or a mixture of two or more kinds of polymeric substances having different release properties selected from the group consisting of hydroxypropylmethyl cellulose phthalate, cellulose acetate phthalate, carboxymethylethyl cellulose, methyl methacrylate-methacrylic acid copolymer, methacrylic acid-ethyl acrylate copolymer, methacrylic acid-methyl acrylate-methyl methacrylate copolymer, hydroxypropyl cellulose acetate succinate, polyvinyl acetate phthalate and shellac; said polymeric substance is soluble in the pH range of 6.0 to 7.5, and (ii) a tablet, granule or fine granule comprising a core particle containing an active ingredient and enteric coat which is dissolved, thereby an active ingredient being released in the pH range of no less than 5.0, nor more than 6.0. 42. The capsule according to claim 41, wherein the pH-dependently soluble release-controlled coating-layer is formed on an intermediate layer which is formed on the core particle containing an active ingredient. 43. The capsule according to claim 41, wherein the active ingredient is lansoprazole. 44. The capsule according to claim 41, wherein the active ingredient is an optically active R-isomer of lansoprazole. 45. The capsule according to claim 41, wherein the active ingredient is an optically active S-isomer of lansoprazole. 46. The capsule according to claim 41, wherein the core particle containing an active ingredient contains a stabilizer of basic inorganic salt. 47. The capsule according to claim 41, wherein the pH-dependently soluble release-controlled coating-layer of the tablet, granule or fine granule in which the release of an active ingredient is controlled is a layer soluble in the pH range of no less than 6.5, nor more than 7.0. 48. The capsule according to claim 47, wherein the pH-dependently soluble release-controlled coating-layer contains a mixture of two or more kinds of methyl methacrylate-methacrylic acid copolymers having different release properties. 49. The capsule according to claim 41, which further contains a gel-forming polymer.
TECHNICAL FIELD The present invention relates to a controlled release preparation, in particular a capsule comprising a tablet, granule or fine granule wherein the release of active ingredient is controlled and a gel-forming polymer which delays the migration speed in the gastrointestinal tract. BACKGROUND ART An oral formulation is a dosage form which is used most frequently among pharmaceutical agents. Lots of preparations for oral administration wherein the drug efficacy thereof is sustained with the administration of once or twice a day have been developed from the viewpoint of improving QOL in these years. The compound having a kinetics of sustained drug efficacy with the administration of once or twice a day is tried to synthesize in the synthetic stage of compound itself, while quite a lot of attempts to modify the kinetics are made with designing controlled release preparation by contriving formulation. As the dosage form of oral controlled release preparation, various release-controlled systems such as a release control by a release-controlled coating-layer or a diffusion control of compound by a matrix, a release control of compound by erosion of matrix (base material), a pH-dependent release control of compound and a time-dependent release control wherein the compound is released after a certain lag time, are developed and applied. It is considered that a further extension of sustainability becomes possible by combining the above-mentioned release-controlled system with a control of migration speed in the gastrointestinal tract. The preparation containing a medicament having an acid-labile property as an active ingredient such as a benzimidazole compound having a proton pump inhibitor (hereinafter sometimes referred to as PPI) action needs to be enteric-coated. That is, a composition containing a benzimidazole compound having a proton pump inhibitor action is needed to disintegrate rapidly in the small intestine, so the composition is preferred to formulate into a granule or fine granule which has a broader surface area than a tablet and is easy to disintegrate or dissolve rapidly. In the case of a tablet, it is desirable to reduce the size of tablet (for example, see JP-A 62-277322). After administered orally, the tablet, granule or fine granule migrates through gastrointestinal tract with releasing an active ingredient to stomach, duodenum, jejunum, ileum and colon sequentially. And in the meantime, the active ingredient is absorbed at the each absorption site. A controlled release preparation is designed to control the absorption by delaying the release of active ingredient in some way. It is considered that a further extension of sustainability becomes possible by combining a release-controlled system with a function to control the migration speed in gastrointestinal tract such as adherability, floatability etc. These prior arts are disclosed in WO 01/89483, JP-A 2001-526213, U.S. Pat. No. 6,274,173, U.S. Pat. No. 6,093,734, U.S. Pat. No. 4,045,563, U.S. Pat. No. 4,686,230, U.S. Pat. No. 4,873,337, U.S. Pat. No. 4,965,269, U.S. Pat. No. 5,021,433 and the like. DISCLOSURE OF INVENTION OBJECT OF THE INVENTION An object of the present invention is to provide a controlled release preparation wherein the release of active ingredient of drug is controlled, which releases an active ingredient for an extended period of time with staying or slowly migrating in the gastrointestinal tract. SUMMARY OF THE INVENTION That is, the present invention provides: (1) A capsule comprising a tablet, granule or fine granule wherein the release of active ingredient is controlled and a gel-forming polymer; (2) The capsule according to the above-mentioned (1), wherein the release of active ingredient is controlled by a release-controlled coating-layer formed on a core particle containing an active ingredient; (3) The capsule according to the above-mentioned (2), wherein the release-controlled coating-layer contains a pH-dependently soluble polymer; (4) The capsule according to the above-mentioned (2), wherein the release-controlled coating-layer is a diffusion-controlled layer; (5) The capsule according to the above-mentioned (1), wherein the release of active ingredient is controlled by dispersing an active ingredient into a release-controlled matrix composing tablet, granule or fine granule; (6) The capsule according to the above-mentioned (3) or (4), wherein the tablet, granule or fine granule in which the release of active ingredient is controlled has a disintegrant layer containing disintegrant formed on the core particle containing an active ingredient and a release-controlled coating-layer formed on said disintegrant layer, and the release of active ingredient is initiated after a certain lag time; (7) The capsule according to any one of the above-mentioned (3) to (6), wherein the tablet, granule or fine granule in which the release of active ingredient is controlled is coated with a gel-forming polymer; (8) The capsule according to the above-mentioned (7) which further contains a gel-forming polymer; (9) The capsule according to any one of the above-mentioned (1) to (7), which comprises two kinds of tablet, granule or fine granule having different release properties of active ingredient; (10) The capsule according to the above-mentioned (9), which comprises a tablet, granule or fine granule having an enteric coat that releases an active ingredient at the pH of about 5.5 and a tablet, granule or fine granule having a release-controlled coating-layer that releases an active ingredient at the pH of about 6.0 or above; (11) The capsule according to the above-mentioned (1), (7) or (8), wherein the gel-forming polymer is a polymer whose viscosity of 5% aqueous solution is about 3,000 mPa·s or more at 25° C.; (12) The capsule according to the above-mentioned (1), (7) or (8), wherein the gel-forming polymer is a polymer having molecular weight of 400,000 to 10,000,000; (13) The capsule according to any one of the above-mentioned (2) to (4) or (6), wherein the release-controlled coating-layer is a layer containing one or more kinds of polymeric substances selected from the group consisting of hydroxypropylmethyl cellulose phthalate, cellulose acetate phthalate, carboxymethylethyl cellulose, methyl methacrylate-methacrylic acid copolymer, methacrylic acid-ethyl acrylate copolymer, ethyl acrylate-methyl methacrylate-trimethylammoniumethyl methacrylate chloride copolymer, methyl methacrylate-ethyl acrylate copolymer, methacrylic acid-methyl acrylate-methyl methacrylate copolymer, hydroxypropyl cellulose acetate succinate and polyvinyl acetate phthalate; (14) The capsule according to the above-mentioned (13), wherein the release-controlled coating-layer is comprised of 2 or more kinds of layers; (15) The capsule according to the above-mentioned (1), wherein the release-controlled granule or fine granule has a particle size of about 100-1,500 μm; (16) The capsule according to the above-mentioned (1), wherein the active ingredient is a proton pump inhibitor (PPI); (17) The capsule according to (16), wherein the PPI is an imidazole compound represented by the formula (I′): wherein ring C′ is an optionally substituted benzene ring or an optionally substituted aromatic monocyclic heterocyclic ring, R0 is a hydrogen atom, an optionally substituted aralkyl group, acyl group or acyloxy group, R1, R2 and R3 are the same or different and are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted amino group, and Y represents a nitrogen atom or CH; or a salt thereof or an optically active isomer thereof; (18) The capsule according to the above-mentioned (17), wherein the imidazole compound is lansoprazole; (19) The capsule according to the above-mentioned (17), wherein PPI is an optically active R-isomer of lansoprazole; (20) The capsule according to any one of the above-mentioned (1), (7) or (8), wherein the gel-forming polymer is one or more kinds of substances selected from the group consisting of polyethylene oxide (PEO, molecular weight: 400,000-10,000,000), hydroxypropylmethyl cellulose (HPMC), carboxymethyl cellulose (CMC-Na), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose and carboxyvinyl polymer; (21) The capsule according to any one of the above-mentioned (1), (7) or (8), wherein the gel-forming polymer is polyethylene oxide (molecular weight: 400,000-10,000,000); (22) The capsule according to the above-mentioned (1) or (8), wherein the gel-forming polymer is added as a powder, fine granule or granule; (23) The capsule according to the above-mentioned (3), wherein the pH-dependently soluble polymer is methyl methacrylate-methacrylic acid copolymer; (24) A tablet, granule or fine granule wherein the release of active ingredient is controlled, said tablet, granule or fine granule comprising a core particle containing an imidazole compound represented by the formula (I′): wherein ring C′ is an optionally substituted benzene ring or an optionally substituted aromatic monocyclic heterocyclic ring, R0 is a hydrogen atom, an optionally substituted aralkyl group, acyl group or acyloxy group, R1, R2 and R3 are the same or different and are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted amino group, and Y represents a nitrogen atom or CH; or a salt thereof or an optically active isomer thereof as an active ingredient, and a pH-dependently soluble release-controlled coating-layer which comprises one kind of polymeric substance or a mixture of two or more kinds of polymeric substances having different release properties selected from the group consisting of hydroxypropylmethyl cellulose phthalate, cellulose acetate phthalate, carboxymethylethyl cellulose, methyl methacrylate-methacrylic acid copolymer, methacrylic acid-ethyl acrylate copolymer, methacrylic acid-methyl acrylate-methyl methacrylate copolymer, hydroxypropyl cellulose acetate succinate, polyvinyl acetate phthalate and shellac, and said polymeric substance is soluble in the pH range of 6.0 to 7.5; (25) The tablet, granule or fine granule according to the above-mentioned (24), wherein the pH-dependently soluble release-controlled coating-layer is formed on an intermediate layer which is formed on a core particle; (26) The capsule comprising the tablet, granule or fine granule according to the above-mentioned (24); (27) The capsule comprising the tablet, granule or fine granule according to the above-mentioned (24) and an enteric-coated tablet, granule or fine granule containing a compound represented by the formula (II); (28) The tablet, granule or fine granule according to the above-mentioned (24), wherein the active ingredient is lansoprazole; (29) The tablet, granule or fine granule according to the above-mentioned (24), wherein the active ingredient is an optically active R-isomer of lansoprazole; (30) The tablet, granule or fine granule according to the above-mentioned (24), wherein the active ingredient is an optically active S-isomer of lansoprazole; (31) The tablet, granule or fine granule according to the above-mentioned (24), wherein the active ingredient is a derivative of lansoprazole; (32) The tablet, granule or fine granule according to the above-mentioned (24), wherein the active ingredient is a derivative of optically active R-isomer of lansoprazole; (33) The tablet, granule or fine granule according to any one of the above-mentioned (24), (25) or (28) to (32), comprising having an enteric coat on the core particle containing an active ingredient, a disintegrant layer containing disintegrant on said enteric coat and a release-controlled coating-layer on said disintegrant layer; (34) The tablet, granule or fine granule according to any one of the above-mentioned (28) to (33), which is coated with a gel-forming polymer; (35) An extended release capsule comprising the tablet, granule or fine granule according to any one of the above-mentioned (28) to (32) and a gel-forming polymer; (36) A tablet, granule or fine granule according to the above-mentioned (24) wherein the release of active ingredient is controlled by two or more kinds of release-controlled coating-layers, and the outermost release-controlled coating-layer is soluble at higher pH than the inner release-controlled coating-layer; (37) The tablet, granule or fine granule according to the above-mentioned (36), wherein the inner release-controlled coating-layer is soluble in the pH range of 6.0-7.0 and the outermost release-controlled coating-layer is soluble at the pH of 7.0 or above; (38) The tablet, granule or fine granule according to the above-mentioned (36), wherein the inner release-controlled coating-layer is soluble in the pH range of 6.5-7.0 and the outermost release-controlled coating-layer is soluble at the pH of 7.0 or above; (39) The tablet, granule or fine granule according to the above-mentioned (36), wherein the thickness of the outermost release-controlled coating-layer is 100 μm or less; (40) The granule or fine granule according to the above-mentioned (36), wherein the release-controlled granule or fine granule has a particle size of about 100-1,500 μm; (41) A capsule comprising (i) a tablet, granule or fine granule in which the release of active ingredient is controlled; said tablet, granule or fine granule comprises a core particle containing an imidazole compound represented by the formula (I′): wherein ring C′ is an optionally substituted benzene ring or an optionally substituted aromatic monocyclic heterocyclic ring, R0 is a hydrogen atom, an optionally substituted aralkyl group, acyl group or acyloxy group, R1, R2 and R3 are the same or different and are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted amino group, and Y represents a nitrogen atom or CH; or a salt thereof or an optically active isomer thereof as an active ingredient, and a pH-dependently soluble release-controlled coating-layer which comprises one kind of polymeric substance or a mixture of two or more kinds of polymeric substances having different release properties selected from the group consisting of hydroxypropylmethyl cellulose phthalate, cellulose acetate phthalate, carboxymethylethyl cellulose, methyl methacrylate-methacrylic acid copolymer, methacrylic acid-ethyl acrylate copolymer, methacrylic acid-methyl acrylate-methyl methacrylate copolymer, hydroxypropyl cellulose acetate succinate, polyvinyl acetate phthalate and shellac; said polymeric substance is soluble in the pH range of 6.0 to 7.5, and (ii) a tablet, granule or fine granule comprising a core particle containing an active ingredient and enteric coat which is dissolved, thereby an active ingredient being released in the pH range of no less than 5.0, nor more than 6.0; (42) The capsule according to the above-mentioned (41), wherein the pH-dependently soluble release-controlled coating-layer is formed on an intermediate layer which is formed on the core particle containing an active ingredient; (43) The capsule according to the above-mentioned (41), wherein the active ingredient is lansoprazole; (44) The capsule according to the above-mentioned (41), wherein the active ingredient is an optically active R-isomer of lansoprazole; (45) The capsule according to the above-mentioned (41), wherein the active ingredient is an optically active S-isomer of lansoprazole; (46) The capsule according to the above-mentioned (41), wherein the core particle containing an active ingredient contains a stabilizer of basic inorganic salt; (47) The capsule according to the above-mentioned (41), wherein the pH-dependently soluble release-controlled coating-layer of the tablet, granule or fine granule in which the release of an active ingredient is controlled is a layer soluble in the pH range of no less than 6.5, nor more than 7.0; (48) The capsule according to the above-mentioned (47), wherein the pH-dependently soluble release-controlled coating-layer contains a mixture of two or more kinds of methyl methacrylate-methacrylic acid copolymers having different release properties; and (49) The capsule according to the above-mentioned (41), which further contains a gel-forming polymer. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a pharmaceutical composition containing a tablet, granule or fine granule wherein the release of active ingredients is controlled, or a pharmaceutical composition containing these tablet, granule or fine granule and a gel-forming polymer which delays digestive tract migration speed. The pharmaceutical composition of the present invention may be these tablet, granule or fine granule itself, or a form of a mixture of a tablet, granule or fine granule and a gel-forming polymer, or a capsule filled in capsule, but a capsule is preferred in particular. It has been cleared that the persistence of blood levels after oral administration is remarkably prolonged by these combinations. The release control of active ingredient in “a tablet, granule or fine granule wherein the release of active ingredient is controlled” of the present invention is performed by coating the active ingredient in a tablet, granule or fine granule with a layer controlling the release of active ingredient, or by dispersing the active ingredient in release-controlled matrices. Further, the “tablet, granule or fine granule wherein the release of active ingredient is controlled” of the present invention include also a tablet, granule or fine granule which is coated with a usual enteric coat which is dissolved at a pH of about 5.5, and tablets containing these granules or fine granules. On the other hand, when the “release-controlled coating-layer” is mentioned in the present specification, it indicates a coating-layer having a function of further delaying or extending the release of active ingredient, such as a pH-dependently soluble layer which is dissolved at a higher pH region than a usual enteric coating which is dissolved at a pH of about 5.5, and a diffusion-controlled layer whose layer itself is not dissolved and which releases an active ingredient through pores which are formed in the layer. It does not include a usual enteric coat and layer which is dissolved at a pH of about 5.5, rapidly dissolved in the intestinal juice and release an active ingredient. Further, the pH mentioned here means a pH of the Mcilvaine solution or Clark-Lubs solution. Hereinafter, the pH of a pH-dependently soluble layer means the pH of these solutions. The coating-layer of the “release-controlled coating-layer” inlcudes coating layers in a film form and those having larger thickness. Also, the coating-layer includes not only a coating-layer which entirely coats the inner core or layer but also the coating layers in which a part of the inner core or layer is not covered but most of the inner core or layer is coated (coating-layer which covers at least about 80% or more of the surface of the inner core or layer, and preferably covers the surface entirely). The absorption from the digestive tract of the active ingredient from the pharmaceutical composition of the present invention is controlled by two kind of systems utilizing (1) a release control of active ingredient by a controlled release tablet, granule or fine granule and (2) retentive prolongation in the digestive tract of a tablet, granule or fine granule by a gel-forming polymer, or their combinations. Among the pharmaceutical composition of the present invention, the composition containing a gel-forming polymer forms adhesive gels by rapidly absorbing water by the gel-forming polymer in the digestive tract when orally administrated, and the tablet, granule or fine granule is retained on the surface of gels or in the gels to be gradually migrated through the digestive tract. The release of active ingredient is controlled in the meanwhile, the active ingredient is released continuously or in a pulsatile manner from the tablet, granule or fine granule by a controlled system, and as a result, the incidences of prolonged absorption and drug efficacy are attained. The above-mentioned system enabling the persistence of therapeutic effective levels by controlling the release over a long time has advantages of therapeutic effectiveness at a low dose and reduction of side effects caused by initial rise of blood level and the like, as well as the reduction of administration times. The gel-forming polymer may be a polymer which rapidly forms highly viscous gels by contacting with water and prolongs the retention time in the digestive tract. Such gel-forming polymer is preferably a polymer having a viscosity of about 3000 mPa·s or more for 5% aqueous solution at 25° C. Further, the gel-forming polymer is preferably a polymer usually having a molecular weight of about 400000 to 10000000 in general. As the gel-forming polymer, powder, granular or fine granular polymer is preferable for producing formulations. The gel-forming polymer includes a polyethylene oxide (PEO, for example, Polyox WSR 303 (molecular weight: 7000000), Polyox WSR Coagulant (molecular weight: 5000000), Polyox WSR 301 (molecular weight: 4000000), Polyox WSR N-60K (molecular weight: 2000000), and Polyox WSR 205 (molecular weight: 600000); manufactured by Dow Chemical Co., Ltd.), hydroxypropyl methylcellulose (HPMC, Metlose 90SH10000, Metlose 90SH50000, and Metlose 90SH30000; manufactured by Shin-Etsu Chemical Co., Ltd.), carboxymethylcellulose (CMC-Na, Sanlose F-1000MC), hydroxypropyl cellulose (HPC, for example, HPC-H, manufactured by Nippon Soda Co., Ltd.), hydroxyethyl cellulose (HEC), carboxyvinyl polymer (HIVISWAKO (R) 103, 104 and 105 manufactured by Wako Pure Chemical Industries Ltd.; CARBOPOL 943 manufactured by Goodrich Co., Ltd.), chitosan, sodium alginate, pectin and the like. These may be used alone or as a mixture of at least 2 or more of powders by mixing at an appropriate proportion. In particular, PEO, HPMC, HPC, CMC-Na, carboxyvinyl polymer and the like are preferably used as a gel-forming polymer. One preferable form of a tablet, granule or fine granule wherein the release of active ingredient is controlled includes a tablet, granule or fine granule wherein a core particle containing at least one active ingredient is coated with a release-controlled coating-layer and a tablet containing these granules or fine granules. In order to prepare such core-possessing tablet, granule or fine granule, as a core particle can be used the tablet, granule or fine granule wherein an active ingredient is coated on a core which is an inactive carrier such as NONPAREIL (NONPAREIL-101 (particle diameter: 850-710, 710-500, and 500-355), NONPAREIL-103 (particle diameter: 850-710, 710-500, and 500-355), NONPAREIL-105 (particle diameter: 710-500, 500-355 and 300-180); manufactured by Freund Industrial Co., Ltd.) and Celphere (CP-507 (particle diameter: 500-710), and CP-305 (particle diameter: 300-500); manufactured by Asahi Kasei Corporation); or the tablet prepared by using these granules or fine granules; or the particle obtained by granulation using an active ingredient and an excipient usually used for formulation. For example, they can be produced by the method disclosed in JP-A 63-301816. For example, when a core particle is prepared by coating an active ingredient on a core of an inactive carrier, core particles containing an active ingredient can be produced by wet granulation, using, for example, a centrifugal fluid-bed granulator (CF-mini, CF-360, manufactured by Freund Industrial Co., Ltd.) or a centrifugal fluidized coating granulator (POWREX MP-10), or the like. Further, coating may be carried out by dusting an active ingredient while adding a solution containing a binder and the like on the core of an inactive carrier with spray and the like. The production apparatuses are not limited and for example, it is preferable in the latter coating to produce them using a centrifugal fluid-bed granulator and the like. An active ingredient may be coated at two steps by carrying out the coating using the above-mentioned two apparatuses in combination. When an inactive carrier core is not used, a core particle can be produced by granulating excipient such as lactose, white sugar, mannitol, corn starch and crystalline cellulose and an active ingredient, using binders such as hydroxypropyl methylcellulose, hydroxypropyl cellulose, methyl cellulose, a polyvinyl alcohol, Macrogol, Pullronic F68, gum arabic, gelatin and starch, if necessary, adding disintegrants such as sodium carboxymethyl cellulose, calcium carboxymethyl cellulose, sodium cross carboxymethyl cellulose (Ac-Di-Sol, manufactured by FMC International Co., Ltd.), polyvinyl pyrrolidone and low substituted hydroxypropyl cellulose, with a stirring granulator, a wet extruding granulator, a fluidized bed granulator and the like. Particles having desired sizes can be obtained by sieving the granules or fine granules obtained. The core particle may be prepared by dry granulation with a roller compactor and the like. Particles having a particle size of 50 μm to 5 mm, preferably 100 μm to 3 mm and more preferably 100 μm to 2 mm are used. The active ingredient-containing core particle thus obtained may be further coated to provide an intermediate coating layer, and the particle may be used as a core particle. It is preferable from the viewpoint of improving the stability of drugs that the intermediate coating layer is provided to intercept the direct contact of active ingredient-containing core particle with the release-controlled coating-layer when the active ingredient is an unstable drug against an acid, such as PPI and the like, etc. The intermediate coating layer may be formed by a plural number of layers. The coating materials for the intermediate coating layer include those obtained by appropriately compounding polymeric materials such as low substituted hydroxypropyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose (for example, TC-5 and the like), polyvinylpyrrolidone, polyvinyl alcohol, methylcellulose and hydroxyethyl methylcellulose with saccharides such as sucrose [purified sucrose (pulverized (powdered sugar), not pulverized) and the like], starch saccharide such as corn starch, lactose, sugar alcohol (D-mannitol, erythritol and the like). Excipients (for example, masking agents (titanium oxide and the like) and antistatic agents (titanium oxide, talc and the like) may be suitably added to the intermediate coating layer for the preparations mentioned below, if necessary. The coating amount of the intermediate coating layer is usually about 0.02 part by weight to about 1.5 parts by weight based on 1 part by weight of granules containing an active ingredient, and preferably about 0.05 part by weight to about 1 part by weight. The coating can be carried out by conventional methods. For example, preferably, the components of the intermediate coating layer are diluted with purified water and sprayed to coat in liquid form. Then, it is preferable to carry out the coating while spraying a binder such as hydroxypropyl cellulose. As the controlled release tablet, granule or fine granule contained in the pharmaceutical composition of the present invention, it is preferable to coat the above-mentioned core particle with a coating material which is pH-dependently dissolved/eluted to control the release, and to prepare the tablet, granule or fine granule having a release-controlled coating-layer, or the tablet containing these controlled release granules or fine granules. Herein, the “pH-dependently” means that the coating material is dissolved/eluted under the circumstances of more than a certain pH value to release an active ingredient. A usual enteric coat is eluted at a pH of about 5.5 to initiate the release of drug, while the coating material of the present invention is preferably a substance which is dissolved at a higher pH (preferably a pH of 6.0 or above and 7.5 or below, and more preferably a pH of 6.5 or above and below 7.2) and controls more favorably the release of drug in the stomach. As a coating material for controlling pH-dependently the release of medical active ingredient, polymers such as hydroxypropyl methylcellulose phthalate (HP-55, HP-50 manufactured by Shin-Etsu Chemical Co., Ltd.), cellulose acetate phthalate, carboxymethyl ethylcellulose (CMEC manufactured by Freund Industrial Co., Ltd.), methyl methacrylate-methacrylic acid copolymer (Eudragit L100 (methacrylic acid copolymer L) or Eudragit S100 (methacrylic acid copolymer S); manufactured by Rohm Co.), methacrylic acid-ethyl acrylate copolymer (Eudragit L100-55 (dried methacrylic acid copolymer LD) or Eudragit L30D-55 (methacrylic acid copolymer LD); manufactured by Rohm Co.), methacrylic acid-methyl acrylate-methyl methacrylate copolymer (Eudragit FS30D manufactured by Rohm Co.), hydroxypropyl cellulose acetate succinate (HPMCAS manufactured by Shin-Etsu Chemical Co., Ltd.), polyvinyl acetate phthalate and shellac are used. The tablet, granule or fine granule may be those having two or more kinds of release-controlled coating-layers which have different release properties of active ingredient. The polymer as the above-mentioned coating material may be used alone or at least 2 or more kinds of the polymers may be used to coat in combination, or at least 2 or more kinds of the polymers may be coated sequentially to prepare multi-layers. It is desirable that the coating material is used alone or, if necessary, in combination so that the polymer is dissolved preferably at a pH of 6.0 or above, more preferably at a pH of 6.5 or above, and further more preferably at a pH of 6.75 or above. Further, more desirably, a polymer soluble at a pH of 6.0 or above and a polymer soluble at a pH of 7.0 or above are used in combination, and furthermore desirably, a polymer soluble at a pH of 6.0 or above and a polymer soluble at a pH of 7.0 or above are used in combination at a ratio of 1:0.5 to 1:5. Further, plasticizers such as a polyethylene glycol, dibutyl sebacate, diethyl phthalate, triacetin and triethyl citrate, stabilizers and the like may be used for coating, if necessary. The amount of coating material is 5% to 200% based on the core particle, preferably 20% to 100% and more preferably 30% to 60%. The rate of elution of active ingredient from the active ingredient release-controlled tablet, granule or fine granule thus obtained is desirably 10% or less for 5 hours in a solution of pH 6.0, and 5% or less for one hour and 60% or more for 8 hours in a solution of pH 6.8. The controlled release tablet, granule or fine granule (hereinafter, sometimes referred to simply as a controlled release granule) may be a tablet, granule or fine granule wherein a material which becomes viscous by contact with water, such as polyethylene oxide (PEO, for example, Polyox WSR 303 (molecular weight: 7000000), Polyox WSR Coagulant (molecular weight: 5000000), Polyox WSR 301 (molecular weight: 4000000), Polyox WSR N-60K (molecular weight: 2000000), and Polyox WSR 205 (molecular weight: 600000); manufactured by Dow Chemical Co., Ltd.), hydroxypropyl methylcellulose (HPMC, Metlose 90SH10000, Metlose 90SH50000, Metlose 90SH30000; manufactured by Shin-Etsu Chemical Co., Ltd.), carboxymethyl cellulose (CMC-Na, Sanlose F-1000MC), hydroxypropyl cellulose (HPC, for example, HPC-H manufactured by Nippon Soda Co., Ltd.), hydroxyethyl cellulose (HEC), carboxyvinyl polymer (HIVISWAKO (R) 103, 104, 105: manufactured by Wako Pure Chemical Industries Ltd.; CARBOPOL 943 manufactured by Goodrich Co., Ltd.), chitosan, sodium alginate and pectin, is coated on the active ingredient release-controlled tablet, granule or fine granule thus obtained. The controlled release granule may be a form in which the core particle containing an active ingredient is coated with a diffusion-controlled layer having an action of controlling the release of active ingredient by diffusion. The materials for these diffusion-controlled layer include ethyl acrylate-methyl methacrylate-trimethylammoniumethyl methacrylate chloride copolymer (Eudragit RS (aminoalkyl methacrylate copolymer RS) or Eudragit RL (aminoalkyl methacrylate copolymer RL); manufactured by Rohm Co.), methyl methacrylate-ethyl acrylate copolymer (Eudragit NE30D manufactured by Rohm Co.), ethyl cellulose and the like. Further, these materials for layer may be mixed at an appropriate ratio, and can be used by mixing with hydrophilic pore forming substances such as HPMC, HPC, carboxyvinyl polymer, polyethylene glycol 6000, lactose, mannitol and organic acid at a fixed ratio. Further, in order to prepare the tablet, granule or fine granule wherein the release of active ingredient is controlled to initiate after a fixed lag time, a disintegrant layer is provided between the core particle containing an active ingredient and the release-controlled coating-layer by coating a swelling substance such as a disintegrant previously before coating the above-mentioned diffusion-controlled layer. For example, preferably, a swelling substance such as cross carmelose sodium (Ac-Di-Sol, manufactured by FMC International Co.), carmelose calcium (ECG 505, manufactured by Gotoku Chemicals Co.), CROSSPOVIDON (ISP Inc.) and low substituted hydroxypropyl cellulose (L-HPC manufactured by Shin-Etsu Chemical Co., Ltd.) is primarily coated on a core particle, and then the resulting coated particle is secondarily coated with a diffusion-controlled layer which is prepared by mixing at a fixed ratio one or more kinds of polymers selected from ethyl acrylate-methyl methacrylate-trimethylammoniumethyl methacrylate chloride copolymer (Eudragit RS or Eudragit RL; manufactured by Rohm Co.), methyl methacrylate-ethyl acrylate copolymer (Eudragit NE30D manufactured by Rohm Co.), ethyl cellulose and the like; with hydrophilic pore forming substances such as HPMC, HPC, carboxyvinyl polymer, polyethylene glycol 6000, lactose, mannitol and an organic acid. The secondary coating material may be enteric polymers which release pH-dependently an active ingredient, such as hydroxypropyl methylcellulose phthalate (HP-55, HP-50; manufactured by Shin-Etsu Chemical Co., Ltd.), cellulose acetate phthalate, carboxymethyl ethylcellulose (CMEC; manufactured by Freund Industrial Co., Ltd.), methyl methacrylate-methacrylic acid copolymer (Eudragit L100 (methacrylic acid copolymer L) or Eudragit S100 (methacrylic acid copolymer S); manufactured by Rohm Co.), methacrylic acid-ethyl acrylate copolymer (Eudragit L100-55 (dried methacrylic acid copolymer LD) or Eudragit L30D-55 (methacrylic acid copolymer LD); manufactured by Rohm Co.), methacrylic acid-methyl acrylate-methyl methacrylate copolymer (Eudragit FS30D; manufactured by Rohm Co.), hydroxypropyl cellulose acetate succinate (HPMCAS; manufactured by Shin-Etsu Chemical Co., Ltd.), polyvinyl acetate and shellac. The amount of coating material is 1% to 200% based on the core particle, preferably 20% to 100% and more preferably 30% to 60%. Plasticizers such as polyethylene glycol, dibutyl sebacate, diethyl phthalate, triacetin and triethyl citrate, stabilizers and the like may be used for coating, if necessary. The controlled release tablet, granule or fine granule may be a tablet, granule or fine granule wherein a material which becomes viscous by contact with water, such as polyethylene oxide (PEO, for example, Polyox WSR 303 (molecular weight: 7000000), Polyox WSR Coagulant (molecular weight: 5000000), Polyox WSR 301 (molecular weight: 4000000), Polyox WSR N-60K (molecular weight: 2000000), and Polyox WSR 205 (molecular weight: 600000); manufactured by Dow Chemical Co., Ltd.), hydroxypropyl methylcellulose (HPMC, Metlose 90SH10000, Metlose 90SH50000, Metlose 90SH30000; manufactured by Shin-Etsu Chemical Co., Ltd.), carboxymethyl cellulose (CMC-Na, Sanlose F-1000MC), hydroxypropyl cellulose (HPC, for example, HPC-H manufactured by Nippon Soda Co., Ltd.), hydroxyethyl cellulose (HEC), carboxyvinyl polymer (HIVISWAKO (R) 103, 104, 105: manufactured by Wako Pure Chemical Industries Ltd.; CARBOPOL 943 manufactured by Goodrich Co., Ltd.), chitosan, sodium alginate and pectin, is coated on the active ingredient release-controlled tablet, granule or fine granule thus obtained. In the tablet, granule or fine granule having 2 or more kinds of release-controlled coating-layers having different release properties of active ingredient, a layer containing an active ingredient may be set up between said release-controlled coating-layers. A form of these multi-layer structure containing an active ingredient between release-controlled coating-layers includes a tablet, granule or fine granule which is prepared by coating an active ingredient on the tablet, granule or fine granule wherein the release of active ingredient is controlled by the release-controlled coating-layer of the present invention, followed by further coating with the release-controlled coating-layer of the present invention. Another form of the tablet, granule or fine granule wherein the release of at least one of the active ingredients is controlled may be a tablet, granule or fine granule in which the active ingredients are dispersed in a release-controlled matrix. These controlled release tablet, granule or fine granule can be produced by homogeneously dispersing the active ingredients into hydrophobic carriers such as waxes such as hardened castor oil, hardened rape seed oil, stearic acid and stearyl alcohol, and polyglycerin fatty acid ester. The matrix is a composition in which the active ingredients are homogeneously dispersed in a carrier. If necessary, excipients such as lactose, mannitol, corn starch and crystalline cellulose which are usually used for preparation of a drug may be dispersed with the active ingredients. Further, powders of polyoxyethylene oxide, cross-linked acrylic acid polymer (HIVISWAKO (R) 103, 104 and 105, CARBOPOL), HPMC, HPC, chitosan and the like which form viscous gels by contact with water may be dispersed into the matrix together with the active ingredients and excipients. As the preparation method, they can be prepared by methods such as spray dry, spray chilling and melt granulation. The controlled release tablet, granule or fine granule may be a tablet, granule or fine granule wherein a material which becomes viscous by contact with water, such as polyethylene oxide (PEO, for example, Polyox WSR 303 (molecular weight: 7000000), Polyox WSR Coagulant (molecular weight: 5000000), Polyox WSR 301 (molecular weight: 4000000), Polyox WSR N-60K (molecular weight: 2000000), and Polyox WSR 205 (molecular weight: 600000); manufactured by Dow Chemical Co., Ltd.), hydroxypropyl methylcellulose (HPMC, Metlose 90SH10000, Metlose 90SH50000, Metlose 90SH30000; manufactured by Shin-Etsu Chemical Co., Ltd.), carboxymethyl cellulose (CMC-Na, Sanlose F-1000MC), hydroxypropyl cellulose (HPC, for example, HPC-H manufactured by Nippon Soda Co., Ltd.), hydroxyethyl cellulose (HEC), carboxyvinyl polymer (HIVISWAKO (R) 103, 104, 105: manufactured by Wako Pure Chemical Industries Ltd.; CARBOPOL 943 manufactured by Goodrich Co., Ltd.), chitosan, sodium alginate and pectin, is coated on the active ingredient release-controlled tablet, granule or fine granule thus obtained. These materials which become viscous by contact with water may be coexisted in one preparation such as a capsule and the like as well as using for coat. The tablet, granule or fine granule of the present invention wherein the release of active ingredient is controlled may be a form having the above-mentioned various kinds of release-controlled coating-layers, release-controlled matrixes and the like in combination. As the size of tablet, granule or fine granule wherein the release of active ingredient is controlled, particles having a particle size of 50 μm to 5 mm, preferably 100 μm to 3 mm and more preferably 100 μm to 2 mm are used. Granules or fine granules having a particle size of about 100 μm to 1500 μm are most preferred. Further, additives such as excipients for providing preparations (for example, glucose, fructose, lactose, sucrose, D-mannitol, erythritol, multitol, trehalose, sorbitol, corn starch, potato starch, wheat starch, rice starch, crystalline cellulose, silicic acid anhydride, calcium metaphosphorate, sedimented calcium carbonate, calcium silicate, and the like), binders (for example, hydroxypropyl cellulose, hydroxypropyl methylcellulose, polyvinyl pyrrolidone, methyl cellulose, polyvinyl alcohol, carboxymethyl cellulose sodium, partial α starch, α starch, sodium alginate, pullulan, gum arabic powder, gelatin and the like), disintegrants (for example, low substituted hydroxypropyl cellulose, carmelose, carmelose calcium, carboxymethylstarch sodium, cross carmelose sodium, crosspovidon, hydroxypropylstarch and the like), flavoring agents (for example, citric acid, ascorbic acid, tartaric acid, malic acid, aspartame, acesulfam potassium, thaumatin, saccharin sodium, glycylrrhizin dipotassium, sodium glutamate, sodium 5′-inosinate, sodium 5′-guanylate and the like), surfactants (for example, polysolvate (polysolvate 80 and the like), polyoxyethylene-polyoxypropylene copolymer, sodium laurylsulfate and the like), perfumes (for example, lemon oil, orange oil, menthol, peppermint oil and the like), lubricants (for example, magnesium stearate, sucrose fatty acid eater, sodium stearylfumarate, stearic acid, talc, polyethylene glycol and the like), colorants (for example, titanium oxide, edible Yellow No.5, edible Blue No.2, iron (III) oxide, yellow iron (III) oxide, and the like), antioxidants (for example, sodium ascorbate, L-cysteine, sodium bisulfate, and the like), masking agents (for example, titanium oxide and the like), and antistatic agents (for example, talc, titanium oxide and the like) can be used. The particle diameter of raw materials used here are not particularly limited, and particles having a diameter of about 500 μm or less are preferred from the viewpoint of productivity and dosing. The tablet, granule or fine granule thus obtained may be administrated as it is by mixing with a digestive tract retentive gel-forming polymer, or can be formulated as a capsule by filling in capsules. The amount of the gel-forming polymer being retentive in the digestive tract is 0.1% to 100% relative to the controlled release tablet, granule or fine granule, preferably 2% to 50%, more preferably 10% to 40%, and further more preferably 10% to 35%. The pharmaceutical composition of the present invention thus obtained is a composition having a extended activity of drug by a release-controlled system wherein therapeutic effect is revealed for at least 6 hours, preferably 8 hours, more preferably 12 hours and further preferably 16 hours. The active ingredients are not particularly limited, and can be applied irrespective of the region of drug efficacy. Exemplified are anti-inflammatory drugs such as indomethacin and acetaminophen, analgesics such as morphine, cardiovascular agonists such as diazepam and diltiazepam, antihistamines such as chlorophenylamine maleate, antitumors such as fluorouracil and aclarubicin, narcotics such as midazolam, anti-hemostasis agents such as ephedrine, diuretics such as hydrochlorothiazide and furosemide, bronchodilators such as theophyline, antitussives such as codeine, antiarrythmic agents such as quinidine and dizoxin, antidiabetics such as tolbutamide, pioglitazone and troglitazone, vitamins such as ascorbic acid, anticonvulsants such as phenitoin, local anesthetics such as lidocaine, adrenocortical hormones such as hydrocortisone, drugs effective for central nerve such as eisai, hypolipidemic drugs such as pravastatin, antibiotics such as amoxicillin and cephalexin, digestive tract exitomotory agents such as mosapride and cisapride, H2 blockers such as famotidine, ranitidine and cimetidine which are the remedies of gastritis, symptomatic gastroesophageal reflux disease, and gastric and duodenal ulcers, and benzimidazole proton pump inhibitors (PPI) represented by lansoprazole and optically active isomers thereof (R-isomer and S-isomer, preferably R-isomer (hereinafter, occasionally referred to as Compound A)), omeprazole and optically active isomers thereof (S-isomer: S omeprazole), rabeprazole and optically active isomers thereof, pantoprazole and optically active isomers thereof and the like, and imidazopyridine PPI represented by tenatoprazole and the like. According to the present invention, the preparations which contain, as an active ingredient, a PPI such as acid-labile imidazole compounds represented by the following general formula (I′) such as lansoprazole and optically active isomers thereof, in particular, acid-labile benzimidazole compounds represented by the following formula (I), and relatively acid-stable imidazole compound derivatives (prodrug type PPI) represented by the following general formula (II) or (III) or salts thereof or optically active isomers thereof have an excellent sustainability of drug efficacy. As a result, dosing compliance is also improved and therapeutic effect is increased. Wherein ring C′ indicates a benzene ring optionally having a substituent group or an aromatic monocyclic heterocyclic ring optionally having a substituent group; R0 indicates a hydrogen atom, an aralkyl group optionally having a substituent group, an acyl group or an acyloxy group; R1, R2 and R3 are the same or different and indicate a hydrogen atom, an alkyl group optionally having a substituent group, an alkoxy group optionally having a substituent group or an amino group optionally having a substituent group, respectively; and Y indicates a nitrogen atom or CH. Among the compounds represented by the above-mentioned formula (I′), the compound in which the ring C′ is a benzene ring optionally having a substituent group is particularly represented by the following formula (I). Namely, in the formula (I), ring A indicates a benzene ring optionally having a substituent group, and R0, R1, R2R3 and Y have the same meaning as in the above-mentioned formula (I′). In the above-mentioned formula (I), the preferable compound is a compound wherein ring A is a benzene ring which may have a substituent group selected from a halogen atom, an optionally halogenated C1-4 alkyl group, an optionally halogenated C1-4 alkoxy group and a 5- or 6-membered heterocyclic group; R0 is a hydrogen atom, an optionally substituted aralkyl group, an acyl group or an acyloxy group; R1 is a C1-6 alkyl group, a C1-6 alkoxy group, a C1-6 alkoxy-C1-6 alkoxy group or a di-C1-6 alkylamino group; R2 is a hydrogen atom, a C1-6 alkoxy-C1-6 alkoxy group, or an optionally halogenated C1-6 alkoxy group; R3 is a hydrogen atom or a C1-6 alkyl group, and Y is a nitrogen atom. In particular, the preferable compound is a compound represented by the formula (Ia); wherein R1 indicates a C1-3 alkyl group or a C1-3 alkoxy group; R2 indicates a C1-3 alkoxy group which may be halogenated or may be substituted with a C1-3 alkoxy group; R3 indicates a hydrogen atom or a C1-3 alkyl group, and R4 indicates a hydrogen atom, an optionally halogenated C1-3 alkoxy group or a pyrrolyl group (for example, 1-, 2- or 3-pyrrolyl group). In the formula (Ia), the compound wherein R1 is a C1-3 alkyl group; R2 is an optionally halogenated C1-3 alkoxy group; R3 is a hydrogen atom and R4 is a hydrogen atom or an optionally halogenated C1-3 alkoxy group is particularly preferred. In the compound represented by the above-mentioned formula (I) (hereinafter, referred to as Compound (I)), the “substituent group” of the “benzene ring optionally having a substituent group” represented by ring A includes, for example, a halogen atom, a nitro group, an alkyl group optionally having a substituent group, a hydroxy group, an alkoxy group optionally having a substituent group, an aryl group, an aryloxy group, a carboxy group, an acyl group, an acyloxy group, a 5- to 10-membered heterocyclic group and the like. The benzene ring may be substituted with about 1 to 3 of these substituent groups. When the number of substituents is 2 or more, each substituent groups may be the same or different. Among these substituent groups, a halogen atom, an alkyl group optionally having a substituent group, an alkoxy group optionally having a substituent group and the like are preferred. The halogen atom includes fluorine, chlorine, bromine atom and the like. Among these, fluorine is preferred. As the “alkyl group” of the “alkyl group optionally having a substituent group”, for example, a C1-7 alkyl group (for example, a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl group and the like) is exemplified. As the “substituent group” of the “alkyl group optionally having a substituent group”, for example, a halogen atom, a hydroxy group, a C1-6 alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy and the like), a C1-6 alkoxy-carbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and the like), a carbamoyl group and the like can be exemplified, and the number of these substituent groups may be about 1 to 3. When the number of substituent group is 2 or more, each substituent groups may be the same or different. The “alkoxy group” of the “alkoxy group optionally having a substituent group” includes, for example, a C1-6 alkoxy group (for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy and the like) and the like. The “substituent group” of the “alkoxy group optionally having a substituent group” are exemplified by those for the above-mentioned “substituent group” of the “alkyl group optionally having a substituent group”, and the number of the substituent group is the same. The “aryl group” include, for example, a C6-14 aryl group (for example, a phenyl, 1-naphthyl, 2-naphthyl, biphenyl, 2-anthryl group and the like) and the like. The “aryloxy group” includes, for example, a C6-14 aryloxy group (for example, a phenyloxy, 1-naphthyloxy, 2-naphthyloxy and the like) and the like. The “acyl group” includes, for example, a formyl, alkylcarbonyl, alkoxycarbonyl, carbamoyl, alkylcarbamoyl, alkylsulfinyl, alkylsulfonyl group and the like. The “alkylcarbonyl group” includes, a C1-6 alkyl-carbonyl group (for example, acetyl, propionyl group and the like) and the like. The “alkoxycarbonyl group” includes, for example, a C1-6 alkoxy-carbonyl group (for example, a methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl group and the like) and the like. The “alkylcarbamoyl group” include, a N—C1-6 alkyl-carbamoyl group (for example, methylcarbamoyl, ethylcarbamoyl group and the like), a N,N-diC1-6 alkyl-carbamoyl group (for example, N,N-dimethylcarbamoyl, N,N-diethylcarbamoyl group and the like), and the like. The “alkylsulfinyl group” includes, for example, a C1-7 alkylsulfinyl group (for example, a methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl group and the like) and the like. The “alkylsulfonyl group” includes, for example, a C1-7 alkylsulfonyl group (for example, a methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl group and the like) and the like. The “acyloxy group” includes, for example, an alkylcarbonyloxy group, an alkoxycarbonyloxy group, a carbamoyloxy group, an alkylcarbamoyloxy group, an alkylsulfinyloxy group, an alkylsulfonyloxy group and the like. The “alkylcarbonyloxy group” includes, a C1-6 alkyl-carbonyloxy group (for example, acetyloxy, propionyloxy group and the like) and the like. The “alkoxycarbonyloxy group” includes, for example, a C1-6 alkoxy-carbonyloxy group (for example, methoxycarbonyloxy, ethoxycarbonyloxy, propoxycarbonyloxy, butoxycarbonyloxy group and the like) and the like. The “alkylcarbamoyloxy group” includes, a C1-6 alkyl-carbamoyloxy group (for example, methylcarbamoyloxy, ethylcarbamoyloxy group and the like) and the like. The “alkylsulfinyloxy group” includes, for example, a C1-7 alkylsulfinyloxy group (for example, methylsulfinyloxy, ethylsulfinyloxy, propylsulfinyloxy, isopropylsulfinyloxy group and the like) and the like. The “alkylsulfonyloxy group” includes, for example, a C1-7 alkylsulfonyloxy group (for example, methylsulfonyloxy, ethylsulfonyloxy, propylsulfonyloxy, isopropylsulfonyloxy group and the like) and the like. The 5- to 10-membered heterocyclic group include, for example, a 5- to 10-membered (preferably 5- or 6-membered) heterocyclic group which contains one or more (for example, one to three) hetero atoms selected from a nitrogen atom, a sulfur atom and an oxygen atom in addition to a carbon atom. Specific example includes 2- or 3-thienyl group, 2-, 3- or 4-pyridyl group, 2- or 3-furyl group, 1-, 2- or 3-pyrrolyl group, 2-, 3-, 4-, 5- or 8-quinolyl group, 1-, 3-, 4- or 5-isoquinolyl group, 1-, 2- or 3-indolyl group; Among these, 5- or 6-membered heterocyclic groups such as 1-, 2- or 3-pyrrolyl groups are preferred. Ring A is preferably a benzene ring which may have 1 or 2 substituent groups selected from a halogen atom, an optionally halogenated C1-4 alkyl group, an optionally halogenated C1-4 alkoxy group and 5- or 6-membered heterocyclic group. In the above-mentioned formula (I′), the “aromatic monocyclic heterocyclic ring” of the “optionally substituted aromatic monocyclic heterocyclic ring” represented by ring C′ includes, for example, 5- to 6-membered aromatic monocyclic heterocyclic rings such as furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, furazane, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, pyridine, pyridazine, pyrimidine, pyrazine and triazine. As the “aromatic monocyclic heterocyclic ring” represented by ring C′, “a benzene ring which may have a substituent group” represented by the above-mentioned ring A and “a pyridine ring optionally having a substituent group” are particularly preferred. The “pyridine ring optionally having a substituent group” represented by ring C′ may have 1 to 4 of the same substituent groups as those exemplified with respect to the “benzene ring which may have a substituent group” represented by the above-mentioned ring A at substitutable positions. The position wherein “aromatic monocyclic heterocyclic ring” of the “aromatic monocyclic heterocyclic ring optionally having a substituent group” is condensed with an imidazole moiety is not specifically limited. In the above-mentioned formula (I′) or (I), the “aralkyl group” of the “aralkyl group optionally having a substituent group” represented by R0 includes, for example, a C7-16 aralkyl group (for example, C6-10 arylC1-6 alkyl group such as benzyl and phenethyl and the like) and the like. Examples of the “substituent group” of the “aralkyl group optionally having a substituent group” include the same groups as those exemplified with respect to the “substituent group” of the above-mentioned “alkyl group optionally having a substituent group”, and the number of the substituent groups is 1 to about 4. When the number of the substituent group is 2 or more, each substituent groups may be the same or different. The “acyl group” represented by R0 includes, for example, the “acyl group” described as the substituent group of the above-mentioned ring A. The “acyloxy group” represented by R0 includes, for example, the “acyloxy group” described as the substituent group of the above-mentioned ring A. The preferable R0 is a hydrogen atom. In the above-mentioned formula (I′) or (I), the “alkyl group optionally having a substituent group” represented by R1, R2 or R3 includes the “alkyl group optionally having a substituent group” described as the substituent group of the above-mentioned ring A. The “alkoxy group optionally having a substituent group” represented by R1, R2 or R3 includes the “alkoxy group optionally having a substituent group” described as the substituent group of the above-mentioned ring A. The “amino group optionally having a substituent group” represented by R1, R2 or R3 includes, for example, an amino group, a mono-C1-6 alkylamino group (for example, methylamino, ethylamino and the like), a mono-C6-14 arylamino group (for example, phenylamino, 1-naphthylamino, 2-naphthylamino and the like), a di-C1-6 alkylamino group (for example, dimethylamino, diethylamino and the like), a di-C6-14 arylamino group (for example, diphenylamino and the like) and the like. The preferable R1 is a C1-6 alkyl group, a C1-6 alkoxy group, a C1-6 alkoxy-C1-6 alkoxy group and a di-C1-6 alkylamino group. Further preferable R2 is a C1-3 alkyl group or a C1-3 alkoxy group. The preferable R2 is a hydrogen atom, a C1-6 alkoxy-C1-6 alkoxy group or an optionally halogenated C1-6 alkoxy group. Further preferable R3 is a C1-3 alkoxy group which may be optionally halogenated or may be optionally substituted with a C1-3 alkoxy group. The preferable R3 is a hydrogen atom or a C1-6 alkyl group. Further preferable R3 is a hydrogen atom or a C1-3 alkyl group (in particular, a hydrogen atom). The preferable Y is a nitrogen atom. As the specific example of the compound (I), the following compounds are exemplified. 2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridinyl]methyl]sulfinyl]-1H-benzimidazole (lansoprazole), 2-[[(3,5-dimethyl-4-methoxy-2-pyridinyl)methyl]sulfinyl]-5-methoxy-1H-benzimidazole, 2-[[[4-(3-methoxypropoxy)-3-methyl-2-pyridinyl]methyl]sulfinyl]-1H-benzimidazole sodium salt, 5-difluoromethoxy-2-[[(3,4-dimethoxy-2-pyridinyl)methyl]sulfinyl]-1H-benzimidazole and the like. Among these compounds, lansoprazole, namely 2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridinyl]methyl]sulfinyl]-1H-benzimidazole is preferable in particular. The present invention is preferably applied to the PPI of imidazopyridine compound in addition to the PPI of the above-mentioned benzimidazole compound. As the PPI of the imidazopyridine compound, for example, tenatoprazole is exemplified. Further, the above-mentioned compound (I) and compound (I′) including the imidazopyridine compound may be racemic, and optically active compounds such as R-isomer and S-isomer. For example, the optically active compounds such as optically active compound of lansoprazole, that is, (R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridinyl]methyl]sulfinyl]-1H-benzimidazole and (S)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridinyl]methyl]sulfinyl]-1H-benzimidazole are preferable for the present invention in particular. Further, for lansoprazole, lansoprazole R-isomer and lansoprazole S-isomer, crystals are usually preferred, but since they are stabilized by preparation itself as described later and stabilized by compounding a basic inorganic salt and further providing an intermediate layer, those being amorphous as well as crystalline can be also used. The salt of compound (I′) and compound (I) is preferably a pharmacologically acceptable salt, and for example, a salt with an inorganic base, a salt with an organic base, a salt with a basic amino acid and the like are mentioned. The preferable salt with an inorganic base includes, for example, alkali metal salts such as sodium salt and potassium salt; alkali earth metal salts such as calcium salt and magnesium salt; ammonium salt and the like. The preferable example of the salt with an organic base includes, for example, salts with an alkylamine (trimethylamine, triethylamine and the like), a heterocyclic amine (pyridine, picoline and the like), an alkanolamine (ethanolamine, diethanolamine, triethanolamine and the like), dicyclohexylamine, N,N′-dibenzylethylenediamine and the like. The preferable example of the salt with a basic amino acid includes, for example, salts with arginine, lysine, ornithine and the like. Among these salts, an alkali metal salt and an alkali earth metal salt are preferred. A sodium salt is preferred particularly. The compound (I′) or (I) can be produced by known methods, and are produced by methods disclosed in, for example, JP-A 61-50978, U.S. Pat. No. 4,628,098, JP-A 10-195068, WO 98/21201, JP-A 52-62275, JP-A 54-141783 and the like, or analogous methods thereto. Further, the optically active compound (I) can be obtained by optical resolution methods (a fractional recrystallization method, a chiral column method, a diastereomer method, a method using microorganism or enzyme, and the like) and an asymmetric oxidation method, etc. Further, lansoprazole R-isomer can be produced according to production methods described in, for example, WO 00-78745, WO 01/83473 and the like. The benzimidazole compound having antitumor activity used in the present invention is preferably lansoprazole, omeprazole, rabeprazole, pantoprazole, leminoprazole, tenatoprazole (TU-199) and the like, or optically active compounds thereof and pharmacologically acceptable salts thereof. Lansoprazole or an optically active compound thereof, in particular R-isomer is preferred. Lansoprazole or an optically active compound thereof, in particular R-isomer is preferably in a form of crystal, but may be an amorphous form. Further, they are also suitably applied to the prodrug of these PPIs. Examples of these preferable prodrugs include the compound represented by the following general formula (II) and (III) in addition to the prodrug which is included in compound (I) or (I′). In the compound represented by the above formula (II) (hereinafter, referred to as compound (II)), ring B designates a “pyridine ring optionally having substituents”. The pyridine ring of the “pyridine ring optionally having substituents” represented by ring B may have 1 to 4 substituents at substitutable positions thereof. As the substituent, for example, a halogen atom (e.g., fluorine, chlorine, bromine, iodine etc.), a hydrocarbon group optionally having substituents (e.g., alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, n-propyl group etc., and the like), an amino group optionally having substituents (e.g., amino; amino group mono- or di-substituted by alkyl group having 1 to 6 carbon atoms, such as methylamino, dimethylamino, ethylamino, diethylamino group etc., and the like), an amide group (e.g., C1-3 acylamino group such as formamide, acetamide etc., and the like), a lower alkoxy group optionally having substituents (e.g., alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy, 2,2,2-trifluoroethoxy, 3-methoxypropoxy group and the like), a lower alkylenedioxy group (e.g., C1-3 alkylenedioxy group such as methylenedioxy, ethylenedioxy etc., and the like) and the like can be mentioned. As the substituent, which is the substituent of the “pyridine ring optionally having substituents” represented by ring B can have, for example, a halogen atom (e.g., fluorine, chlorine, bromine, iodine etc.), a lower alkyl group (e.g., alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl group and the like), a lower alkenyl group (e.g., alkenyl group having 2 to 6 carbon atoms such as vinyl, allyl group and the like), a lower alkynyl group (e.g., alkynyl group having 2 to 6 carbon atoms such as ethynyl, propargyl group and the like), a cycloalkyl group (e.g., cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl group and the like), a lower alkoxy group (e.g., alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy group and the like), a nitro group, a cyano group, a hydroxy group, a thiol group, a carboxyl group, a lower alkanoyl group (e.g., formyl; C1-C6 alkyl-carbonyl group, such as acetyl, propionyl, butyryl group and the like), a lower alkanoyloxy group (e.g., formyloxy; C1-C6 alkyl-carbonyloxy group, such as acetyloxy, propionyloxy group and the like), a lower alkoxycarbonyl group (e.g., C1-C6 alkoxy-carbonyl group, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl group and the like), an aralkyloxycarbonyl group (e.g., C7-C11 aralkyloxy-carbonyl group, such as benzyloxycarbonyl group and the like), an aryl group (e.g., aryl group having 6 to 14 carbon atoms such as phenyl, naphthyl group and the like), an aryloxy group (e.g., aryloxy group having 6 to 14 carbon atoms such as phenyloxy, naphthyloxy group and the like), an arylcarbonyl group (e.g., C6-C14 aryl-carbonyl group, such as benzoyl, naphthoyl group and the like), an arylcarbonyloxy group (e.g., C6-C14 aryl-carbonyloxy group, such as benzoyloxy, naphthoyloxy group and the like), a carbamoyl group optionally having substituents (e.g., carbamoyl; carbamoyl group mono- or di-substituted by alkyl group having 1 to 6 carbon atoms, such as methylcarbamoyl, dimethylcarbamoyl group etc., and the like), an amino group optionally having substituents (e.g., amino; amino group mono- or di-substituted by alkyl group having 1 to 6 carbon atoms, such as methylamino, dimethylamino, ethylamino, diethylamino group etc., and the like) and the like, can be mentioned, wherein the number of substituents and the position of the substitution are not particularly limited. While the number of substituents and the position of substitution of the “pyridine ring optionally having substituents” represented by ring B are not particularly limited, 1 to 3 substituents mentioned above preferably substitute any of the 3-, 4- and 5-positions of the pyridine ring. As the “pyridine ring optionally having substituents” represented by ring B, 3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl is preferable. In the present invention, ring C represents a “benzene ring optionally having substituents” or an “aromatic monocyclic heterocycle optionally having substituents”, which is condensed with an imidazole part. Of these, the former is preferable. The benzene ring of the “benzene ring optionally having substituents” represented by ring C may have 1 to 4 substituents at substitutable positions thereof. As the substituent, for example, a halogen atom (e.g., fluorine, chlorine, bromine, iodine etc.), a hydrocarbon group optionally having substituents (e.g., alkyl group having 1 to 6 carbon atoms selected from methyl group, ethyl group, n-propyl group etc., and the like), an amino group optionally having substituents (e.g., amino; amino group mono- or di-substituted by alkyl group having 1 to 6 carbon atoms, such as methylamino, dimethylamino, ethylamino, diethylamino group etc., and the like), an amide group (e.g., C1-3 acylamino group such as formamide, acetamide etc., and the like), a lower alkoxy group optionally having substituents (e.g., alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, difluoromethoxy group etc., and the like), a lower alkylenedioxy group (e.g., C1-3 alkylenedioxy group such as methylenedioxy, ethylenedioxy etc., and the like), and the like can be mentioned. As the substituent, which is the substituent of the “benzene ring optionally having substituents” represented by ring C can have, for example, a halogen atom (e.g., fluorine, chlorine, bromine, iodine etc.), a lower alkyl group (e.g., alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl group and the like), a lower alkenyl group (e.g., alkenyl group having 2 to 6 carbon atoms such as vinyl, allyl group and the like), a lower alkynyl group (e.g., alkynyl group having 2 to 6 carbon atoms such as ethynyl, propargyl group and the like), a cycloalkyl group (e.g., cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl group and the like), a lower alkoxy group (e.g., alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy group and the like), a nitro group, a cyano group, a hydroxy group, a thiol group, a carboxyl group, a lower alkanoyl group (e.g., formyl; C1-6 alkyl-carbonyl group, such as acetyl, propionyl, butyryl group and the like), a lower alkanoyloxy group (e.g., formyloxy; C1-6 alkyl-carbonyloxy group, such as acetyloxy, propionyloxy group and the like), a lower alkoxycarbonyl group (e.g., C1-6 alkoxy-carbonyl group, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl group and the like), an aralkyloxycarbonyl group (e.g., C7-17 aralkyloxy-carbonyl group, such as benzyloxycarbonyl group and the like), an aryl group (e.g., aryl group having 6 to 14 carbon atoms such as phenyl, naphthyl group and the like), an aryloxy group (e.g., aryloxy group having 6 to 14 carbon atoms such as phenyloxy, naphthyloxy group and the like), an arylcarbonyl group (e.g., C6-14 aryl-carbonyl group, such as benzoyl, naphthoyl group and the like), an arylcarbonyloxy group (e.g., C6-14 aryl-carbonyloxy group, such as benzoyloxy, naphthoyloxy group and the like), a carbamoyl group optionally having substituents (e.g., carbamoyl; carbamoyl group mono- or di-substituted by alkyl group having 1 to 6 carbon atoms such as methylcarbamoyl, dimethylcarbamoyl group etc., and the like), an amino group optionally having substituents (e.g., amino; amino group mono- or di-substituted by alkyl group having 1 to 6 carbon atoms such as methylamino, dimethylamino, ethylamino, diethylamino group etc., and the like) and the like can be mentioned, wherein the number of substituents and the position of the substitution are not particularly limited. As the “benzene ring optionally having substituents” represented by ring C, a benzene ring is preferable. As the “aromatic monocyclic heterocycle” of the “aromatic monocyclic heterocycle optionally having substituents” represented by ring C, for example, a 5- or 6-membered aromatic monocyclic heterocycle such as furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, furazan, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, 1,2,3-triazole, 1,2,4-triazole, tetraxole, pyridine, pyridazine, pyrimidine, pyrazine, triazine etc., and the like can be mentioned. As the “aromatic monocyclic heterocycle” represented by ring C, a pyridine ring is particularly preferable. It may have, at substitutable positions thereof, 1 to 4 substituents similar to those for the “benzene ring optionally having substituents” represented by ring C. The position where the “aromatic monocyclic heterocycle” of the “aromatic monocyclic heterocycle optionally having substituents” is condensed with the imidazole part is not particularly limited. In the present invention, X1, and X2 represent an oxygen atom and a sulfur atom, respectively. Both X1, and X2 preferably represent an oxygen atom. In the present invention, W represents a “divalent chain hydrocarbon group optionally having substituents”, or the formula: —W1-Z-W2— wherein W1 and W2 are each a “divalent chain hydrocarbon group” or a bond, and Z is a divalent group such as a “divalent hydrocarbon ring group optionally having substituents”, a “divalent heterocyclic group optionally having substituents”, an oxygen atom, SOn wherein n is 0, 1 or 2 or >N-E wherein E is a hydrogen atom, a hydrocarbon group optionally having substituents, a heterocyclic group optionally having substituents, a lower alkanoyl group, a lower alkoxycarbonyl group, an aralkyloxycarbonyl group, a thiocarbamoyl group, a lower alkylsulfinyl group, a lower alkylsulfonyl group, a sulfamoyl group, a mono-lower alkylsulfamoyl group, a di-lower alkylsulfamoyl group, an arylsulfamoyl group, an arylsulfinyl group, an arylsulfonyl group, an arylcarbonyl group, or a carbamoyl group optionally having substituents, when Z is an oxygen atom, SOn or >N-E, W1 and W2 are each a “divalent chain hydrocarbon group”. Particularly, W is preferably a “divalent chain hydrocarbon group optionally having substituents”. As the “divalent chain hydrocarbon group” of the “divalent chain hydrocarbon group optionally having substituents” represented by W and “divalent chain hydrocarbon group” represented by W1 and W2, for example, a C1-6 alkylene group (e.g., methylene, ethylene, trimethylene etc.), a C2-6 alkenylene group (e.g., ethenylene etc.), a C2-6 alkynylene group (e.g., ethynylene etc.) and the like can be mentioned. The divalent chain hydrocarbon group for W may have 1 to 6 substituents similar to those for the “benzene ring optionally having substituents” represented by ring C at substitutable positions thereof. As the “divalent chain hydrocarbon group” of the “divalent chain hydrocarbon group optionally having substituents” represented by W and “divalent chain hydrocarbon group” represented by W1 and W2, a methylene group and an ethylene group are preferable. As W, an ethylene group is particularly preferable. When Z is an oxygen atom, SOn or >N-E (n and E are as defined above), the “divalent chain hydrocarbon group” represented by W1 is preferably a hydrocarbon group having 2 or more carbon atoms. As the “hydrocarbon ring” of the “divalent hydrocarbon ring group optionally having substituents” represented by Z, for example, an alicyclic hydrocarbon ring, an aromatic hydrocarbon ring and the like can be mentioned, with preference given to one having 3 to 16 carbon atoms, which may have 1 to 4 substituents similar to those for the “benzene ring optionally having substituents” represented by ring C at substitutable positions thereof. As the hydrocarbon ring, for example, cycloalkane, cycloalkene, arene and the like are used. As a cycloalkane in the “divalent hydrocarbon ring group optionally having substituents” represented by Z, for example, a lower cycloalkane and the like are preferable, and, for example, C3-10 cycloalkane such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, bicyclo[2.2.1]heptane, adamantane etc., and the like are generally used. As a cycloalkene in the “divalent hydrocarbon ring group optionally having substituents” represented by Z, for example, a lower cycloalkene is preferable, and, for example, C4-9 cycloalkene such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene etc., and the like are generally used. As an arene in the “divalent hydrocarbon ring group optionally having substituents” represented by Z, for example, a C6-14 arene such as benzene, naphthalene, phenanthrene etc., and the like are preferable, and, for example, phenylene and the like are generally used. As a heterocycle in the “divalent heterocyclic group optionally having substituents” represented by Z, a 5- to 12-membered “aromatic heterocycle” or “saturated or unsaturated non-aromatic heterocycle” containing, as ring-constituting atom (ring atom), 1 to 3 (preferably 1 or 2) kinds of at least 1 (preferably 1 to 4, more preferably 1 or 2) hetero atoms selected from oxygen atom, sulfur atom and nitrogen atom etc., and the like can be mentioned, which may have 1 to 4 substituents similar to those for the “benzene ring optionally having substituents” represented by ring C at substitutable positions thereof. As an aromatic heterocycle in the “divalent heterocyclic group optionally having substituents” represented by Z, an aromatic monocyclic heterocycle, an aromatic fused heterocycle and the like can be mentioned. As the “aromatic monocyclic heterocycle”, for example, a 5- or 6-membered aromatic monocyclic heterocycle such as furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, furazan, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine etc., and the like can be mentioned. As the “aromatic fused heterocycle”, for example, a 8-to 12-membered aromatic fused heterocycle such as benzofuran, isobenzofuran, benzothiophene, isobenzothiophene, indole, isoindole, 1H-indazole, benzimidazole, benzoxazole, 1,2-benzisoxazole, benzothiazole, 1,2-benzisothiazole, 1H-benzotriazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, phthalazine, naphthyridine, purine, pteridine, carbazole, carboline, acridine, phenoxazine, phenothiazine, phenazine, phenoxathiin, thianthrene, phenanthridine, phenanthroline, indolizine, pyrrolo[1,2-b]pyridazine, pyrazolo[1,5-a]pyridine, imidazo[1,2-a]pyridine, imidazo[1,5-a]pyridine, imidazo[1,2-b]pyridazine, imidazo[1,2-a]pyrimidine, 1,2,4-triazolo[4,3-a]pyridine, 1,2,4-triazolo[4,3-b]pyridazine etc., and the like can be mentioned. As a saturated or unsaturated non-aromatic heterocycle in the “divalent heterocyclic group optionally having substituents” represented by Z, for example, a 3- to 8-membered (preferably 5- or 6-membered) saturated or unsaturated (preferably saturated) non-aromatic heterocycle (aliphatic heterocycle) such as oxylane, azetidine, oxetane, thietane, pyrrolidine, tetrahydrofuran, tetrahydrothiophene, piperidine, tetrahydropyran, tetrahydrothiopyran, morpholine, thiomorpholine, piperazine, azepane, oxepane, thiene, oxazepane, thiazepane, azocane, oxocane, thiocane, oxazocane, thiazocane etc., and the like can be mentioned. These may be oxo-substituted and may be, for example, 2-oxoazetidine, 2-oxopyrrolidine, 2-oxopiperidine, 2-oxazepane, 2-oxazocane, 2-oxotetrahydrofuran, 2-oxotetrahydropyran, 2-oxotetrahydrothiophene, 2-oxothiane, 2-oxopiperazine, 2-oxooxepane, 2-oxooxazepane, 2-oxothiepane, 2-oxothiazepane, 2-oxooxocane, 2-oxothiocane, 2-oxooxazocane, 2-oxothiazocane and the like. The two bonds from the “hydrocarbon ring group” of the “divalent hydrocarbon ring group optionally having substituents” or the “heterocyclic group” of the “divalent heterocyclic group optionally having substituents” represented by Z may be present at any possible position. The “hydrocarbon group optionally having substituents” and “heterocyclic group optionally having substituents” represented by E is as defined in the following. As the “lower alkanoyl group” represented by E, for example, formyl, a C1-6 alkyl-carbonyl group such as acetyl, propionyl, butyryl, isobutyryl etc., and the like can be used. As the “lower alkoxycarbonyl group” represented by E, for example, a C1-6 alkoxy-carbonyl group such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl etc., and the like are used. As the “aralkyloxycarbonyl” represented by E, for example, a C7-11 aralkyloxy-carbonyl group such as benzyloxycarbonyl etc., and the like are used. As the “lower alkylsulfinyl group” represented by E, for example, a C1-6 alkylsulfinyl group such as methylsulfinyl, ethylsulfinyl etc., and the like are used. As the “lower alkylsulfonyl group” represented by E, for example, a C1-6 alkylsulfonyl group such as methylsulfonyl, ethylsulfonyl etc., and the like are used. As the “mono-lower alkylsulfamoyl group” represented by E, for example, a mono-C1-6 alkylsulfamoyl group such as methylsulfamoyl, ethylsulfamoyl etc., and the like are used. As the “di-lower alkylsulfamoyl group” represented by E, for example, a di-C1-6 alkylsulfamoyl group such as dimethylsulfamoyl, diethylsulfamoyl etc., and the like are used. As the “arylsulfamoyl group” represented by E, for example, a C6-10 arylsulfamoyl group such as phenylsulfamoyl, naphthylsulfamoyl etc., and the like are used. As the “arylsulfinyl group” represented by E, for example, a C6-10 arylsulfinyl group such as phenylsulfinyl, naphthylsulfinyl etc., and the like are used. As the “arylsulfonyl group” represented by E, for example, a C6-10 arylsulfonyl group such as phenylsulfonyl, naphthylsulfonyl etc., and the like are used. As the “arylcarbonyl group” represented by E, for example, C6-10 aryl-carbonyl group such as benzoyl, naphthoyl etc., and the like are used. The “carbamoyl group optionally having substituents” represented by E is, for example, a group of the formula CONR2R3 wherein R2 and R3 are each a hydrogen atom, a hydrocarbon group optionally having substituents or a heterocyclic group optionally having substituents, and in the formula —CONR2R3, R2 and R3 may form a ring together with the adjacent nitrogen atom, and the like. In the present invention, R is a “hydrocarbon group optionally having substituents” or a “heterocyclic group optionally having substituents”, and R can be bonded to W. Of these, a C1-6 hydrocarbon group optionally having substituents is preferable and a lower (C1-6) alkyl group is particularly preferable. The “hydrocarbon group optionally having substituents” and “heterocyclic group optionally having substituents” represented by R are as defined in the following. A detailed explanation of the case where R is bonded to W is given in the following. In the present invention, D1 and D2 are each a bond, an oxygen atom, a sulfur atom or >NR1, and in the formula, R1 is a hydrogen atom or a hydrocarbon group optionally having substituents. However, the present invention excludes a case where D1 and D2 are both respectively a bond. Among others, each of D1 and D2 is preferably a bond or an oxygen atom, and particularly preferably, D1 is an oxygen atom and D2 is an oxygen atom or a bond. The “hydrocarbon group optionally having substituents” represented by R1 is as defined in the following. In the present invention, G is a “hydrocarbon group optionally having substituents” or a “heterocyclic group optionally having substituents”. Of these, a C1-6 hydrocarbon group optionally having substituents or a saturated heterocyclic group optionally having substituents, which contains, as ring-constituting atom, 1 to 4 hetero atoms selected from oxygen atom, sulfur atom and nitrogen atom is preferable. As G, among others, a C1-6 hydrocarbon group optionally having substituents or a saturated oxygen-containing heterocyclic group optionally having substituents, which further contains, as ring-constituting atom, 1 to 3 hetero atoms selected from oxygen atom, sulfur atom and nitrogen atom is preferable. The “hydrocarbon group optionally having substituents” and “heterocyclic group optionally having substituents” represented by G are as defined in the following. As the “hydrocarbon group” of the “hydrocarbon group optionally having substituents” represented by the above-mentioned E, R, R1 and G, for example, a saturated or unsaturated aliphatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a saturated or unsaturated alicyclic-aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aromatic-saturated or unsaturated alicyclic hydrocarbon group and the like can be mentioned, with preference given to those having 1 to 16, more preferably 1 to 6, carbon atoms. Specific examples thereof include alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, cycloalkylalkyl group, cycloalkenylalkyl group, aryl group and arylalkyl group and the like. For example, the “alkyl group” is preferably a lower alkyl group (C1-6 alkyl group) and the like, and, for example, a C1-6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-ethylpropyl, hexyl etc., and the like are generally used. For R, a lower alkyl group (C1-6 alkyl group) is preferable, particularly a methyl group is preferable. For example, the “alkenyl group” is preferably a lower alkenyl group and the like, and, for example, a C2-7 alkenyl group such as vinyl, 1-propenyl, allyl, isopropenyl, butenyl, isobutenyl, 2,2-dimethyl-pent-4-enyl etc., and the like are generally used. For example, the “alkynyl group” is preferably a lower alkynyl group and the like, and, for example, a C2-6 alkynyl group such as ethynyl, propargyl, 1-propynyl etc., and the like are generally used. For example, the “cycloalkyl group” is preferably a lower cycloalkyl group and the like, and, for example, a C3-10 cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptanyl and adamantyl etc., and the like are generally used. For example, the “cycloalkenyl group” is preferably a lower cycloalkenyl group, and, for example, a C3-10 cycloalkenyl group such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, bicyclo[2.2.1]hept-5-en-2-yl etc., and the like are generally used. For example, the “cycloalkylalkyl group” is preferably a lower cycloalkylalkyl group, and, for example, a C4-9 cycloalkylalkyl group such as cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl and cyclohexylethyl etc., and the like are generally used. For example, the “cycloalkenylalkyl group” is preferably a lower cycloalkenylalkyl group, and, for example, C4-9 cycloalkenylalkyl such as cyclopentenylmethyl, cyclohexenylmethyl, cyclohexenylethyl, cyclohexenylpropyl, cycloheptenylmethyl, cycloheptenylethyl and bicyclo[2.2.1]hept-5-en-2-ylmethyl etc., and the like are generally used. For example, the “aryl group” is preferably a C6-14 aryl group such as phenyl, 1-naphthyl, 2-naphthyl, biphenylyl, 2-anthryl etc., and the like, and, for example, phenyl group and the like are generally used. The “arylalkyl group” contains, as the aryl moiety, the “aryl group” defined above, and as the alkyl moiety, the “alkyl group” defined above. Of these, for example, a C6-14 aryl-C1-6 alkyl group is preferable, and, for example, benzyl, phenethyl and the like are generally used. As the substituent that the “hydrocarbon group” of the “hydrocarbon group optionally having substituents” represented by the above-mentioned E, R, R1 and G may have, for example, a halogen atom (e.g., fluorine, chlorine, bromine, iodine etc.), a nitro group, a cyano group, a hydroxy group, a thiol group, a sulfo group, a sulphino group, a phosphono group, an optionally halogenated lower alkyl group (e.g., C1-6 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-ethylpropyl, hexyl and the like, a mono-, di- or tri-halogeno-C1-6 alkyl group such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 5,5,5-trifluoropentyl, 6,6,6-trifluorohexyl etc., and the like), an oxo group, an amidino group, an imino group, an alkylenedioxy group (e.g., C1-3 alkylenedioxy group such as methylenedioxy, ethylenedioxy etc., and the like), a lower alkoxy group (e.g., C1-6 alkoxy group such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentyloxy, hexyloxy etc., and the like), an optionally halogenated lower alkoxy group (e.g., a mono-, di- or tri-halogeno-C1-6 alkoxy group such as chloromethyloxy, dichloromethyloxy, trichloromethyloxy, fluoromethyloxy, difluoromethyloxy, trifluoromethyloxy, 2-bromoethyloxy, 2,2,2-trifluoroethyloxy, pentafluoroethyloxy, 3,3,3-trifluoropropyloxy, 4,4,4-trifluorobutyloxy, 5,5,5-trifluoropentyloxy, 6,6,6-trifluorohexyloxy etc., and the like), a lower alkylthio group (e.g., a C1-6 alkylthio group such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, pentylthio, hexylthio etc., and the like), a carboxyl group, a lower alkanoyl group (e.g., formyl; a C1-6 alkyl-carbonyl group such as acetyl, propionyl, butyryl, isobutyryl etc., and the like), a lower alkanoyloxy group (e.g., formyloxy; a C1-6 alkyl-carbonyloxy group such as acetyloxy, propionyloxy, butyryloxy, isobutyryloxy etc., and the like), a lower alkoxycarbonyl group (e.g., a C1-6 alkoxy-carbonyl group such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl etc., and the like), aralkyloxycarbonyl group (e.g., a C7-11 aralkyloxy-carbonyl group such as benzyloxycarbonyl etc., and the like), a thiocarbamoyl group, a lower alkylsulfinyl group (e.g., a C1-6 alkylsulfinyl group such as methylsulfinyl, ethylsulfinyl etc., and the like), a lower alkylsulfonyl group (e.g., a C1-6 alkylsulfonyl group such as methylsulfonyl, ethylsulfonyl etc., and the like), a sulfamoyl group, a mono-lower alkylsulfamoyl group (e.g., a mono-C1-6 alkylsulfamoyl group such as methylsulfamoyl, ethylsulfamoyl etc., and the like), di-lower alkylsulfamoyl group (e.g., a di-C1-6 alkylsulfamoyl group such as dimethylsulfamoyl, diethylsulfamoyl etc., and the like), an arylsulfamoyl group (e.g., a C6-10 arylsulfamoyl group such as phenylsulfamoyl, naphthylsulfamoyl etc., and the like), an aryl group (e.g., a C6-10 aryl group such as phenyl, naphthyl etc., and the like), an aryloxy group (e.g., a C6-10 aryloxy group such as phenyloxy, naphthyloxy etc., and the like), an arylthio group (e.g., a C6-10 arylthio group such as phenylthio, naphthylthio etc., and the like), an arylsulfinyl group (e.g., a C6-10 arylsulfinyl group such as phenylsulfinyl, naphthylsulfinyl etc., and the like), an arylsulfonyl group (e.g., a C6-10 arylsulfonyl group such as phenylsulfonyl, naphthylsulfonyl etc., and the like), an arylcarbonyl group (e.g., a C6-10 aryl-carbonyl group such as benzoyl, naphthoyl etc., and the like), an arylcarbonyloxy group (e.g., a C6-10 aryl-carbonyloxy group such as benzoyloxy, naphthoyloxy etc., and the like), an optionally halogenated lower alkylcarbonylamino group (e.g., an optionally halogenated C1-6 alkyl-carbonylamino group such as acetylamino, trifluoroacetylamino etc., and the like), a carbamoyl group optionally having substituents (e.g., a group of the formula —CONR2R3 wherein R2 and R3 are each a hydrogen atom, a hydrocarbon group optionally having substituents or a heterocyclic group optionally having substituents and in the formula —CONR2R3, R2 and R3 may form a ring together with the adjacent nitrogen atom), an amino group optionally having substituents (e.g., a group of the formula —NR2R3 wherein R2 and R3 are as defined above and in the formula —NR2R3, R2 and R3 may form a ring together with the adjacent nitrogen atom), a ureido group optionally having substituents (e.g., a group of the formula —NHCONR2R3 wherein R2 and R3 are as defined above and in the formula —NHCONR2R3, R2 and R3 may form a ring together with the adjacent nitrogen atom), a carboxamide group optionally having substituents (e.g., a group of the formula —NR2COR3 wherein R2 and R3 are as defined above), a sulfonamide group optionally having substituents (e.g., a group of the formula —NR2SO2R3 wherein R2 and R3 are as defined above), a heterocyclic group optionally having substituents (as defined for R2 and R3) and the like are used. As the “hydrocarbon group” of the “hydrocarbon group optionally having substituents” for R2 and R3, for example, a lower alkyl group (e.g., alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl group and the like), a lower alkenyl group (e.g., alkenyl group having 2 to 6 carbon atoms such as vinyl, allyl group and the like), a lower alkynyl group (e.g., alkynyl group having 2 to 6 carbon atoms such as ethynyl, propargyl group and the like), a cycloalkyl group (e.g., cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl group and the like), a cycloalkenyl group (e.g., cycloalkenyl group having 3 to 8 carbon atoms such as cyclobutenyl, cyclopentenyl, cyclohexenyl group and the like), a cycloalkylalkyl group (e.g., C3-C8 cycloalkyl—C1-C6 alkyl group, such as cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl group and the like), a cycloalkenylalkyl group (e.g., C3-C8 cycloalkenyl —C1-C6 alkyl group, such as cyclobutenylmethyl, cyclopentenylmethyl, cyclohexenylmethyl group and the like), an aryl group (e.g., aryl group having 6 to 14 carbon atoms such as phenyl, naphthyl group and the like), an arylalkyl group (e.g., C6-C14 aryl —C1-C6 alkyl group, such as benzyl, naphthylmethyl group and the like) and the like can be mentioned. As the “heterocyclic group” of the “heterocyclic group optionally having substituents” represented by R2 and R3, a 5- to 12-membered monocyclic or fused heterocyclic group containing 1 or 2 kinds of 1 to 4 hetero atoms selected from nitrogen atom, sulfur atom and oxygen atom such as pyridyl, pyrrolidinyl, piperazinyl, piperidinyl, 2-oxazepinyl, furyl, decahydroisoquinolyl, quinolyl, indolyl, isoquinolyl, thienyl, imidazolyl, morpholinyl etc., and the like can be mentioned. As the substituent for the “hydrocarbon group optionally having substituents” and “heterocyclic group optionally having substituents” for R2 and R3, for example, a halogen atom (e.g., fluorine, chlorine, bromine, iodine etc.), a lower alkyl group (e.g., alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl group and the like), a lower alkenyl group (e.g., alkenyl group having 2 to 6 carbon atoms such as vinyl, allyl group and the like), a lower alkynyl group (e.g., alkynyl group having 2 to 6 carbon atoms such as ethynyl, propargyl group and the like), a cycloalkyl group (e.g., cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl group and the like), a lower alkoxy group (e.g., alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy group and the like), a nitro group, a cyano group, a hydroxy group, a thiol group, a carboxyl group, a lower alkanoyl group (e.g., formyl; C1-6 alkyl-carbonyl group, such as acetyl, propionyl, butyryl group and the like), a lower alkanoyloxy group (e.g., formyloxy; C1-6 alkyl-carbonyloxy group, such as acetyloxy, propionyloxy group and the like), a lower alkoxycarbonyl group (e.g., C1-6 alkoxy-carbonyl group, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl group and the like), an aralkyloxycarbonyl group (e.g., C7-17 aralkyloxy-carbonyl group, such as benzyloxycarbonyl group and the like), an aryl group (e.g., C6-14 aryl group, such as phenyl, naphthyl group and the like), an aryloxy group (e.g., C6-14 aryloxy group having, such as phenyloxy, naphthyloxy group and the like), an arylcarbonyl group (e.g., C6-14 aryl-carbonyl group, such as benzoyl, naphthoyl group and the like), an arylcarbonyloxy group (e.g., C6-14 aryl-carbonyloxy group, such as benzoyloxy, naphthoyloxy group and the like), a carbamoyl group optionally having substituents (e.g., carbamoyl; carbamoyl group mono- or di-substituted by alkyl group having 1 to 6 carbon atoms such as methylcarbamoyl, dimethylcarbamoyl group etc., and the like), an amino group optionally having substituents (e.g., amino; amino group mono- or di-substituted by alkyl group having 1 to 6 carbon atoms such as methylamino, dimethylamino, ethylamino, diethylamino group etc., and the like) and the like can be mentioned. The number and the position of the substitutions are not particularly limited. As the ring formed by R2 and R3 together with the adjacent nitrogen atom, for example, pyrrolidine, piperidine, homopiperidine, morpholine, piperazine, tetrahydroquinoline, tetrahydroisoquinoline and the like can be mentioned. The “hydrocarbon group” of the “hydrocarbon group optionally having substituents” represented by the above-mentioned E, R, R1 and G may have 1 to 5, preferably 1 to 3, the aforementioned substituent at substitutable positions of the hydrocarbon group, wherein, when the number of substituents is not less than 2, each substituents are the same or different. As the “heterocyclic group” of the “heterocyclic group optionally having substituents” represented by the above-mentioned E, R and G, a 5- to 12-membered aromatic heterocyclic group and saturated or unsaturated non-aromatic heterocyclic group containing, as ring-constituting atom (ring atom), 1 to 3 (preferably 1 or 2) kinds of at least 1 (preferably 1 to 4, more preferably 1 to 3) hetero atoms selected from oxygen atom, sulfur atom and nitrogen atom and the like can be mentioned. As the mentioned above, as the “heterocyclic group” of the “heterocyclic group optionally having substituents” represented by G, a saturated oxygen-containing heterocyclic group containing, as ring atoms, 1 to 4, more preferably 1 to 3, hetero atoms selected from oxygen atom, sulfur atom and nitrogen atom etc., and the like are preferable, particularly a 5- to 12-membered saturated oxygen-containing heterocyclic group and the like are preferable. As the “aromatic heterocyclic group”, an aromatic monocyclic heterocyclic group, an aromatic fused heterocyclic group and the like can be mentioned. As the “aromatic monocyclic heterocyclic group”, for example, a 5- or 6-membered aromatic monocyclic heterocyclic group such as furyl, thienyl, pyrrolyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, furazanyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl etc., and the like can be mentioned. As the “aromatic fused heterocyclic group”, for example, a 8- to 12-membered aromatic fused heterocyclic group (preferably a heterocyclic group wherein the aforementioned 5- or 6-membered aromatic monocyclic heterocyclic group is condensed with a benzene ring, or a heterocyclic group wherein the same or different two heterocyclic groups of the aforementioned 5- or 6-membered aromatic monocyclic heterocyclic group are condensed), such as benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, 1,2-benzoisoxazolyl, benzothiazolyl, 1,2-benzoisothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthylidinyl, purinyl, pteridinyl, carbazolyl, α-carbolinyl, β-carbolinyl, γ-carbolinyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiinyl, thianthrenyl, phenanthridinyl, phenanthrolinyl, indolizinyl, pyrrolo[1,2-b]pyridazinyl, pyrazolo[1,5-a]pyridyl, imidazo[1,2-a]pyridyl, imidazo[1,5-a]pyridyl, imidazo[1,2-b]pyridazinyl, imidazo[1,2-a]pyrimidinyl, 1,2,4-triazolo[4,3-a]pyridyl, 1,2,4-triazolo[4,3-b]pyridazinyl etc., and the like can be mentioned. As the “saturated or unsaturated non-aromatic heterocyclic group”, for example, a 3- to 8-membered (preferably 5- or 6-membered) saturated or unsaturated (preferably saturated) non-aromatic heterocyclic group (aliphatic heterocyclic group) such as oxylanyl, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl, tetrahydrofuryl, thiolanyl, piperidinyl, tetrahydropyranyl, thianyl, morpholinyl, thiomorpholinyl, piperazinyl, azepanyl, oxepanyl, thiepanyl, oxazepanyl, thiazepanyl, azocanyl, oxocanyl, thiocanyl, oxazocanyl, thiazocanyl and the like can be mentioned. These may be oxo-substituted and examples thereof include 2-oxoazetidinyl, 2-oxopyrrolidinyl, 2-oxopiperidinyl, 2-oxazepanyl, 2-oxazocanyl, 2-oxotetrahydrofuryl, 2-oxotetrahydropyranyl, 2-oxothiolanyl, 2-oxothianyl, 2-oxopiperazinyl, 2-oxooxepanyl, 2-oxooxazepanyl, 2-oxothiepanyl, 2-oxothiazepanyl, 2-oxooxocanyl, 2-oxothiocanyl, 2-oxooxazocanyl, 2-oxothiazocanyl and the like. A 5-membered non-aromatic heterocyclic group such as 2-oxopyrrolidinyl and the like is preferable. As the substituent that the “heterocyclic group” of the “heterocyclic group optionally having substituents” represented by the above-mentioned E, R and G may have, for example, those similar to the “substituent” of the “hydrocarbon group optionally having substituents” represented by the aforementioned E, R, R1 and G and the like are used. The “heterocyclic group” of the “heterocyclic group optionally having substituents” represented by E, R and G may each have 1 to 5, preferably 1 to 3, substituents mentioned above at substitutable positions of the heterocyclic group, and when the number of substituents is two or more, the substituents are the same or different. The bond between R and W in the compound of the present invention is explained below. When R and W are bonded, the position of the bond between R and W is not particularly limited as long as R and W can be bonded. The bondable position of R is the position where the “hydrocarbon group” and “substituent” of the “hydrocarbon group optionally having substituents” defined above for R can be bonded, and the position where the “heterocyclic group” and “substituent” of the “heterocyclic group optionally having substituents” defined above for R can be bonded. As the bondable position of W, a bondable position of the “divalent chain hydrocarbon group” of the “divalent chain hydrocarbon group optionally having substituents” defined above for W, a bondable position of the “divalent chain hydrocarbon group” defined above for W1 and W2, a bondable position of the “hydrocarbon ring” of the “hydrocarbon ring optionally having substituents” defined above for ring Z, and a bondable position of the “heterocyclic group” of the “heterocyclic group optionally having substituents” defined above for ring Z can be mentioned. R and W can be bonded at the bondable position thereof and can form a ring together with the adjacent nitrogen atom. As such ring, for example, a saturated nitrogen-containing ring (e.g., azetidine, pyrrolidine, piperidine, homopiperidine etc.), an unsaturated nitrogen-containing ring (e.g., tetrahydropyridine etc.), an aromatic nitrogen-containing ring (e.g., pyrrole etc.), a hetero ring (e.g., piperazine, morpholine etc.) containing, besides the nitrogen atom to which R and W are adjacent, at least one hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, a fused ring (e.g., indole, indoline, isoindole, isoindoline, tetrahydroquinoline, tetrahydroisoquinoline etc.) and the like can be mentioned. Of these, a 4- to 7-membered ring is preferable. The ring formed by R and W, which are bonded at each bondable position thereof, together with the adjacent nitrogen atom may have 1 to 4 substituents at substitutable positions thereof. When the number of substituents is 2 or more, the substituents are the same or different. As the substituent, the substituents of the “hydrocarbon group optionally having substituents” and “heterocyclic group optionally having substituents” defined for R, and the substituents of the “divalent chain hydrocarbon group optionally having substituents” defined for W can be mentioned. Specifically, a halogen atom (e.g., fluorine, chlorine, bromine, iodine etc.), a C1-6 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-ethylpropyl, hexyl etc., and the like can be mentioned. By the bond between R and W, for example, and the like are formed, but the ring is not limited to these. These may have substituents as defined above, and it would be understood for those of ordinary skill in the art that they may also have an isomer. In the present invention, X represents a leaving group, such as a halogen atom, a benzotriazolyl group, a (2,5-dioxypyrrolidin-1-yl)oxy group and the like. Of these, a halogen atom such as fluorine, chlorine, bromine, iodine and the like is preferable, and chlorine is particularly preferable. In the present invention, M represents a hydrogen atom, a metal cation or a quaternary ammonium ion. In the present invention, the “metal cation” is exemplified by alkali metal ion (e.g., Na+, K+, Li+, Cs+ and the like), with preference given to Na+. In the present invention, the “quaternary ammonium ion” is exemplified by tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion and the like, with preference given to tetrabutylammonium ion. In the compound (II), a pharmacologically acceptable basic salt can be formed between an acidic group in a molecule and an inorganic base or an organic base etc, and a pharmacologically acceptable acid addition salt can be formed between a basic group in a molecule and an inorganic acid or an organic acid etc. Examples of the inorganic basic salt of compound (II) include salt with alkali metal (e.g., sodium, potassium and the like), alkaline earth metal (e.g., calcium and the like), ammonia etc., and the like, and examples of the organic basic salt of compound (II) include salt with dimethylamine, triethylamine, piperazine, pyrrolidine, piperidine, 2-phenylethylamine, benzylamine, ethanolamine, diethanolamine, pyridine, collidine etc., and the like. Examples of the acid addition salt of compound (II) include inorganic acid salt (e.g., hydrochloride, sulfate, hydrobromide, phosphate and the like), organic acid salt (e.g., acetate, trifluoroacetate, succinate, maleate, fumarate, propionate, citrate, tartrate, lactate, oxalate, methanesulfonate, p-toluenesulfonate and the like) and the like. The compound (II) of the present invention encompasses hydrates. Examples of the “hydrate” include 0.5 hydrate-5.0 hydrate. Of these, 0.5 hydrate, 1.0 hydrate, 1.5 hydrate and 2.0 hydrate are preferable. The compound (II) of the present invention encompasses racemates and optically active compounds. As the optically active compound, such compound wherein one enantiomer is in enantiomer excess (e.e.) of not less than 90% is preferable, more preferably in enantiomer excess of not less than 99%. As an optically active form, an (R)-form represented by the formula: wherein each symbol is as defined above, is preferable. As the preferable compounds encompassed in compound (II), for example, the following specific compounds can be mentioned. That is, 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl acetate, 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl trimethylacetate, 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl cyclohexanecarboxylate, 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl benzoate, 2-[methyl[[2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl benzoate, 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl 4-methoxybenzoate, 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl 3-chlorobenzoate, 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl 3,4-difluorobenzoate, 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl 4-trifluoromethoxybenzoate, 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl 4-fluorobenzoate, 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl 3,4,5-trimethoxybenzoate, 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl 2-pyridinecarboxylate, 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl methoxyacetate, ethyl 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate, isopropyl 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate, isopropyl 2-[methyl[[2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate, benzyl 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate, 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl tetrahydropyran-4-yl carbonate, 2-methoxyethyl 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate, 2-[ethyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl acetate, 2-[isopropyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl acetate, ethyl 2-[isopropyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate, 2-[cyclohexyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl acetate, 2-[cyclohexyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl ethyl carbonate, 2-[[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](phenyl)amino]ethyl acetate, 2-[[[2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](phenyl)amino]ethyl acetate, tert-butyl [2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]-3-pyridyl]methyl carbonate, 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]benzyl acetate, 2-[[2-(acetyloxy)ethyl][[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl acetate, [(2S)-1-[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]-2-pyrrolidinyl]methyl acetate, ethyl [methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]acetate, 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-benzoimidazol-1-yl]carbonyl](methyl)amino]ethyl benzoate, 3-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]propyl benzoate, 2-[methyl[[2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl tetrahydropyran-4-yl carbonate, ethyl 2-[methyl[[2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate, ethyl 2-[methyl[[(S)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate, ethyl 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-3H-imidazo[4,5-b]pyridin-3-yl]carbonyl](methyl)amino]ethyl carbonate, 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-3H-imidazo[4,5-b]pyridin-3-yl]carbonyl](methyl)amino]ethyl acetate, 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-3H-imidazo[4,5-b]pyridin-3-yl]carbonyl](phenyl)amino]ethyl acetate, 4-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]butyl acetate, ethyl 4-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]butyl carbonate, ethyl 3-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]propyl carbonate, 3-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]propyl acetate, 3-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]propane-1,2-diyl diacetate, diethyl 3-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]propane-1,2-diyl biscarbonate, 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-3H-imidazo[4,5-b]pyridin-3-yl]carbonyl](methyl)amino]ethyl 3-chlorobenzoate, 2-[methyl[[2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl acetate, 2-ethoxyethyl 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate, 3-methoxypropyl 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate, 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl N,N-dimethylglycinate, S-[2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl]thioacetate, ethyl 2-[2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethoxy]ethyl carbonate, ethyl 2-[methyl[[2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethoxy]carbonyl]amino]ethyl carbonate, ethyl 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](methyl)amino]ethyl carbonate, 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](phenyl)amino]ethyl acetate, ethyl 2-[[[(S)-5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](methyl)amino]ethyl carbonate, ethyl 2-[[[2-[[[4-(3-methoxypropoxy)-3-methyl-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](methyl)amino]ethyl carbonate, 2-[[[2-[[[4-(3-methoxypropoxy)-3-methyl-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](phenyl)amino]ethyl acetate, 2-[[[5-(difluoromethoxy)-2-[[(3,4-dimethoxy-2-pyridyl)methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](methyl)amino]ethyl ethyl carbonate, 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl 1-methylpiperidine-4-carboxylate, 2-[[4-(aminocarbonyl)phenyl][[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl acetate, 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl 1-methyl-4-piperidinyl carbonate, 2-[[4-(aminocarbonyl)phenyl][[2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl acetate, (−)-ethyl 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-3H-imidazo[4,5-b]pyridin-3-yl]carbonyl](methyl)amino]ethyl carbonate and (+)-ethyl 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-3H-imidazo[4,5-b]pyridin-3-yl]carbonyl](methyl)amino]ethyl carbonate, a salt thereof and the like can be mentioned. Of these, the following compounds and salts thereof are preferable. 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl acetate, ethyl 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate, 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl tetrahydropyran-4-yl carbonate, 2-[methyl[[2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl tetrahydropyran-4-yl carbonate, ethyl 2-[methyl[[2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate, ethyl 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-3H-imidazo[4,5-b]pyridin-3-yl]carbonyl](methyl)amino]ethyl carbonate, 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-3H-imidazo[4,5-b]pyridin-3-yl]carbonyl](methyl)amino]ethyl acetate, 2-[methyl[[2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl acetate, ethyl 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](methyl)amino]ethyl carbonate, ethyl 2-[[[(S)-5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](methyl)amino]ethyl carbonate, ethyl 2-[[[2-[[[4-(3-methoxypropoxy)-3-methyl-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](methyl)amino]ethyl carbonate, and 2-[[[5-(difluoromethoxy)-2-[[(3,4-dimethoxy-2-pyridyl)methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](methyl)amino]ethyl ethyl carbonate. The compound (II) can be produced by the following method A or B. (Method A) The compound (II) or a salt thereof can be obtained by condensation of compound (IV) or a salt thereof with compound (V) or a salt thereof in the presence or absence of a base. The salt of compound (IV) and the salt of compound (V) here are exemplified by the above-mentioned salts of compound (II). For example, acid addition salts such as inorganic acid salt (e.g., hydrochloride, sulfate, hydrobromide, phosphate and the like), organic acid salt (e.g., acetate, trifluoroacetate, succinate, maleate, fumarate, propionate, citrate, tartrate, lactate, oxalate, methanesulfonate, p-toluenesulfonate and the like), and the like can be mentioned. wherein each symbol is as defined above. The reaction of Method A is generally conducted in a solvent, and a solvent that does not inhibit the reaction of Method A is selected as appropriate. Examples of such solvent include ethers (e.g., dioxane, tetrahydrofuran, diethyl ether, tert-butyl methyl ether, diisopropyl ether, ethylene glycol dimethyl ether and the like), esters (e.g., ethyl formate, ethyl acetate, butyl acetate and the like), halogenated hydrocarbons (e.g., dichloromethane, chloroform, carbon tetrachloride, trichlene, 1,2-dichloroethane and the like), hydrocarbons (e.g., n-hexane, benzene, toluene and the like), amides (e.g., formamide, N,N-dimethylformamide, N,N-dimethylacetamide and the like), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone and the like), nitrites (e.g., acetonitrile, propionitrile and the like) and the like, as well as dimethyl sulfoxide, sulfolane, hexamethylphosphoramide, water and the like, which may be used alone or as a mixed solvent. The amount of the solvent to be used is not particularly limited as long as the reaction mixture can be stirred, which is generally 2-to 100-fold amount by weight, preferably 5- to 50-fold amount by weight, relative to 1 mole of compound (IV) or a salt thereof. The amount of compound (IV) or a salt thereof to be used is generally 1-10 mole, preferably 1-3 mole, relative to 1 mole of compound (IV) or a salt thereof. The reaction of Method A is carried out within a temperature range of from about 0° C. to 100° C., preferably 20° C. to 80° C. The reaction time of Method A varies depending on the kind of compounds (IV), (V) or a salt thereof and solvent, reaction temperature and the like, but it is generally 1 min.-96 hrs., preferably 1 min.-72 hrs., more preferably 15 min.-24 hrs. The base in Method A is, for example, an inorganic base (e.g., sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogen carbonate etc.), a tertiary amine (e.g., triethylamine, tripropylamine, tributylamine, cyclohexyldimethylamine, pyridine, lutidine, γ-collidine, N,N-dimethylaniline, N-methylpiperidine, N-methylpyrrolidine, N-methylmorpholine, 4-dimethylaminopyridine and the like); alkylene oxides (e.g., propylene oxide, epichlorohydrin etc.) and the like. The amount of the base to be used is generally 1 mole-10 mole, preferably 1 mole-3 mole, relative to 1 mole of compound (V) or a salt thereof. The compound (IV) or a salt thereof can be produced according to the method described in JP-A-61-50978, U.S. Pat. No. 4,628,098 and the like or a method similar thereto. The compound (V) or a salt thereof can be produced according to a method known per se or a method analogous thereto. For example, when X is a chlorine atom, compound (V) can be obtained by reacting a compound represented by the formula (VII): wherein each symbol is as defined above, or a salt thereof with phosgene, trichloromethyl chloroformate, bis(trichloromethyl)carbonate, thiophosgene and the like in the presence of an acid scavenger in a solvent (e.g., tetrahydrofuran, acetonitrile, dichloromethane etc.). Alternatively, compound (V) can be also obtained by treating ethylcarbamate, which is obtained by reacting compound (VII) or a salt thereof with ethyl chloroformate, with phosphorus oxychloride according to the method described in Synthetic Communications, vol. 17, p. 1887 (1987) or a method analogous thereto. As the salt of compound (VII), for example, acid addition salts such as inorganic acid salts (e.g., hydrochloride, sulfate, hydrobromide, phosphate etc.), organic acid salts (e.g., acetate, trifluoroacetate, succinate, maleate, fumarate, propionate, citrate, tartrate, lactate, oxalate, methanesulfonate, p-toluenesulfonate etc.), and the like can be mentioned. As the acid scavenger used here, for example, inorganic bases (e.g., sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogen carbonate etc.), tertiary amine (e.g., triethylamine, tripropylamine, tributylamine, cyclohexyldimethylamine, pyridine, lutidine, γ-collidine, N,N-dimethylaniline, N-methylpiperidine, N-methylpyrrolidine, N-methylmorpholine, 4-dimethylaminopyridine etc.) and the like can be mentioned. The compound (VII) and a salt thereof can be produced according to a method known per se or a method analogous thereto. For example, when D1, is other than a bond, compound (VII) can be obtained by condensing a compound represented by the formula (VIII): wherein R4 is a hydrogen atom or nitrogen-protecting group, and other symbols are as defined above, or a salt thereof with carboxylic acid or thionic acid represented by the formula (IX): wherein each symbol is as defined above, or a reactive derivative thereof (e.g., anhydride, halide etc.), or a salt thereof in a suitable solvent (e.g., ethyl acetate, tetrahydrofuran, dichloromethane, N,N-dimethylformamide etc., followed by deprotection as necessary. As the salt of compound (VIII), for example, acid addition salts such as inorganic acid salts (e.g., hydrochloride, sulfate, hydrobromide, phosphate etc.), organic acid salts (e.g., acetate, trifluoroacetate, succinate, maleate, fumarate, propionate, citrate, tartrate, lactate, oxalate, methanesulfonate, p-toluenesulfonate etc.) etc., and the like can be mentioned. Alternatively, when D1 is a bond, compound (VII) can be obtained by condensing carboxylic acid or thionic acid represented by the formula (X): wherein each symbol is as defined above, or a reactive derivative thereof (e.g., anhydride, halide etc.), or a salt thereof with a compound represented by G-D2-H in a suitable solvent (e.g., ethyl acetate, tetrahydrofuran, dichloromethane, N,N-dimethylformamide etc.), followed by deprotection, as necessary. As the salt of compound (X), for example, acid addition salts such as inorganic acid salts (e.g., hydrochloride, sulfate, hydrobromide, phosphate etc.), organic acid salts (e.g., acetate, trifluoroacetate, succinate, maleate, fumarate, propionate, citrate, tartrate, lactate, oxalate, methanesulfonate, p-toluenesulfonate etc.) and the like, salts with alkali metal (e.g., sodium, potassium etc.), alkaline earth metal (e.g., calcium etc.), ammonia etc., and the like, and for example, organic base such as dimethylamine, triethylamine, piperazine, pyrrolidine, piperidine, 2-phenylethylamine, benzylamine, ethanolamine, diethanolamine, pyridine, collidine etc., and the like can be mentioned. As the protecting group represented by R4 in the formula (VIII) and the formula (X), for example, a formyl group, a C1-6 alkyl-carbonyl group (e.g., acetyl, ethylcarbonyl etc.), a benzyl group, a tert-butyloxycarbonyl group, a benzyloxycarbonyl group, an allyloxycarbonyl group, a C7-10 aralkyl-carbonyl group (e.g., benzylcarbonyl etc.), a trityl group and the like are used. These groups may be substituted by 1 to 3 halogen atoms (e.g., fluorine, chlorine, bromine etc.), a nitro group and the like. As a method for removing such protecting groups, a method known per se or a method analogous thereto is used, which is, for example, a method using an acid, a base, reduction, UV light, palladium acetate etc., and the like are used. (Method B) The compound (II) and a salt thereof can be obtained by subjecting compound (VI) or a salt thereof to oxidization reaction. wherein each symbol is as defined above. The reaction in Method B can be carried out using an oxidant such as nitric acid, hydrogen peroxide, peroxyacid, peroxyacid ester, ozone, dinitrogen tetraoxide, iodosobenzene, N-halosuccinimide, 1-chlorobenzotriazole, tert-butyl hypochlorite, diazabicyclo[2.2.2]octane-bromine complex, sodium metaperiodate, selenium dioxide, manganese dioxide, chromic acid, cerium ammonium nitrate, bromine, chlorine, sulfuryl chloride, magnesium monoperoxyphthalate and the like. The amount of the oxidant to be used is generally 0.5 mole-2 mole, preferably 0.8 mole-1.2 mole, per 1 mole of compound (VI) or a salt thereof. The oxidization may be carried out using the above-mentioned oxidant such as hydrogen peroxide and peroxyacids in the presence of a catalyst such as vanadium acetate, vanadium oxide acetylacetonate, titanium tetraisopropoxide and the like. The reaction of Method B is generally carried out in a solvent inert to the above-mentioned oxidation reaction. Examples of the “inert solvent” include water, alcohols (e.g., methanol, ethanol, 1-propanol, 2-propanol etc.), ketones (e.g., acetone, methyl ethyl ketone etc.), nitrites (e.g., acetonitrile, propionitrile etc.), amides (e.g., formamide, N,N-dimethylformamide etc.), ethers (e.g., diethyl ether, tert-butyl methyl ether, diisopropyl ether, dioxane, tetrahydrofuran etc.), sulfoxides (e.g., dimethyl sulfoxide etc.) and polar solvents (e.g., sulfolane, hexamethylphosphoramide etc.), which may be used alone or as a mixed solvent thereof. The “inert solvent” is used in generally 1- to 100-fold amount by weight of compound (VI) or a salt thereof. The reaction temperature is generally from −80° C. to 80° C., preferably from 0° C. to 30° C. The reaction time is generally 1 min.-6 hrs., preferably 15 mins.-1 hr. The compound (VI), which is a starting material in Method B, can be obtained by a reaction similar to that in Method A, by the use of, for example, a compound represented by the following formula (XI): wherein each symbol is as defined above, instead of compound (IV). The compound (XI) can be synthesized according to the methods described in the following references or a method analogous thereto: JP-A-61-50978, JP-A-54-141783, JP-A-61-22079, JP-A-1-6270, JP-A-63-146882. The salt of compound (VI) is exemplified by the above-mentioned salts of the compound (II), which are acid addition salts such as inorganic acid salt (e.g., hydrochloride, sulfate, hydrobromide, phosphate and the like), organic acid salt (e.g., acetate, trifluoroacetate, succinate, maleate, fumarate, propionate, citrate, tartrate, lactate, oxalate, methanesulfonate, p-toluenesulfonate and the like) and the like. The compound (II) or a salt thereof obtained by the above-mentioned methods A or B can be isolated and purified from the reaction mixture by a separation means known per se (e.g., concentration, concentration under reduced pressure, solvent extraction, crystallization, recrystallization, phase transfer, chromatography and the like). Since compound (II) and a salt thereof obtained by the above-mentioned methods A or B encompass any isomers thereof, optically pure compound (II) and a salt thereof can be obtained by, for example, subjecting compound (II) or a salt thereof to optical resolution, or asymmetric oxidation of compound (VI) or a salt thereof. The method of optical resolution includes methods known per se, such as a fractional recrystallization method, a chiral column method, a diastereomer method, and so forth. Asymmetric oxidation includes methods known per se, such as the method described in WO96/02535 and the like. The “fractional recrystallization method” includes a method in which a salt is formed between a racemate and an optically active compound [e.g., (+)-mandelic acid, (−)-mandelic acid, (+)-tartaric acid, (−)-tartaric acid, (+)-1-phenethylamine, (−)-1-phenethylamine, cinchonine, (−)-cinchonidine, brucine, etc.], which salt is separated by fractional recrystallization etc., and, if desired, subjected to a neutralization process to give a free optical isomer. The “chiral column method” includes a method in which a racemate or a salt thereof is applied to a column for optical isomer separation (chiral column). In the case of liquid chromatography, for example, optical isomers are separated by adding a racemate to a chiral column such as ENANTIO-OVM (produced by Tosoh Corporation), the DAICEL CHIRAL series (produced by Daicel Corporation) and the like, and developing the racemate in water, a buffer (e.g., phosphate buffer), an organic solvent (e.g., hexane, ethanol, methanol, isopropanol, acetonitrile, trifluoroacetic acid, diethylamine, triethylamine, etc.), or a solvent mixture thereof. In the case of gas chromatography, for example, a chiral column such as CP-Chirasil-DeX CB (produced by GL Science) and the like is used to separate optical isomers. The “diastereomer method” includes a method in which a racemate and an optically active reagent are reacted to give a diastereomeric mixture, which is then subjected to ordinary separation means (e.g., fractional recrystallization, chromatography, etc.) to obtain either diastereomer, which is subjected to a chemical reaction (e.g., acid hydrolysis, base hydrolysis, hydrogenolysis, etc.) to cut off the optically active reagent moiety, whereby the desired optical isomer is obtained. Said “optically active reagent” includes, for example, optically active organic acids such as MTPA [α-methoxy-α-(trifluoromethyl)phenylacetic acid], (−)-menthoxyacetic acid and the like, optically active alkoxymethyl halides such as (1R-endo)-2-(chloromethoxy)-1,3,3-trimethylbicyclo[2.2.1]heptane etc., and the like. Further, a benzimidazole compound represented by the following general formula (III) or a salt thereof is also mentioned as the specific example of the above-mentioned prodrug. In the above-mentioned formula (III), D indicates an oxygen atom or a bond, and Q indicates a hydrocarbon group optionally having a substituent group. The “hydrocarbon group” of the “hydrocarbon group optionally having a substituent group” represented by Q includes an aliphatic or aromatic hydrocarbon group, and an aliphatic hydrocarbon group mentioned here means a saturated or unsaturated, linear, branched or cyclic hydrocarbon group. The hydrocarbon group is preferably a hydrocarbon group having 1 to 14 carbon atoms, and for example, a C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, a C3-8 cycloalkyl group and a C6-14 aryl group are exemplified. A C1-6 alkyl group, a C3-8 cycloalkyl group and a C6-14 aryl group are preferred, and above all a C1-6 alkyl group and a C3-8 cycloalkyl group are more preferred. The above-mentioned “alkyl group” is a linear or branched alkyl group, preferably an alkyl group having 1 to 6 carbon atoms (“C1-6 alkyl group”) and for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, 1-methylpropyl, n-hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 3,3-dimethylpropyl, 2-ethylbutyl and the like are exemplified. An alkyl group having 1 to 4 carbon atoms is preferred. Among these, in Q, methyl, ethyl, isopropyl and tert-butyl are preferred, and tert-butyl is preferred particularly. The above-mentioned “C2-6 alkenyl group” is a linear or branched alkenyl group having 2 to 6 carbon atoms. Example thereof includes vinyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, sec-butenyl, tert-butenyl, n-pentenyl, isopentenyl, neopentenyl, 1-methylpropenyl, n-hexenyl, isohexenyl, 1,1-dimethylbutenyl, 2,2-dimethylbutenyl, 3,3-dimethylbutenyl, 3,3-dimethylpropenyl, 2-ethylbutenyl and the like. An alkenyl group having 2 to 4 carbon atoms is preferred and vinyl, n-propenyl and isopropenyl are preferred particularly. The above-mentioned “C2-6 alkinyl group” is a linear or branched alkinyl group having 2 to 6 carbon atoms. Example thereof includes ethynyl, n-propynyl (1-propynyl), isopropynyl (2-propynyl), n-butynyl, isobutynyl, sec-butynyl, tert-butynyl, n-pentynyl, isopentynyl, neopentynyl, 1-methylpropynyl, n-hexynyl, isohexynyl, 1,1-dimethylbutynyl, 2,2-dimethylbutynyl, 3,3-dimethylbutynyl, 3,3-dimethylpropynyl, 2-ethylbutynyl and the like. An alkynyl group having 2 to 3 carbon atoms is preferred and ethynyl, 1-propynyl and 2-propynyl are preferred particularly. The above-mentioned “C3-8 cycloalkyl group” is a cycloalkyl group having 3 to 8 carbon atoms. Example thereof includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. A cycloalkyl group having 5 to 7 carbon atoms is preferred and among them, cyclopentyl, cyclohexyl and cycloheptyl are preferred. Cyclohexyl is preferred particularly. The above-mentioned “aryl group” is a monocyclic or condensed polycyclic aromatic hydrocarbon group, and preferably an aromatic hydrocarbon group having 6 to 14 carbon atoms (“C6-14 aryl group”). Example thereof includes phenyl, naphthyl, anthryl, phenanthryl and acenaphthylenyl. An aromatic hydrocarbon group having 6 to 10 carbon atoms is preferred, and phenyl is particularly preferred in Q. The above-mentioned “hydrocarbon group” may be substituted, and examples of the substituent group include, for example, a C6-14 aryl group, a hydroxyl group, a halogen, an optionally halogenated C1-6 alkoxy group, a C7-12 aralkyloxy group, a C1-5 alkoxy-carbonyl group, an optionally halogenated C1-6 alkyl group, an amino group which may be substituted with a C1-6 alkyl group, and the like. Examples of the substituent group in the “alkyl group optionally having a substituent group” include, for example, an aryl group, a hydroxyl group, a halogen, an alkoxy group which may be substituted with 1 to 5 halogens, a C7-12 aralkyloxy group, a C1-5 alkoxy-carbonyl group, and the like. The number of said substituent group is 1 to 5 and preferably 1 to 3. Examples of the substituent group in the “aryl group optionally having a substituent group” include a halogen, an alkyl group which may be substituted with 1 to 5 halogens, an aryl group, a hydroxyl group, an alkoxy group which may be substituted with 1 to 5 halogens, a C7-12 aralkyloxy group, a C1-5 alkoxy-carbonyl group, and the like. The number of said substituent group is 1 to 5 and preferably 1 to 3. The above-mentioned “C1-6 alkyl group”, “C2-6 alkenyl group” and “C2-6 alkinyl group” may be substituted, and examples of the substituent group include (i) a C6-14 aryl group, (ii) a hydroxyl group, (iii) a halogen, (iv) an optionally halogenated C1-6 alkoxy group, (v) a C7-12 aralkyloxy group, (vi) a C1-5 alkoxy-carbonyl group, (vii) an acylamino group, (viii) an amino group which may be substituted with a C1-6 alkyl group, and the like, and among these, (i) to (vii) are preferred. The number of said substituent group is 1 to 5 and preferably 1 to 3. The above-mentioned “C3-8 cycloalkyl group” and “C6-14 aryl group” may be substituted, and examples of the substituent group include (i) a C6-14 aryl group, (ii) a hydroxyl group, (iii) a halogen, (iv) an optionally halogenated C1-6 alkoxy group, (v) a C7-12 aralkyloxy group, (vi) a C1-5 alkoxy-carbonyl group, (vii) a C1-6 alkyl group which may be substituted with halogen, (viii) an amino group which may be substituted with a C1-6 alkyl group, and the like, and among these, (i) to (vii) are preferred particularly. The number of said substituent group is 1 to 5 and preferably 1 to 3. In the formula (III), Q is preferably a C1-6 alkyl group, a C2-6 alkenyl group and a C2-6 alkinyl group, which may have a substituent group selected from a group consisting of (i) a C6-14 aryl group, (ii) a hydroxyl group, (iii) a halogen, (iv) an optionally halogenated C1-6 alkoxy group, (v) a C7-12 aralkyloxy group, (vi) a C1-6 alkoxy-carbonyl group and (vii) an acylamino group, or a C3-8 cycloalkyl group or a C6-14 aryl group, which may have a substituent selected from the group consisting of (i) a C6-14 aryl group, (ii) a hydroxyl group, (iii) a halogen, (iv) an optionally halogenated C1-6 alkoxy group, (v) a C7-12 aralkyloxy group, (vi) a C1-5 alkoxy-carbonyl group, and (vii) an optionally halogenated C1-6 alkyl group. Q is more preferably (1) a C1-6 alkyl group which may have 1 to 5 substituent groups selected from the group consisting of (i) a C6-14 aryl group, (ii) a hydroxyl group, (iii) a halogen, (iv) a C1-6 alkoxy group which may be substituted with 1 to 5 halogens, (v) a C7-12 aralkyloxy group and (vi) a C1-6 alkoxy-carbonyl group, or (2) a C6-14 aryl group which may have 1 to 5 substituent groups selected from the group consisting of (i) a halogen, (ii) a C1-6 alkyl group which may be substituted with 1 to 5 halogens, (iii) a C6-14 aryl group, (iv) a hydroxyl group, (v) a C1-6 alkoxy group which may be substituted with 1 to 5 halogens, (vi) a C7-12 aralkyloxy group and (vii) a C1-5 alkoxy-carbonyl group. Q is further more preferably a C1-6 alkyl group which may have a substituent group selected from the group consisting of (i) a C6-14 aryl group, (ii) a hydroxyl group, (iii) a halogen, (iv) an optionally halogenated C1-6 alkoxy group, (v) a C7-12 aralkyloxy group, (vi) a C1-5 alkoxy-carbonyl group and (vii) an acylamino group; or a C3-8 cycloalkyl group or a C6-14 aryl group, which may have a substituent group selected from the group consisting of (i) a C6-14 aryl group, (ii) a hydroxyl group, (iii) a halogen, (iv) an optionally halogenated C1-6 alkoxy group, (v) a C7-12 aralkyloxy group, (vi) a C1-5 alkoxy-carbonyl group and (vii) an optionally halogenated C1-6 alkyl group. Among these, Q is preferably a C1-6 alkyl group which may be substituted with a C6-14 aryl group or a C6-14 aryl group, and Q is preferably phenyl group, methyl or tert-butyl group in particular. In compound (III), an acidic group in the molecule can form a pharmacologically acceptable base salt with an inorganic salt or an organic salt or the like, and a basic group in the molecule can form a pharmacologically acceptable acid additive salt with an inorganic salt or an organic salt or the like. One preferable form of compound (III) of the present invention includes a compound wherein D is a bond and Q is an alkyl group optionally having a substituent group or an aryl group optionally having a substituent group. Examples of the inorganic base salt of compound (III) include, for example, salts with an alkali metal (for example, sodium, potassium and the like), an alkali earth metal (for example, calcium and the like), ammonia and the like, and Examples of the organic base salt of compound (III) include, for example, salts with dimethylamine, triethylamine, piperazine, pyrrolidine, piperidine, 2-phenylethylamine, benzylamine, ethanolamine, diethanolamine, pyridine, collidine and the like. The acid additive salt of compound (III) includes, for example, inorganic acid salts (for example, hydrochloride, sulfate, hydrobromide, phosphate and the like), organic acid salts (for example, acetate, trifluoroacetate, succinate, maleate, fumarate, propionate, citrate, tartarate, lactate, oxalate, methanesulfoante, p-toluenesulfoante, and the like), etc. The compound (III) of the present invention includes a hydrate. Said “hydrate” includes a 0.5 hydrate to 5.0 hydrates. Among these, 0.5 hydrate, 1.0 hydrate, 1.5 hydrates and 2.0 hydrates are preferred. The compound (III) of the present invention includes a racemic compound and an optically active compound. As the optically active compound, such compound wherein one enantiomer is in enantiomer excess (e.e.) of not less than 90% is preferable, more preferably in enantiomer excess of not less than 99%. As an optically active form, an (R)-isomer represented by the formula: wherein each symbol is as defined above, is preferable. The compound (III) can be produced by known methods per se, and are produced by the methods disclosed in, for example, JP-A 2002-187890, WO 02/30920 and the like, or analogous methods thereto. Further, the optically active compound (III) can be obtained by optical resolution methods (a fractional recrystallization method, a chiral column method, a diastereomer method, a method using microorganism or enzyme, and the like) and an asymmetric oxidation method, etc. As the PPI of other benzimidazole derivative, the present invention can be applied to the compound disclosed in WO 03/27098. Although the compounding amounts of the active ingredient represented by the general formulae (I′), (I), (II) and (III) used in the present invention differ depending on the kinds and doses of the active ingredient, the amounts are, for example, about 1% by weight to about 60% by weight based on the total amount of tablets or granules of the present invention, preferably about 1% by weight to about 50% by weight and further preferably about 8% by weight to about 40% by weight. When the active ingredient is a benzimidazole compound PPI, in particular lansoprazole, the amount is about 8% by weight to about 40% by weight. In case of capsules containing the imidazole PPI, especially benzimidazole PPI represented by the general formula (I′) or (I) such as lansoprazole or an optically active compound thereof (R-isomer and the like) and the imidazole derivative PPI represented by the formula (II) and (III), 2 kinds or more of a tablet, granule or fine granule having different behavior of release (for example, 2 kinds of granules such as granules wherein the active ingredient is released comparatively quickly and granules wherein the active ingredient is released with prolonged time) may be filled in combination, using release-controlled coating-layers which have different release properties and conditions respectively. Further, 2 kinds of these release-controlled coating-layers may be stacked in 2 or more layers in the respective granules or fine granules. The preparation which enhances blood levels at a more earlier stage after administration to reveal drug efficacy and then sustain the drug efficacy by the expression of the drug efficacy of the release-controlled granule can be provided, by preparing a preparation (preferably a capsule) which contains a granule having an intermediate layer on the core particle containing the above-mentioned active ingredient and only one layer of enteric coat on said intermediate layer (accordingly, among the above-mentioned release-controlled granule or fine granule by the present invention, the granule in which the release of active ingredient is comparatively rapid.), in addition to a tablet, granule or fine granule having the release-controlled coating-layers of the present invention and the digestive tract retentive gel-forming polymer; or by administering capsules containing a tablet, granule or fine granule having the release control layer of the present invention and the digestive tract retentive gel-forming polymer, together with a preparation containing only granules having a usual enteric coat. Further, when the tablet (in this case, small size tablet is preferable), granule or fine granule to be filled has an enough release-controlling function, the capsules of the present invention may not always contain the gel-forming polymer. Capsules may be prepared using only the release-controlled tablet, granule or fine granule, or by combining the release-controlled tablet, granule or fine granule with a fast-releasing type granule having only enteric coat. In case of such combined preparations and combined administration, there can be prepared the preparations by which the blood level is preferably enhanced at a more earlier stage to achieve drug efficacy and to reach the first maximal blood level, and then the second maximal blood level is reached by the release of active ingredient from granules in which the release was controlled, that is, two peaks are expressed. Further, the controlled release preparation such as the above-mentioned controlled release capsule of the present invention and a usual capsule wherein the active ingredient is comparatively released quickly may be administered at the same time or at an interval. A high blood level of active ingredient can be maintained over a long time by such combined administration. Usual enteric-coated Granules can be produced, for example, according to the method described in JP-A 63-301826. Further, it is preferable to prepare a stabilized preparation according to the method described in JP-A 62-277322. Further, the granule which contains lansoprazole or optically active form thereof and the like at a higher concentration and is sufficiently stabilized can be produced as follow. Namely, there are produced the granules having an active ingredient layer, an intermediate layer formed on said active ingredient layer and an enteric coated layer formed on said intermediate layer, wherein said active ingredient layer contains about 10% by weight to about 40% by weight of lansoprazole and the like based on the total amount of the granule and a basic inorganic salt as a stabilizer and average particle diameter is about 600 μm to about 2500 μm, using known granulation methods such as a fluid-bed granulation method (for example, a centrifugal fluid-bed granulation method), a fluidized granulation method and a stirring granulation method (for example, a fluid-bed fluidized granulation method). Specifically, the active ingredient layer can be obtained, for example, by coating a core particle with a dusting powder containing the imidazole PPI, a basic metal salt, an excipient, a disintegrant and the like while spraying a binding solution such as hydroxypropylcellulose and the like on the core particle. As said core particle, for example, Nonpareil prepared by coating sucrose (75 parts by weight) with corn starch (25 parts by weight) by a known method per se, a spherical core granule using crystalline cellulose and the like are exemplified. Further, a core granule itself may be the above-mentioned active ingredient of drug. The average particle size of said granules is 14 to 80 mesh in general. As the core, a spherically granulated product of sucrose and starch, a spherically granulated product of crystalline cellulose, a spherically granulated product of crystalline cellulose and lactose and the like are exemplified. The ratio of coating layer relative to the core can be selected within a range of being able to control the elution property of active ingredient and the particle size of granules. For example, it is usually about 0.2 part by weight to about 5 parts by weight based on 1 part by weight of core, and preferably about 0.1 part by weight to about 5 parts by weight. Then, the intermediate layer is formed on the active ingredient layer obtained by a conventional method. For example, the component of the intermediate layer is diluted with purified water and the like, and the mixture is sprayed in liquid form to coat the active ingredient layer. At this time, it is preferable to coat the layer while spraying a binding agent such as hydroxypropylcellulose. Examples of the intermediate layer include, for example, a layer in which sugars such as sucrose (purified white sugar (those pulverized (powder sugar) and those not pulverized) and the like), starch sugar such as corn starch, lactose, honey and sugar alcohol (D-mannitol, erythritol and the like) are appropriately compounded with polymeric base materials such as low substituted hydroxypropylcellulose, hydroxypropylcellulose, hydroxypropyl methylcellulose (for example, TC-5 and the like), polyvinyl pyrrolidone, polyvinyl alcohol, methylcellulose and hydroxyethyl methylcellulose. Excipients (for example, masking agent (titanium oxide and the like)) and antistatic agents (titanium oxide, talc and the like) which are added to prepare a preparation may be further appropriately added in the intermediate coating layer, if necessary. The coat amount of the intermediate coating layer is usually, for example, about 0.02 part by weight to about 1.5 parts by weight based on 1 part by weight of granules containing the benzimidazole PPI, and preferably about 0.05 part by weight to about 1 part by weight. Further, the granules which contain lansoprazole and the like at a high concentration and are sufficiently stabilized can be produced by forming a enteric coated layer on the intermediate coating layer by a conventional method. As the component of the enteric coated layer, for example, sustained release base materials such as aqueous enteric polymer base materials such as cellulose acetate phthalate (CAP), hydroxypropyl methylcellulose phthalate, hydroxymethylcellulose acetate succinate, ethyl acrylate-methyl methacrylate-trimethylammoniumethyl methacrylate chloride copolymer (Eudragit RS or RL; manufactured by Rohm Co.), methyl methacrylate-ethyl acrylate copolymer (Eudragit NE30D; manufactured by Rohm Co.), carboxymethyl ethylcellulose and shellac; plasticizers such as water-soluble polymer, triethyl citrate, polyethylene glycol (polyethylene glycol 6000 (trade name: Macrogol 6000, and the like), acetylated monoglyceride, triacetin and castor oil are used. These may be used alone or by mixing 2 kinds or more. The coat amount of the enteric coated layer is about 10% by weight to about 70% by weight based on the total amount of granules before enteric coating, preferably about 10% by weight to about 50% by weight and more preferably about 15% by weight to about 30% by weight. In case of a tablet, for example, the benzimidazole compound, an excipient, a binding agent, a disintegrant, a lubricant and the like are mixed to directly produce tables by compression, or the granules which is produced in same manner as the above-mentioned granules can be compressed into tablet. Further, alternatively, 2 layered tablets may be prepared with a commercially available multilayer tablet machine using the granulated granules. Among the preparations of the present invention, preparations containing the PPI of benzimidazole compound represented by the general formula (I′) such as lansoprazole and optically active form thereof, above all benzimidazole PPI compound represented by the general formula (I), and the PPI of a prodrug-type imidazole compound derivative (in particular, a compound represented by the above-mentioned general formula (II) and (III) and an optically active compound thereof) have superior anti-ulcer effect, gastric juice secretion suppressing effect, mucosa protective effect, anti-Helicobacter pylori effect and the like in vivo, and are useful as a medicine because of low toxicity. In particular, since the imidazole compound represented by the above-mentioned general formula (II) is stable to an acid, it is unnecessary to prepare an enteric preparation for oral administration, the cost of preparing enteric preparations is reduced, and the patients with weak deglutition, in particular, aged people and children are easily dosed because the size of the preparations becomes small. Further, since the absorption is faster than enteric preparations, gastric juice secretion suppressing effect is rapidly expressed, and since it is gradually converted to its original compound in vivo, it has a sustainability and is useful as anti-ulcer agents and the like. The PPI compound of compound (I′) of the present invention or a salt thereof is less toxic, and can be orally or parenterally (for example, local, rectal, vein administration) and safely administered as it is or as a pharmaceutical composition by mixing with a pharmacologically acceptable carrier according to a known method per se, that is, for example, as a preparation such as a tablet (including sugar coated tablet and film coated tablet), powder, granule, capsule (including soft capsule), intraoral disintegrating tablet, liquid, injection, suppository, sustained-release agent and liniment. The tablet, granule or fine granule of the present invention can be orally administrated to mammals (for example, human, monkey, sheep, horse, dog, cat, rabbit, mouse and the like) for the treatment and prevention of digestive ulcer (for example, gastric ulcer, duodenum ulcer, marginal ulcer and the like), Zollinger-Ellison syndrome, gastritis, reflux esophagitis, Symptomatic Gastroesophageal Reflux Disease (symptomatic GERD) with no esophagitis, NUD (Non Ulcer Dyspepsia), gastric cancer (including gastric cancer accompanied with the production promotion of interleukin-1β caused by gene polymorphism of interleukin-1), gastric MALT lymphoma and the like; the eradication of Helicobacter pylori, the suppression of upper digestive tract hemorrhage caused by the digestive ulcer, acute stress ulcer and hemorrhagic gastritis; the suppression of upper digestive tract hemorrhage caused by invasive stress (stress caused by major operation which requires intensive management after operation and by cerebro-vascular accident, head lesion, multiorgan disorder and wide range burn which require intensive care), and the treatment and prevention of ulcer caused by non steroid anti-inflammatories; the treatment and prevention of hyperchylia and ulcers caused by stress after operation, etc. The granules and capsules of the present invention may be used in combination with other active ingredients (for example, 1 to 3 active ingredients) for the eradication of Helicobacter pylori and the like. Examples of the “other active ingredients” include, for example, an antibacterial such as an anti-Helicobacter pylori active substance, an imidazole compound and a quinolone compound, and bismuth salts. In particular, pharmaceuticals obtained by combining the granules and capsules of the present invention with the antibacterials are preferable. Among these, the combination with an antibacterial such as an anti-Helicobacter pylori active substance and an imidazole compound is preferable. Examples of the anti-Helicobacter pylori active substance include, for example, penicillin antibiotic (for example, amoxicillin, benzylpenicillin, piperacillin, mecillinam and the like), cephem antibiotic (for example, cefixime, cephachlor and the like), macrolide antibiotic (for example, erythromycin antibiotic such as erythromycin and clarithromycin), tetracycline antibiotic (for example, tetracycline, minocycline, streptomycin and the like), aminoglycoside antibiotic (for example, gentamicin, amikacin and the like), imipenem etc. In particular, penicillin antibiotic, macrolide antibiotic and the like are preferred. Examples of the “imidazole compound” include, for example, metronidazole, miconazole and the like. Examples of the “bismuth salt” include, for example, there are mentioned bismuth acetate, bismuth citrate and the like. The antibacterial of “quinolone compound” is also preferable, and for example, ofloxacin, ciproxacin and the like are exemplified. In particular, it is preferable to use the granules and capsules of the present invention together with penicillin antibiotic (for example, amoxicillin and the like) and/or erythromycin antibiotic (for example, clarithromycin and the like) for the eradication of Helicobacter pylori. Further, for example, in case of lansoprazole, capsules containing 15 mg of crystalline lansoprazole have been often filled in No.3 capsules, and capsules containing 30 mg have been often filled in No.1 capsules. However, the granules containing an active ingredient at high concentration are unexpectedly obtained by providing an intermediate coating layer, compounding a basic inorganic salt stabilizer and further controlling the particle size of granules without damaging the stability of the active ingredient and preparation. Thus, since the amount of components other than the active ingredient can be reduced, capsules containing 15 mg can be miniaturized to No.4 to No.5 capsules and capsules containing 30 mg can be miniaturized to No.3 to No.5 capsules. Further, No.1 to No.3 capsule can be also used for the capsule containing 60 mg. Further, in case of the optically active compound of lansoprazole, No.3 to No.5 capsule, No.2 to No.4 capsule and No.1 to No.3 capsule can be used for the capsule containing 30 mg, 40 mg and 60 mg respectively. For example, since the capsule containing 60 mg of lansoprazole or lansoprazole R-isomer contains the active ingredient at high concentration and the capsule is miniaturized, it is easy to take and suitable for treatment of acid excessive secretion symptom including Zollinger-Ellison syndrome in particular. Dose per day differs depending on the extent of symptom, age for administration objective, sexuality, body weight, timing of administration, interval, the kind of active ingredient and the like, and are not specifically limited. For example, when the drug is orally administrated to adults (60 kg) as an anti-ulcer agent, the dose is about 0.5 to 1500 mg/day and preferably about 5 to 150 mg/day as active ingredient. These preparations containing these benzimidazole or imidazole compound may be divided to administer once a day or 2 to 3 times a day. Further, the form of package may be also stabilized in order to improve the stability of the solid preparation of the present invention at storage or transportation. For example, the stabilization of the capsule preparation containing the benzimidazole or imidazole compound of the present invention can be improved by using package form such as package suppressing the permeation of oxygen and moisture, package replaced with gas (namely, package replaced with gas other than oxygen), vacuum package and package enclosed with a deoxidizer. The stabilization is improved by reducing oxygen amount with which the solid preparation is directly brought in contact, using these package forms. When a deoxidizer is enclosed, the pharmaceutical solid preparation is packed with an oxygen permeating material, and then another packing may be carried out together with the package. EXAMPLES The present invention is explained in detail in the following by referring to Reference Examples, Synthetic Examples, Examples and Experiment Examples. The present invention is not limited by the Examples. The corn starch, hydroxypropyl cellulose (HPC-L), polyethylene glycol 6000 and titanium oxide used in the following Examples of Preparation are the conformed materials to the 14th revised Japanese Pharmacopoeia. In the following Reference Examples and Synthetic Examples, room temperature means about 15-30° C. 1H-NMR spectra were determined with CDCl3, DMSO-d6 and CD3OD as the solvent using Varian Gemini-200 and Mercury-300; data are shown in chemical shift δ (ppm) from the internal standard tetramethylsilane. Other symbols in the present specification mean the following. s: singlet d: doublet t: triplet q: quartet m: multiplet br: broad bs: broad singlet bm: broad multiplet J: coupling constant Reference Example 1 tert-Butyl 2-hydroxyethyl(methyl)carbamate To a mixture of 2-(methylamino)ethanol (30.04 g) and ethyl acetate (90 mL) was dropwise added a mixture of di-tert-butyl dicarbonate (87.30 g) and ethyl acetate (10 mL) under ice-cooling. After stirring at room temperature for 2 hrs., the mixture was concentrated under reduced pressure. The residue was dissolved in ethyl acetate (150 mL), washed with water (100 mL) and dried over anhydrous magnesium sulfate. Concentration under reduced pressure gave the title compound (66.19 g) as a colorless oil. 1H-NMR(CDCl3): 1.47(9H,s), 2.92(3H,s), 3.40(2H,t,J=5.1 Hz), 3.72-3.80(2H,m). Reference Example 2 2-(Methylamino)ethyl acetate hydrochloride To a mixture of 2-(methylamino)ethanol (1.50 g) and ethyl acetate (20 mL) was added di-tert-butyl dicarbonate (4.37 g) under ice-cooling. After stirring under ice-cooling for 1.5 hrs., acetic anhydride (2.08 mL), pyridine (1.78 mL) and 4-dimethylaminopyridine (0.12 g) were added. After stirring at room temperature for 2 hrs., ethyl acetate (50 mL) was added to the reaction mixture, and the mixture was washed with water (50 mL), a 5% aqueous citric acid solution (50 mL) and saturated brine (50 mL). After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure. To the residue was added a 4N hydrogen chloride—ethyl acetate solution (20 mL), and the mixture was stirred at room temperature for 2 hrs. Diethyl ether (10 mL) was added, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to give the title compound (2.93 g) as a white solid. 1H-NMR(DMSO-d6): 2.07(3H,s), 2.53(3H,s), 3.12-3.17(2H,m), 4.24-4.30(2H,m), 9.29(2H,br). Reference Example 3 2-(Methylamino)ethyl trimethylacetate hydrochloride To a mixture of tert-butyl 2-hydroxyethyl(methyl)carbamate (1.75 g) obtained in Reference Example 1 and ethyl acetate (15 mL) was added triethylamine (1.67 mL) and a mixture of trimethylacetyl chloride (1.35 mL), and ethyl acetate (5 mL) was dropwise added. After stirring at room temperature for 2 hrs., pyridine (1.62 mL) was added, and the mixture was stirred overnight at room temperature. Ethyl acetate (50 mL) was added to the reaction mixture, and the mixture was washed with water (50 mL), a 5% aqueous citric acid solution (50 mL) and saturated brine (50 mL), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, a 4N hydrogen chloride—ethyl acetate solution (10 mL) was added to the residue. After stirring at room temperature for 2 hrs., diethyl ether (10 mL) was added, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to give the title compound (1.65 g) as a white solid. 1H-NMR(DMSO-d6): 1.18(9H,s), 2.56(3H,s), 3.17(2H,t,J=10.5 Hz), 4.22-4.28(2H,m), 9.19(2H,br). Reference Example 4 2-(Methylamino)ethyl cyclohexanecarboxylate hydrochloride To a mixture of tert-butyl 2-hydroxyethyl (methyl)carbamate (1.75 g) obtained in Reference Example 1 and ethyl acetate (20 mL)-were added pyridine (0.97 mL) and 4-dimethylaminopyridine (catalytic amount), and cyclohexanecarbonyl chloride (1.60 mL) was dropwise added. After stirring at room temperature for 2 hrs., pyridine (0.65 mL) and cyclohexanecarbonyl chloride (0.58 mL) were added, and the mixture was stirred overnight at room temperature. Ethyl acetate (50 mL) was added to the reaction mixture, and the mixture was washed with water (50 mL), a 5% aqueous citric acid solution (50 mL) and saturated brine (50 mL), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, a 4N hydrogen chloride—ethyl acetate solution (10 mL) was added to the residue. After stirring at room temperature for 2 hrs., diethyl ether (10 mL) was added, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to give the title compound (1.88 g) as a white solid. 1H-NMR(DMSO-d6): 1.10-1.45(5H,m), 1.54-1.73(3H,m), 1.83-1.93(2H,m), 2.29-2.42(1H,m), 2.54(3H,s), 3.12-3.18(2H,m), 4.23-4.29(2H,m), 9.23(2H,br). Reference Example 5 2-(Methylamino)ethyl benzoate hydrochloride To a mixture of 2-(methylamino)ethanol (30.04 g) and ethyl acetate (90 mL) was dropwise added a mixture of di-tert-butyl dicarbonate (87.30 g) and ethyl acetate (10 mL) under ice-cooling. After stirring at room temperature for 1 hr., benzoyl chloride (61.8 g) and pyridine (38.8 mL) were added under ice-cooling. After stirring at room temperature for 1 hr., a solid was filtered off. The solid was washed with ethyl acetate (100 mL) and the filtrate and the washing were combined, which was washed with water (100 mL) and saturated brine (100 mL). After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure. The residue was dissolved in ethyl acetate (100 mL), a 4N hydrogen chloride—ethyl acetate solution (200 mL) was added, and the mixture was stirred at room temperature for 30 min. Diethyl ether (100 mL) was added and a solid was collected by filtration. The solid was washed twice with ethyl acetate (100 mL) and dried under reduced pressure at 60° C. to give the title compound (57.4 g) as a white solid. 1H-NMR(DMSO-d6): 2.62(3H,s), 3.32(2H,m), 4.53(2H,t,J=9.9 Hz), 7.51-7.57(2H,m), 7.68(1H,m), 8.11(2H,d,J=7.8 Hz), 9.26(2H,bs). Reference Example 6 2-(Methylamino)ethyl 4-methoxybenzoate hydrochloride To a mixture of tert-butyl 2-hydroxyethyl (methyl)carbamate (1.75 g) obtained in Reference Example 1 and ethyl acetate (10 mL) were added 4-methoxybenzoyl chloride (1.88 g) and pyridine (0.97 mL). After stirring at room temperature for 14 hrs., 4-methoxybenzoyl chloride (0.70 g) and pyridine (0.97 mL) were added and the mixture was stirred at room temperature for 1 hr. Ethyl acetate (80 mL) was added to the reaction mixture, and the mixture was washed with water (20 mL), a saturated aqueous sodium hydrogen carbonate solution (20 mL) and water (20 mL), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in ethyl acetate (10 mL), and a 4N hydrogen chloride—ethyl acetate solution (10 mL) was added. After stirring at room temperature for 1 hr., diethyl ether (20 mL) was added, and the precipitated solid was collected by filtration. The solid was washed twice with ethyl acetate (15 mL) and dried under reduced pressure at 60° C. to give the title compound (1.99 g) as a white solid. 1H-NMR(DMSO-d6): 2.62(3H,s), 3.32(2H,m), 4.48(2H,t,J=5.0 Hz), 7.07(2H,d,J=8.7 Hz), 8.06(2H,d,J=8.7 Hz), 9.04(2H,bs). Reference Example 7 2-(Methylamino)ethyl 3-chlorobenzoate hydrochloride To a mixture of tert-butyl 2-hydroxyethyl (methyl)carbamate (1.75 g) obtained in Reference Example 1 and ethyl acetate (10 mL) were added 3-chlorobenzoyl chloride (1.92 g) and pyridine (0.97 mL). After stirring at room temperature for 1 hr., the mixture was stirred at 60° C. for 6 hrs. Ethyl acetate (80 mL) was added to the reaction mixture, and the mixture was washed with water (20 mL), a saturated aqueous sodium hydrogen carbonate solution (20 mL) and water (20 mL), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, a 4N hydrogen chloride—ethyl acetate solution (10 mL) was added to the residue. After stirring at room temperature for 22 hrs., diethyl ether (15 mL) was added, and the precipitated solid was collected by filtration. The solid was washed twice with ethyl acetate (15 mL) and dried under reduced pressure at 60° C. to give the title compound (2.01 g) as a white solid. 1H-NMR(DMSO-d6): 2.63(3H,s), 3.32(2H,m), 4.53(2H,t,J=4.9 Hz), 7.60(1H,t,J=8.0 Hz), 7.78(1H,d,J=8.0 Hz), 8.05(1H,d,J=8.0 Hz), 8.15(1H,s), 9.07(2H,bs). Reference Example 8 2-(Methylamino)ethyl 3,4-difluorobenzoate hydrochloride To a mixture of tert-butyl 2-hydroxyethyl(methyl)carbamate (1.75 g) obtained in Reference Example 1 and ethyl acetate (10 mL) were added 3,4-difluorobenzoyl chloride (1.77 g) and pyridine (0.97 mL). After stirring at room temperature for 3 days, ethyl acetate (80 mL) was added to the reaction mixture. The mixture was washed with water (20 mL), a saturated aqueous sodium hydrogen carbonate solution (20 mL) and water (20 mL), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, a 4N hydrogen chloride—ethyl acetate solution (10 mL) was added to the residue. After stirring at room temperature for 4 hrs, the mixture was concentrated under reduced pressure. The residue was washed with ethyl acetate (15 mL), and dried under reduced pressure at 60° C. to give the title compound (2.05 g) as a white solid. 1H-NMR(DMSO-d6): 2.62(3H,s), 3.32(2H,m), 4.53(2H,t,J=5.0 Hz), 7.64(1H,m), 8.00(1H,m), 8.25(1H,m), 9.25(2H,bs). Reference Example 9 2-(Methylamino)ethyl 4-trifluoromethoxybenzoate hydrochloride To a mixture of tert-butyl 2-hydroxyethyl (methyl)carbamate (1.30 g) obtained in Reference Example 1 and ethyl acetate (10 mL) were added 4-trifluoromethoxybenzoyl chloride (1.83 g) and pyridine (0.72 mL). The mixture was stirred at 60° C. for 25 hrs. Ethyl acetate (60 mL) was added to the reaction mixture, and the mixture was washed with water (30 mL), a saturated aqueous sodium hydrogen carbonate solution (20 mL) and water (20 mL), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, a 4N hydrogen chloride—ethyl acetate solution (10 mL) was added to the residue. After stirring at room temperature for 14.5 hrs., the mixture was concentrated under reduced pressure. The residue was washed twice with ethyl acetate (15 mL), and dried under reduced pressure at 60° C. to give the title compound (1.83 g) as a white solid. 1H-NMR(DMSO-d6): 2.63(3H,s), 3.31(2H,m), 4.54(2H,t,J=4.9 Hz), 7.55(2H,d,J=8.5 Hz), 8.24(2H,d,J=8.5 Hz), 9.02(2H,bs). Reference Example 10 2-(Methylamino)ethyl 4-fluorobenzoate hydrochloride To a mixture of tert-butyl 2-hydroxyethyl (methyl)carbamate (1.75 g) obtained in Reference Example 1 and ethyl acetate (10 mL) were added 4-fluorobenzoyl chloride (1.74 g) and pyridine (0.97 mL). The mixture was stirred at room temperature for 6.5 hrs. Ethyl acetate (80 mL) was added to the reaction mixture, and the mixture was washed with water (30 mL), a saturated aqueous sodium hydrogen carbonate solution (30 mL), water (30 mL) and saturated brine (30 mL), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, a 4N hydrogen chloride—ethyl acetate solution (10 mL) was added to the residue. After stirring at room temperature for 1 hr., the precipitated solid was collected by filtration. The solid was washed twice with ethyl acetate (15 mL) and dried under reduced pressure at 60° C. to give the title compound (1.89 g) as a white solid. 1H-NMR(DMSO-d6): 2.62(3H,s), 3.32(2H,m), 4.52(2H,t,J=4.9 Hz), 7.34-7.44(2H,m), 8.16-8.24(2H,m), 9.18(2H,bs) Reference Example 11 2-(Methylamino)ethyl 3,4,5-trimethoxybenzoate hydrochloride To a mixture of tert-butyl 2-hydroxyethyl (methyl)carbamate (1.75 g) obtained in Reference Example 1 and ethyl acetate (10 mL) were added 3,4,5-trimethoxybenzoyl chloride (2.54 g) and pyridine (0.97 mL). After stirring at 60° C. for 14 hrs., 3,4,5-trimethoxybenzoyl chloride (1.30 g), pyridine (0.97 mL) and ethyl acetate (10 mL) were added, and the mixture was stirred at 60° C. for 24 hrs. The reaction mixture was filtered and ethyl acetate (50 mL) and water (30 mL) were added to the filtrate. After partitioning, ethyl acetate layer was washed with 1N hydrochloric acid (30 mL), water (30 mL), an aqueous copper (II) sulfate solution (30 mL), water (30 mL) and saturated brine (30 mL), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=1:1). A 4N hydrogen chloride—ethyl acetate solution (10 mL) was added to the purified product. After stirring at room temperature for 4 hrs, the mixture was concentrated under reduced pressure. Toluene (10 mL) was added, and the mixture was concentrated under reduced pressure. The residue was suspended in ethyl acetate, and the solid was filtrated. After washing with ethyl acetate (15 mL), the solid was dried under reduced pressure to give the title compound (1.79 g) as a white solid. 1H-NMR(DMSO-d6): 2.61(3H,s), 3.28-3.35(2H,m), 3.74(3H,s), 3.87(6H,s), 4.48-4.54(2H,m), 7.40(2H,s), 9.43(2H,br). Reference Example 12 2-(Methylamino)ethyl 2-pyridinecarboxylate dihydrochloride To a solution (100 mL) of tert-butyl 2-hydroxyethyl (methyl)carbamate (1.75 g) obtained in Reference Example 1, 2-pyridinecarbonyl chloride hydrochloride (2.67 g), pyridine (1.21 mL) and 4-dimethylaminopyridine (0.122 g) in tetrahydrofuran was dropwise added triethylamine (2.09 mL) under ice-cooling, and the mixture was stirred at room temperature for 6 hrs. Water (200 mL) was added to the reaction mixture and the mixture was extracted with ethyl acetate (150 mL). The organic layer was washed successively with a 5% aqueous copper (II) sulfate solution (100 mL), water (100 mL) and saturated brine (100 mL), dried over anhydrous sodium sulfate and evaporated under reduced pressure. The residue was dissolved in ethyl acetate (50 mL) and ethanol (100 mL), and a 4N hydrogen chloride—ethyl acetate solution (15 mL) was added. The mixture was stirred at room temperature for 1 hr. The precipitated solid was collected by filtration, washed twice with ethyl acetate (100 mL), and dried under reduced pressure at 60° C. to give the title compound (1.08 g) as a white solid. 1H-NMR(DMSO-d6): 2.62(3H,t,J=5.4 Hz), 3.35(2H,m), 4.63(2H,t,J=5.0 Hz), 5.26(1H,bs), 7.77-7.84(1H,m), 8.14-8.18(1H,m), 8.36-8.40(1H,m), 8.70-8.90(1H,m), 9.48(2H,br). Reference Example 13 2-(Methylamino)ethyl methoxyacetate To a mixture of tert-butyl 2-hydroxyethyl (methyl)carbamate (1.75 g) obtained in Reference Example 1 and ethyl acetate (10 mL) were added methoxyacetyl chloride (1.20 g) and pyridine (0.97 mL). After stirring at room temperature for 3 hrs., ethyl acetate (70 mL) was added to the reaction mixture. The mixture was washed with water (20 mL), a saturated aqueous sodium hydrogen carbonate solution (20 mL) and water (20 mL), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in ethyl acetate (5 mL), and a 4N hydrogen chloride—ethyl acetate solution (10 mL) was added. After stirring at room temperature for 1 hr., the mixture was concentrated under reduced pressure. Water (60 mL) and diethyl ether (30 mL) were added to the residue. After stirring, the aqueous layer was separated and taken. The aqueous layer was basified with sodium hydrogen carbonate and extracted twice with ethyl acetate (40 mL). The ethyl acetate layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give the title compound (1.00 g) as a colorless oil. 1H-NMR(CDCl3): 2.40(1H,bs), 3.06(3H,s), 3.44(3H,s), 3.57(2H,t,J=5.1 Hz), 3.75-3.82(2H,m), 4.13(2H,s). Reference Example 14 Ethyl 2-(methylamino)ethyl carbonate hydrochloride To a mixture of tert-butyl 2-hydroxyethyl (methyl)carbamate (1.75 g) obtained in Reference Example 1 and ethyl acetate (20 mL) were added pyridine (0.97 mL) and 4-dimethylaminopyridine (catalytic amount), and ethyl chlorocarbonate (1.25 mL) was dropwise added. The mixture was stirred overnight at room temperature and ethyl acetate (50 mL) was added. The mixture was washed with water (50 mL), a 5% aqueous citric acid solution (50 mL) and saturated brine (50 mL), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, a 4N hydrogen chloride—ethyl acetate solution (10 mL) was added to the residue. After stirring at room temperature for 2 hrs., diethyl ether (10 mL) was added, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to give the title compound (1.66 g) as a white solid. 1H-NMR(DMSO-d6): 1.23(3H,t,J=7.1 Hz), 2.54(3H,s), 3.16-3.22(2H,m), 4.15(2H,q,J=7.1 Hz), 4.32-4.37(2H,m), 9.25(2H,br). Reference Example 15 Isopropyl 2-(methylamino)ethyl carbonate hydrochloride To a mixture of tert-butyl 2-hydroxyethyl (methyl)carbamate (3.50 g) obtained in Reference Example 1 and ethyl acetate (20 mL) were added isopropyl chlorocarbonate (1.35 g) and pyridine (1.94 mL) under ice-cooling. After stirring under ice-cooling for 3.5 hrs., isopropyl chlorocarbonate (1.84 g) was added, and the mixture was stirred at room temperature for 2.5 hrs. Ethyl acetate (120 mL) was added to the reaction mixture, and the mixture was washed with water (50 mL) and saturated brine (50 mL), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, a 4N hydrogen chloride—ethyl acetate solution (10 mL) was added to the residue. After stirring at room temperature for 2 hrs., the precipitated solid was collected by filtration. The solid was washed with ethyl acetate (15 mL), and dried under reduced pressure at 60° C. to give the title compound (1.38 g) as a white solid. 1H-NMR(DMSO-d6): 1.25(6H,d,J=6.2 Hz), 2.56(3H,s), 3.20(2H,t,J=5.1 Hz), 4.32(2H,t,J=5.1 Hz), 4.80(1H,m), 8.95(2H,bs). Reference Example 16 Benzyl 2-(methylamino)ethyl carbonate hydrochloride To a mixture of tert-butyl 2-hydroxyethyl (methyl)carbamate (1.75 g) obtained in Reference Example 1 and ethyl acetate (20 mL) were added pyridine (0.97 mL) and 4-dimethylaminopyridine (catalytic amount), and benzyl chlorocarbonate (1.57 mL) was dropwise added. After stirring at room temperature for 2 hrs., pyridine (0.65 mL) and benzyl chlorocarbonate (1.28 mL) were added. After stirring at room temperature for 5 days, pyridine (0.81 mL) was added under ice-cooling and a solution (5 mL) of benzyl chlorocarbonate (1.43 mL) in ethyl acetate was dropwise added slowly. After stirring at room temperature for 2 hrs., ethyl acetate (50 mL) was added to the mixture, washed with water (50 mL), a 5% aqueous citric acid solution (50 mL) and saturated brine (50 mL), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, a 4N hydrogen chloride—ethyl acetate solution (10 mL) was added to the residue. After stirring at room temperature for 2 hrs., diethyl ether (10 mL) was added, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to give the title compound (1.99 g) as a white solid. 1H-NMR(DMSO-d6): 2.55(3H,s), 3.21(2H,t,J=5.1 Hz), 4.37(2H,t,J=5.1 Hz), 5.18(2H,s), 7.30-7.50(5H,m), 9.07 (2H,br). Reference Example 17 2-(Methylamino)ethyl tetrahydropyran-4-yl carbonate hydrochloride To a solution (40 mL) of bis(trichloromethyl)carbonate (2.97 g) in tetrahydrofuran was dropwise added a solution (10 mL) of pyridine (2.43 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 10 min., a solution (20 mL) of tetrahydropyran-4-ol (1.91 g) in tetrahydrofuran was dropwise added slowly. After stirring at room temperature for 2 hrs., the mixture was concentrated under reduced pressure, and ethyl acetate (50 mL) and water (50 mL) were added to the residue. The ethyl acetate layer was separated and taken, washed with 0.2N hydrochloric acid (20 mL) and saturated brine (50 mL), and dried over anhydrous magnesium sulfate. Concentration under reduced pressure gave tetrahydropyran-4-yl chlorocarbonate (1.53 g). To a mixture of tert-butyl 2-hydroxyethyl(methyl)carbamate (1.40 g) obtained in Reference Example 1 and tetrahydrofuran (20 mL) was added pyridine (0.78 mL), and a solution (10 mL) of tetrahydropyran-4-yl chlorocarbonate (1.53 g) obtained above in tetrahydrofuran was dropwise added, and the mixture was stirred overnight at room temperature. After concentration of the reaction mixture under reduced pressure, water (50 mL) was added, the mixture was extracted with ethyl acetate (50 mL). The residue was washed with a 5% aqueous citric acid solution (50 mL) and saturated brine (50 mL), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=4:1, then 3:2). The obtained colorless oil (2.03 g) was dissolved in diethyl ether (2 mL), and a 4N hydrogen chloride—ethyl acetate solution (5 mL) was added. After stirring at room temperature for 30 min., diethyl ether (10 mL) was added and the mixture was stirred overnight. The precipitated solid was collected by filtration and dried under reduced pressure to give the title compound (1.20 g) as a white solid. 1H-NMR(DMSO-d6): 1.50-1.65 (2H,m), 1.87-1.98 (2H,m), 2.54(3H,s), 3.20(2H,m), 3.40-3.50(2H,m), 3.74-3.83(2H,m), 4.36(2H,t,J=5.1 Hz), 4.72-4.83(1H,m), 9.32(2H,br). Reference Example 18 2-Methoxyethyl 2-(methylamino)ethyl carbonate hydrochloride To a mixture of tert-butyl 2-hydroxyethyl (methyl)carbamate (1.75 g) obtained in Reference Example 1 and ethyl acetate (20 mL) was added pyridine (1.62 mL) and a solution (5 mL) of 2-methoxyethyl chlorocarbonate (2.77 g) in ethyl acetate was dropwise added slowly, and the mixture was stirred overnight at room temperature. After concentration of the reaction mixture under reduced pressure, water (50 mL) was added, the mixture was extracted with ethyl acetate (50 mL). The mixture was washed with 5% aqueous citric acid solution (50 mL) and saturated brine (50 mL), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in diethyl ether (2 mL), and a 4N hydrogen chloride—ethyl acetate solution (5 mL) was added. After stirring at room temperature for 30 min., diethyl ether (10 mL) was added, and the mixture was stirred overnight. The precipitated solid was collected by filtration, and dried under reduced pressure to give the title compound (1.56 g) as a white solid. 1H-NMR(DMSO-d6): 2.54(3H,s), 3.19(2H,m), 3.26(3H,s), 3.52-3.57(2H,m), 4.20-4.25(2H,m), 4.33-4.39(2H,m), 9.26(2H,br). Reference Example 19 tert-Butyl ethyl(2-hydroxyethyl)carbamate To a mixture of 2-(ethylamino)ethanol (8.91 g) and ethyl acetate (100 mL) was added di-tert-butyl dicarbonate (21.8 g) under ice-cooling. After stirring at room temperature for 3 days, the mixture was washed with saturated brine (100 mL), and dried over anhydrous magnesium sulfate. Concentration under reduced pressure gave the title compound (19.0 g) as a colorless oil. 1H-NMR(CDCl3): 1.11(3H,t,J=7.0 Hz), 1.47(9H,s), 3.27(2H,q,J=7.0 Hz), 3.37(2H,t,J=5.2 Hz), 3.73(2H,q,J=5.2 Hz). Reference Example 20 2-(Ethylamino)ethyl acetate hydrochloride To a mixture of tert-butyl ethyl(2-hydroxyethyl)carbamate (1.89 g) obtained in Reference Example 19 and ethyl acetate (20 mL) were added acetic anhydride (1.04 mL), pyridine (0.89 mL) and 4-dimethylaminopyridine (0.061 g). After stirring at room temperature for 3 hrs., ethyl acetate (50 mL) was added, and the mixture was washed with water (50 mL), a 5% aqueous citric acid solution (50 mL) and saturated brine (50 mL). After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure. A 4N hydrogen chloride—ethyl acetate solution (10 mL) was added to the residue, and the mixture was stirred at room temperature for 1 hr. Ethyl acetate (10 mL) and diethyl ether (20 mL) were added, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to give the title compound (1.54 g) as a white solid. 1H-NMR(DMSO-d6): 1.22(3H,t,J=7.3 Hz), 2.07(3H,s), 2.95(2H,q,J=7.3 Hz), 3.15(2H,t,J=5.3 Hz), 4.24-4.30(2H,m), 9.17(2H,br). Reference Example 21 tert-Butyl 2-hydroxyethyl(isopropyl)carbamate To a solution (30 mL) of 2-(isopropylamino)ethanol (10.0 g) in tetrahydrofuran was added di-tert-butyl dicarbonate (22.2 g), and the mixture was stirred at room temperature for 1 hr. The reaction mixture was concentrated under reduced pressure and water (100 mL) was added to the residue. The mixture was extracted with ethyl acetate (200 mL). The ethyl acetate layer was washed with saturated brine (100 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to give the title compound (21.21 g) as a colorless oil. 1H-NMR(CDCl3): 1.12(6H,d,J=6.6 Hz), 3.30(2H,t,J=5.0 Hz), 3.71(2H,t,J=5.0 Hz), 3.80-4.30(1H,m). Reference Example 22 2-(Isopropylamino)ethyl acetate hydrochloride To a solution (15 mL) of tert-butyl 2-hydroxyethyl (isopropyl)carbamate (5.0 g) obtained in Reference Example 21 in tetrahydrofuran were added pyridine (6.0 mL) and acetic anhydride (2.79 mL) and the mixture was stirred at room temperature for 18 hrs. The reaction mixture was concentrated under reduced pressure, water (50 mL) was added to the residue, and the mixture was extracted with ethyl acetate (100 mL). The ethyl acetate layer was washed with a 5% aqueous citric acid solution (50 mL) and saturated brine (50 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained colorless oil was dissolved in a 4N hydrogen chloride—ethyl acetate solution (10 mL), and the mixture was stirred at room temperature for 1 hr. The precipitated solid was collected by filtration, and dried under reduced pressure to give the title compound (3.14 g) as a colorless solid. 1H-NMR(DMSO-d6): 1.25(6H,d,J=6.6 Hz), 2.08(3H,s), 3.10-3.40(3H,m), 4.29(2H,t,J=6.0 Hz), 9.11(2H,br). Reference Example 23 Ethyl 2-(isopropylamino)ethyl carbonate hydrochloride To a solution (15 mL) of tert-butyl 2-hydroxyethyl (isopropyl)carbamate (5.0 g) obtained in Reference Example 21 in tetrahydrofuran were added pyridine (6.0 mL) and ethyl chlorocarbonate (2.81 mL) and the mixture was stirred at room temperature for 18 hrs. The reaction mixture was concentrated under reduced pressure, and water (50 mL) was added to the residue, and the mixture was extracted with ethyl acetate (100 mL). The ethyl acetate layer was washed with a 5% aqueous citric acid solution (50 mL) and saturated brine (50 mL), dried over anhydrous sodium sulfate and the mixture was concentrated under reduced pressure. The obtained colorless oil was dissolved in a 4N hydrogen chloride—ethyl acetate solution (10 mL), and the mixture was stirred at room temperature for 1 hr. The precipitated solid was collected by filtration and dried under reduced pressure to give the title compound (3.34 g) as a colorless solid. 1H-NMR(DMSO-d6): 1.20-1.30(9H,m), 3.10-3.40(3H,m), 4.17(2H,q,J=7.4 Hz), 4.37(2H,t,J=5.6 Hz), 9.13(2H,br). Reference Example 24 tert-Butyl cyclohexyl(2-hydroxyethyl)carbamate To a solution (200 mL) of 2-(cyclohexylamino)ethanol (14.3 g) in ethanol was dropwise added di-tert-butyl dicarbonate (21.8 g). After stirring at room temperature for 2 days, the mixture was concentrated under reduced pressure. The residue was dissolved in ethyl acetate (200 mL), washed with water (100 mL) and saturated brine (100 mL), and dried over anhydrous sodium sulfate. Concentration under reduced pressure gave the title compound (24.2 g) as a colorless oil. 1H-NMR(CDCl3): 1.26-1.39(4H,m), 1.47(9H,s), 1.61-1.81(6H,m), 3.30-3.40(2H,m), 3.69(2H,t,J=5.4 Hz), 3.66-3.90(2H,br). Reference Example 25 2-(Cyclohexylamino)ethyl acetate hydrochloride To a solution (50 mL) of tert-butyl cyclohexyl(2-hydroxyethyl)carbamate (2.43 g) obtained in Reference Example 24 in tetrahydrofuran were added pyridine (1.05 mL), acetic anhydride (1.23 mL) and 4-dimethylaminopyridine (0.122 g) under ice-cooling, and the mixture was stirred at room temperature for 12 hrs. Ethyl acetate (100 mL) was added to the reaction mixture and the mixture was washed successively with a saturated aqueous sodium hydrogen carbonate solution (100 mL), a 5% aqueous copper (II) sulfate solution (100 mL) and saturated brine (100 mL), and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure. The residue was dissolved in ethyl acetate (15 mL), and a 4N hydrogen chloride—ethyl acetate solution (15 mL) was added. After stirring at room temperature for 3 hrs., diisopropyl ether (20 mL) was added, and the precipitated solid was collected by filtration to give the title compound (1.78 g) as a white solid. 1H-NMR(DMSO-d6): 1.05-2.03(10H,m), 2.07(3H,s), 2.90-3.10(1H,m), 3.17(2H,t,J=5.2 Hz), 4.29(2H,t,J=5.2 Hz), 9.19(2H,br). Reference Example 26 2-(Cyclohexylamino)ethyl ethyl carbonate hydrochloride To a solution (50 mL) of tert-butyl cyclohexyl(2-hydroxyethyl)carbamate (2.43 g) obtained in Reference Example 24 in tetrahydrofuran were added pyridine (1.45 mL), ethyl chlorocarbonate (1.71 mL) and 4-dimethylaminopyridine (0.122 g) under ice-cooling, and the mixture was stirred at room temperature for 15 hrs. Ethyl acetate (100 mL) was added to the reaction mixture, and the mixture was washed successively with a saturated aqueous sodium hydrogen carbonate solution (100 mL), a 5% aqueous copper (II) sulfate solution (100 mL), water (100 mL) and saturated brine (100 mL), and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure and the residue was dissolved in ethyl acetate (15 mL). A 4N hydrogen chloride—ethyl acetate solution (15 mL) was added. After stirring at room temperature for 3 hrs., diisopropyl ether (20 mL) was added, and the precipitated solid was collected by filtration to give the title compound (2.12 g) as a white solid. 1H-NMR(DMSO-d6): 1.01-2.08(10H,m), 1.23(3H,t,J=7.0 Hz), 2.90-3.10(1H,m), 3.21(2H,t,J=5.2 Hz), 4.16(2H,q,J=7.0 Hz), 4.39(2H,t,J=5.2 Hz), 9.27(2H,br). Reference Example 27 2-Anilinoethyl acetate hydrochloride To a solution (700 mL) of 2-anilinoethanol (137 g) in tetrahydrofuran were added pyridine (97.1 mL), acetic anhydride (113.2 mL) and 4-dimethylaminopyridine (12.22 g) under ice-cooling, and the mixture was stirred at room temperature for 20 hrs. Ethyl acetate (1 L) was added to the reaction mixture and the mixture was washed successively with water (1 L), a saturated aqueous sodium hydrogen carbonate solution (1 L), a 5% aqueous copper (II) sulfate solution (1 L) and saturated brine (1 L), dried over anhydrous sodium sulfate, and evaporated under reduced pressure. To a solution of the obtained residue in ethyl acetate (700 mL) was added a 4N hydrogen chloride—ethyl acetate solution (250 mL) under ice-cooling, and the precipitated solid was collected by filtration to give the title compound (156 g) as a white solid. 1H-NMR(CD3OD): 2.11(3H,s), 3.71-3.76(2H,m), 4.32-4.37(2H,m), 7.49-7.64(5H,m). Reference Example 28 tert-Butyl [2-(methylamino)-3-pyridyl]methyl carbonate To a solution (50 mL) of [2-(methylamino)-3-pyridyl]methanol (2 g: synthesized according to the method described in WO 01/32652) in tetrahydrofuran were added di-tert-butyl dicarbonate (3.48 g) and 4-dimethylaminopyridine (0.18 g) and the mixture was refluxed for 1 hr. Water (30 mL) was added to the reaction mixture and extracted with ethyl acetate (50 mL). The obtained organic layer was washed with saturated brine (50 mL), and dried over anhydrous sodium sulfate. The residue obtained by concentration under reduced pressure was purified by flash silica gel column chromatography (eluted with ethyl acetate:hexane=1:5) to give the title compound (1.51 g) as a white solid. 1H-NMR(CDCl3): 1.49(9H,s), 3.02(3H,d,J=4.8 Hz), 4.99(2H,s), 5.00(1H,bs), 6.55(1H,dd,J=7.0,5.0 Hz), 7.37(1H,dd,J=7.0,1.8 Hz), 8.16(1H,dd,J=5.0,1.8 Hz). Reference Example 29 2-(Methylamino)benzyl acetate To a solution (50 mL) of [2-(methylamino)phenyl]methanol (1.37 g: synthesized according to the method described in WO 01/32652) in tetrahydrofuran were added pyridine (1.05 mL), acetic anhydride (1.23 mL) and 4-dimethylaminopyridine (0.18 g), and the mixture was stirred at room temperature for 8 hrs. Water (100 mL) was added to the reaction mixture, and the mixture was extracted with ethyl acetate (100 mL). The organic layer was washed successively with a 5% aqueous copper (II) sulfate solution (50 mL), a saturated aqueous sodium hydrogen carbonate solution (50 mL) and saturated brine (50 mL), and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure and the obtained residue was purified by flash silica gel column chromatography (eluted with ethyl acetate:hexane=1:5, then 1:3) to give the title compound (0.38 g) as a white solid. 1H-NMR(CDCl3): 2.08(3H,s), 2.87(3H,s), 4.40(1H,br), 5.08(2H,s), 6.64-6.74(2H,m), 7.17-7.32(2H,m). Reference Example 30 2-[(2-Acetyloxyethyl)amino]ethyl acetate hydrochloride To a mixture of 2,2′-iminodiethanol (2.10 g) and ethyl acetate (20 mL) was added di-tert-butyl dicarbonate (4.37 g) under ice-cooling. After stirring for 1.5 hrs. under ice-cooling, acetic anhydride (2.08 mL), pyridine (1.78 mL) and 4-dimethylaminopyridine (0.12 g) were added. After stirring at room temperature for 2 hrs., ethyl acetate (50 mL) was added to the reaction mixture and the mixture was washed with water (50 mL), a 5% aqueous citric acid solution (50 mL) and saturated brine (50 mL). After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure. A 4N hydrogen chloride—ethyl acetate solution (20 mL) was added to the residue, and the mixture was stirred at room temperature for 2 hrs. Diethyl ether (10 mL) was added, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to give the title compound (6.18 g) as a white solid. 1H-NMR(DMSO-d6): 2.07 (6H,s), 3.23(4H,t,J=5.3 Hz), 4.27-4.33(4H,m), 9.40(2H,br). Reference Example 31 (S)-2-Pyrrolidinylmethyl acetate hydrochloride To a mixture of (S)-2-pyrrolidinylmethanol (1.01 g) and ethyl acetate (10 mL) was added di-tert-butyl dicarbonate (2.18 g) under ice-cooling. After stirring for 1 hr. under ice-cooling, acetic anhydride (1.04 mL), pyridine (0.89 mL) and 4-dimethylaminopyridine (0.061 g) were added. After stirring at room temperature for 1 hr., ethyl acetate (50 mL) was added to the reaction mixture, and the mixture was washed with water (50 mL), a 5% aqueous citric acid solution (50 mL) and saturated brine (50 mL). After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure. A 4N hydrogen chloride—ethyl acetate solution (10 mL) was added to the residue, and the mixture was stirred at room temperature for 1 hr. Diethyl ether (10 mL) was added and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to give the title compound (1.68 g) as a pale-brown solid. 1H-NMR(DMSO-d6): 1.56-2.10(4H,m), 2.06(3H,s), 3.05-3.24(2H,m), 3.63-3.68(1H,m), 4.15(1H,dd,J=11.8,8.1 Hz), 4.26(1H,dd,J=11.8,4.1 Hz), 9.21(1H,br), 9.87(1H,br). Reference Example 32 3-(Methylamino)propyl benzoate hydrochloride To a mixture of 3-amino-1-propanol (0.75 g) and ethyl acetate (2.25 mL) was added a solution (0.25 mL) of di-tert-butyl dicarbonate (2.18 g) in ethyl acetate under ice-cooling. After stirring at room temperature for 21.5 hrs., benzoyl chloride (1.30 mL), pyridine (0.98 mL) and 4-dimethylaminopyridine (0.012 g) were added. After stirring at room temperature for 5 hrs., ethyl acetate (32.5 mL) was added to the reaction mixture, and the mixture was washed with water (12.5 mL) and saturated brine (12.5 mL). After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure. The residue was dissolved in N,N-dimethylformamide (20 mL), and methyl iodide (5 mL) was added. 60% sodium hydride (0.4 g) was added under ice-cooling. After stirring at room temperature for 3 hrs., the reaction mixture was poured into an ice-cooled aqueous ammonium chloride solution (60 mL). The mixture was extracted with diethyl ether (80 mL) and washed with saturated brine (30 mL). After drying over anhydrous magnesium sulfate, the mixture was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate:hexane=2:1, then ethyl acetate, then acetone:ethyl acetate=1:9) to give 3-[(tert-butoxycarbonyl)(methyl)amino]propyl benzoate (2.52 g) as a colorless oil. A 4N hydrogen chloride—ethyl acetate solution (10 mL) was added, and the mixture was stirred at room temperature for 1 hr. After concentration under reduced pressure, ethyl acetate (10 mL) was added to the residue and the precipitated solid was collected by filtration. After washing with diethyl ether (10 mL), the solid was dried under reduced pressure to give the title compound (1.73 g) as a colorless solid. 1H-NMR(DMSO-d6): 2.02-2.16(2H,m), 2.56(3H,s), 3.05(2H,t,J=7.3 Hz), 4.35(2H,t,J=6.1 Hz), 7.51(2H,m), 7.65-7.73(1H,m), 8.01(2H,d,J=7.2 Hz), 8.95(2H,br). Reference Example 33 2-[(Ethoxycarbonyl)(methyl)amino]ethyl ethyl carbonate To a solution (1000 mL) of 2-(methylamino)ethanol (100 g) in ethyl acetate was added pyridine (222 mL), ethyl chlorocarbonate (240 mL) was dropwise added over 2 hr. under ice-cooling. After the completion of the dropwise addition, the reaction mixture was stirred at room temperature for 18 hrs. Water (300 mL) was added, and the ethyl acetate layer was separated and washed with 1N hydrochloric acid (200 mL) and saturated brine (200 mL). After drying over anhydrous sodium sulfate, the mixture was concentrated under reduced pressure, and the residue was evaporated under reduced pressure to give the title compound (180 g) as a colorless fraction having a boiling point of 95-100° C. (pressure: 0.1-0.2 mmHg). 1H-NMR(CDCl3): 1.20-1.40(6H,m), 2.97(3H,s), 3.50-3.60(2H,m), 4.05-4.35(6H,m). Reference Example 34 2-[(Chlorocarbonyl)(methyl)amino]ethyl ethyl carbonate To a solution (1500 mL) of 2-[(ethoxycarbonyl)(methyl)amino]ethyl ethyl carbonate (150 g) obtained in Reference Example 33 in acetonitrile was added phosphorus oxychloride (200 mL), and the mixture was refluxed for 4 days. The reaction mixture was concentrated under reduced pressure and the residue was added to a mixture of water (500 mL)—ice (700 g)—ethyl acetate (300 mL) by portions with stirring. After stirring for 1 min., saturated brine (500 mL) was added, and the mixture was extracted with ethyl acetate (500 mL). The ethyl acetate layer was washed successively with saturated brine (300 mL), a saturated aqueous sodium hydrogen carbonate solution (300 mL) and saturated brine (300 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was evaporated under reduced pressure to give the title compound (77 g) as a colorless fraction having a boiling point of 100-105° C. (pressure: 0.1-0.2 mmHg). 1H-NMR(CDCl3): 1.33(3H,t,J=7.2 Hz), 3.12(3H×0.4,s), 3.22(3H×0.6,s), 3.68(2H×0.6,t,J=4.8 Hz), 3.78(2H×0.4,t,J=4.8 Hz), 4.23(2H,q,J=7.2 Hz), 4.30-4.40(2H,m). Reference Example 35 tert-Butyl 4-hydroxybutylcarbamate To a mixture of 4-aminobutanol (3.57 g) and ethyl acetate (9 mL) was dropwise added a mixture of di-tert-butyl dicarbonate (8.73 g) and ethyl acetate (1 mL) under ice-cooling. After stirring at room temperature for 24 hrs., the mixture was concentrated under reduced pressure. The residue was dissolved in ethyl acetate (200 mL), and the mixture was washed with water (50 mL), 1N hydrochloric acid (40 mL), water (30 mL) and saturated brine (30 mL) and dried over anhydrous magnesium sulfate. Concentration under reduced pressure gave the title compound (7.54 g) as a colorless oil. 1H-NMR(CDCl3): 1.44(9H,s), 1.47-1.61(4H,m), 3.07-3.22(2H,m), 3.61-3.76(2H,m), 4.62(1H,bs). Reference Example 36 4-[(tert-Butoxycarbonyl)amino]butyl acetate To a mixture of tert-butyl 4-hydroxybutylcarbamate (3.83 g) obtained in Reference Example 35 and ethyl acetate (20 mL) were added pyridine (1.80 mL) and acetic anhydride (2.27 g), and the mixture was stirred at room temperature for 19 hrs. Ethyl acetate (100 mL) was added to the reaction mixture, and the mixture was washed with water (50 mL), an aqueous copper sulfate solution (30 mL), water (30 mL) and saturated brine (30 mL) and dried over anhydrous magnesium sulfate. Concentration under reduced pressure gave the title compound (4.55 g) as a colorless oil. 1H-NMR(CDCl3): 1.44(9H,s), 1.51-1.69(4H,m), 2.05(3H,s), 3.15(2H,m), 4.07(2H,t,J=6.5 Hz), 4.55(1H,bs). Reference Example 37 4-(Methylamino)butyl acetate hydrochloride To a solution (20 mL) of 4-[(tert-butoxycarbonyl)amino]butyl acetate (4.50 g) obtained in Reference Example 36 and methyl iodide (4.85 mL) in N,N-dimethylformamide was added sodium hydride (60% in oil, 0.94 g) under ice-cooling. After stirring at room temperature for 4 hrs., the reaction mixture was poured into an ice—aqueous ammonium chloride solution. The mixture was extracted with diethyl ether (120 mL), and the diethyl ether layer was washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=1:9). To the purified product was added a 4N hydrogen chloride—ethyl acetate solution (20 mL), and the mixture was stirred at room temperature for 2 hrs. Diethyl ether (40 mL) was added, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to give the title compound (2.28 g) as a white solid. 1H-NMR(DMSO-d6): 1.58-1.70(4H,m), 2.01(3H,s), 2.50(3H,s), 2.82-2.90(2H,m), 4.00(2H,t,J=6.0 Hz), 8.90(2H,br). Reference Example 38 4-[(tert-Butoxycarbonyl)amino]butyl ethyl carbonate To a mixture of tert-butyl 4-hydroxybutylcarbamate (3.71 g) obtained in Reference Example 35 and ethyl acetate (20 mL) were added pyridine (1.71 mL) and ethyl chlorocarbonate (2.55 g) under ice-cooling, and the mixture was stirred at room temperature for 24 hrs. Ethyl acetate (100 mL) was added to the reaction mixture, and the mixture was washed with water (50 mL), an aqueous copper sulfate solution (30 mL), water (30 mL) and saturated brine (30 mL) and dried over anhydrous magnesium sulfate. Concentration under reduced pressure gave the title compound (4.92 g) as a colorless oil. 1H-NMR(CDCl3): 1.31(3H,t,J=7.1 Hz), 1.44(9H,s), 1.46-1.80(4H,m), 3.15(2H,m), 4.11-4.25(4H,m), 4.54(1H,bs). Reference Example 39 Ethyl 4-(methylamino)butyl carbonate hydrochloride To a solution (20 mL) of 4-[(tert-butoxycarbonyl)amino]butyl ethyl carbonate (4.90 g) obtained in Reference Example 38 and methyl iodide (4.67 mL) in N,N-dimethylformamide was added sodium hydride (60% in oil, 0.90 g) under ice-cooling. After stirring at room temperature for 6 hrs., the reaction mixture was poured into an ice—aqueous ammonium chloride solution, and extracted with diethyl ether (120 mL). The diethyl ether layer was washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=1:9). To the purified product was added a 4N hydrogen chloride—ethyl acetate solution (20 mL), and the mixture was stirred at room temperature for 2 hrs. Diethyl ether (40 mL) was added, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to give the title compound (2.86 g) as a white solid. 1H-NMR(DMSO-d6): 1.21(3H,t,J=7.1 Hz), 1.51-1.73(4H,m), 2.50(3H,s), 2.82-2.94(2H,m), 4.05-4.15(4H,m), 8.88(2H,br). Reference Example 40 tert-Butyl 3-hydroxypropylcarbamate To a mixture of 3-aminopropanol (7.51 g) and ethyl acetate (30 mL) was dropwise added a mixture of di-tert-butyl dicarbonate (21.8 g) and ethyl acetate (3 mL) under ice-cooling. After stirring at room temperature for 22 hrs., the mixture was concentrated under reduced pressure. The residue was dissolved in ethyl acetate (200 mL), washed with water (80 mL), 1N hydrochloric acid (60 mL), water (50 mL) and saturated brine (50 mL), and dried over anhydrous sodium sulfate. Concentration under reduced pressure gave the title compound (16.01 g) as a colorless oil. 1H-NMR(CDCl3): 1.45(9H,s), 1.62-1.70(2H,m), 3.24(2H,q,J=6.6 Hz), 3.66(2H,q,J=5.1 Hz), 4.73(1H,bs). Reference Example 41 3-[(tert-Butoxycarbonyl)amino]propyl acetate To a mixture of tert-butyl 3-hydroxypropylcarbamate (8.00 g) obtained in Reference Example 40 and ethyl acetate (50 mL) were added pyridine (4.06 mL) and acetic anhydride (5.13 g), and the mixture was stirred at room temperature for 21 hrs. Ethyl acetate (200 mL) was added to the reaction mixture, and the mixture was washed with water (100 mL), an aqueous copper sulfate solution (40 mL), water (60 mL) and saturated brine (60 mL), and dried over anhydrous sodium sulfate. Concentration under reduced pressure gave the title compound (8.34 g) as a colorless oil. 1H-NMR(CDCl3): 1.44(9H,s), 1.77-1.86(2H,m), 2.06(3H,s), 3.20(2H,q,J=6.3 Hz), 4.12(2H,t,J=6.3 Hz), 4.67(1H,bs). Reference Example 42 3-(Methylamino)propyl acetate hydrochloride To a solution (80 mL) of 3-[(tert-butoxycarbonyl)amino]propyl acetate (17.28 g) obtained in Reference Example 41 and methyl iodide (19.8 mL) in N,N-dimethylformamide was added sodium hydride (60% in oil, 3.82 g) under ice-cooling. After stirring at room temperature for 15 hrs., the reaction mixture was poured into an ice—aqueous ammonium chloride solution and extracted with diethyl ether (300 mL). The diethyl ether layer was washed with saturated brine (100 mL), and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=1:8). To the purified product was added a 4N hydrogen chloride—ethyl acetate solution (40 mL), and the mixture was stirred at room temperature for 2 hrs. Diethyl ether (100 mL) was added, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to give the title compound (2.93 g) as a white solid. 1H-NMR(DMSO-d6): 1.85-1.97(2H,m), 2.02(3H,s), 2.50(3H,s), 2.87-2.96(2H,m), 4.06(2H,t,J=6.3 Hz), 8.87(2H,br). Reference Example 43 3-[(tert-Butoxycarbonyl)amino]propyl ethyl carbonate To a mixture of tert-butyl 3-hydroxypropylcarbamate (8.00 g) obtained in Reference Example 40 and ethyl acetate (50 mL) were added pyridine (4.06 mL) and ethyl chlorocarbonate (5.95 g) under ice-cooling, and the mixture was stirred at room temperature for 24 hrs. Ethyl acetate (100 mL) was added to the reaction mixture, and the mixture was washed with water (50 mL), an aqueous copper sulfate solution (30 mL), water (30 mL) and saturated brine (30 mL), and dried over anhydrous sodium sulfate. Concentration under reduced pressure gave the title compound (9.31 g) as a colorless oil. 1H-NMR(CDCl3): 1.31(3H,t,J=7.1 Hz), 1.44(9H,s), 1.82-1.90(2H,m), 3.22(2H,t,J=6.3 Hz), 4.15-4.23(4H,m), 4.68(1H,bs). Reference Example 44 Ethyl 3-(methylamino)propyl carbonate hydrochloride To a solution (40 mL) of 3-[(tert-butoxycarbonyl)amino]propyl ethyl carbonate (9.31 g) obtained in Reference Example 43 and methyl iodide (9.00 mL) in N,N-dimethylformamide was added sodium hydride (60% in oil, 1.82 g) under ice-cooling. After stirring at room temperature for 12 hrs., the reaction mixture was poured into an ice—aqueous ammonium chloride solution and the mixture was extracted with diethyl ether (200 mL). The diethyl ether layer was washed with saturated brine (100 mL), and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=1:8). To the purified product was added a 4N hydrogen chloride—ethyl acetate solution (40 mL), and the mixture was stirred at room temperature for 2 hrs. Diethyl ether (200 mL) was added, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to give the title compound (4.98 g) as a white solid. 1H-NMR(DMSO-d6): 1.21(3H,t,J=7.1 Hz), 1.91-2.00(2H,m), 2.50(3H,s), 2.88-2.98(2H,m), 4.08-4.16(4H,m), 8.90(2H,br). Reference Example 45 tert-Butyl (2,3-dihydroxypropyl)methylcarbamate To a mixture of 3-(methylamino)-1,2-propanediol (24.5 g) and ethyl acetate (50 mL) was dropwise added a mixture of di-tert-butyl dicarbonate (51.4 g) and ethyl acetate (10 mL) under ice-cooling. After stirring at room temperature for 15 hrs., the mixture was concentrated under reduced pressure. The residue was dissolved in ethyl acetate (150 mL), and the solution was washed with water (80 mL), 1N hydrochloric acid (60 mL), water (50 mL) and saturated brine (50 mL), and dried over anhydrous sodium sulfate. Concentration under reduced pressure gave the title compound (26.9 g) as a colorless oil. 1H-NMR(CDCl3): 1.47(9H,s), 2.92(3H,s), 3.20-3.36(2H,m), 3.41(2H,bs), 3.50-3.62(2H,m), 3.73-3.88(1H,m). Reference Example 46 3-(Methylamino)propane-1,2-diyl diacetate hydrochloride To a mixture of tert-butyl (2,3-dihydroxypropyl)methylcarbamate (10.26 g) obtained in Reference Example 45 and ethyl acetate (50 mL) were added pyridine (10.11 mL) and acetic anhydride (12.76 g), and the mixture was stirred at room temperature for 24 hrs. Ethyl acetate (300 mL) was added to the reaction mixture, and the mixture was washed with water (150 mL), an aqueous copper sulfate solution (100 mL), water (100 mL) and saturated brine (100 mL), and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=1:8). To the purified product was added a 4N hydrogen chloride—ethyl acetate solution (40 mL), and the mixture was stirred at room temperature for 3 hrs. Diethyl ether (100 mL) was added, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to give the title compound (2.76 g) as a white solid. 1H-NMR(DMSO-d6): 2.03(3H,s), 2.07(3H,s), 2.55(3H,s), 3.18-3.22(2H,m), 4.09-4.28(2H,m), 5.20-5.27(1H,m), 9.01(2H,br). Reference Example 47 Diethyl 3-(methylamino)propane-1,2-diyl biscarbonate hydrochloride To a mixture of tert-butyl (2,3-dihydroxypropyl)methylcarbamate (15.53 g) obtained in Reference Example 45 and ethyl acetate (100 mL) were added pyridine (18.35 mL) and ethyl chlorocarbonate (24.62 g) under ice-cooling, and the mixture was stirred at room temperature for 96 hrs. Ethyl acetate (300 mL) was added to the reaction mixture, and the mixture was washed with water (150 mL), an aqueous copper sulfate solution (100 mL), water (100 mL) and saturated brine (100 mL), and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=1:6). To the purified product was added a 4N hydrogen chloride—ethyl acetate solution (80 mL), and the mixture was stirred at room temperature for 3 hrs. Diethyl ether (200 mL) was added, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to give the title compound (5.93 g) as a white solid. 1H-NMR(DMSO-d6): 1.20-1.28(6H,m), 2.57(3H,s), 3.12-3.28(2H,m), 4.10-4.43(6H,m), 5.13-5.22(1H,m), 9.14(2H,br). Reference Example 48 2-Ethoxyethyl 2-(methylamino)ethyl carbonate hydrochloride To a solution (20 mL) of bis(trichloromethyl)carbonate (2.97 g) in tetrahydrofuran was dropwise added a solution (10 mL) of 2-ethoxyethanol (1.80 g) in tetrahydrofuran under ice-cooling. Then a solution (10 mL) of pyridine (2.43 mL) in tetrahydrofuran was added dropwise, and the mixture was stirred at room temperature for 2 hrs. The reaction mixture was concentrated under reduced pressure and water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with 0.2N hydrochloric acid (20 mL) and saturated brine (50 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to give 2-ethoxyethyl chlorocarbonate (1.29 g). A solution (15 mL) of tert-butyl 2-hydroxyethyl(methyl)carbamate (1.23 g) obtained in Reference Example 1 in tetrahydrofuran was added pyridine (0.68 mL), and a solution (5 mL) of 2-ethoxyethyl chlorocarbonate obtained above in tetrahydrofuran was dropwise added to the mixture, and the mixture was stirred at room temperature for 3 days. After concentration of the reaction mixture under reduced pressure, water (50 mL) was added thereto and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with a 5% aqueous citric acid solution (50 mL) and saturated brine (50 mL), dried over anhydrous magnesium sulfate. The mixture was concentrated under reduced pressure and the residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=1:5, then 2:3). The purified product (1.60 g) was dissolved in diethyl ether (3 mL) and a 4N hydrogen chloride—ethyl acetate solution (3 mL) was added. The mixture was stirred overnight at room temperature, and the precipitated solid was collected by filtration and dried under reduced pressure to give the title compound (0.94 g) as a white solid. 1H-NMR(DMSO-d6): 1.10(3H,t,J=7.0 Hz), 2.57(3H,s), 3.18-3.25(2H,m), 3.44(2H,q,J=7.0 Hz), 3.56-3.60(2H,m), 4.19-4.24(2H,m), 4.30-4.37(2H,m), 8.79(2H,br). Reference Example 49 3-Methoxypropyl 2-(methylamino)ethyl carbonate hydrochloride To a mixture of lithium aluminum hydride (2.85 g) and diethyl ether (100 mL) was dropwise added slowly a solution (50 mL) of methyl 3-methoxypropanoate (11.8 g) in tetrahydrofuran under ice-cooling. After stirring at room temperature for 1 hr., the mixture was again ice-cooled and water (3 mL) and a 10% aqueous sodium hydroxide solution (3 mL) were dropwise added. The mixture was allowed to reach room temperature, and water (9 mL) was dropwise added. The mixture was stirred for a while. The precipitate was filtered off and the filtrate was concentrated under reduced pressure to give 3-methoxypropanol (7.64 g) as a colorless oil. 1H-NMR(CDCl3): 1.83(2H,quintet,J=5.8 Hz), 2.43(1H,t,J=5.3 Hz), 3.36(3H,s), 3.57(2H,t,J=6.0 Hz), 3.77(2H,q,J=5.5 Hz). To a solution (50 mL) of bis(trichloromethyl)carbonate (4.45 g) in tetrahydrofuran was dropwise added N-ethyldiisopropylamine (5.75 mL) under ice-cooling. After stirring for a while, a solution (15 mL) of 3-methoxypropanol (2.70 g) obtained above in tetrahydrofuran was dropwise added. The mixture was stirred for 30 min. under ice-cooling and at room temperature for 1 day. After concentration of the reaction mixture under reduced pressure, diluted hydrochloric acid (50 mL) was added to the residue, and the mixture was extracted with ethyl acetate (80 mL). The ethyl acetate layer was washed with 0.2N hydrochloric acid (30 mL) and saturated brine (30 mL), dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 3-methoxypropyl chlorocarbonate (4.39 g). To a solution (20 mL) of tert-butyl 2-hydroxyethyl(methyl)carbamate (1.75 g) obtained in Reference Example 1 in tetrahydrofuran was added pyridine (0.97 mL) and a solution (5 mL) of a 3-methoxypropyl chlorocarbonate (1.83 g) obtained above in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 2 hrs. A solution (5 mL) of pyridine (0.65 mL) and 3-methoxypropyl chlorocarbonate (1.22 g) in tetrahydrofuran was added and the mixture was further stirred for 1 hr. The reaction mixture was concentrated under reduced pressure and water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (80 mL), and the ethyl acetate layer was washed with a 5% aqueous citric acid solution (50 mL) and saturated brine (50 mL), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=1:9, then 3:7). The purified product (3.40 g) was dissolved in diethyl ether (5 mL) and a 4N hydrogen chloride—ethyl acetate solution (5 mL) was added. The mixture was stirred overnight at room temperature and the reaction mixture was concentrated under reduced pressure. Diethyl ether was added for crystallization to give the title compound (2.06 g) as a colorless solid. 1H-NMR(DMSO-d6): 1.78-1.90(2H,m), 2.54(3H,s), 3.15-3.25(2H,m), 3.23(3H,s), 3.33-3.42(2H,m), 4.16(2H,t,J=6.0 Hz), 4.36(2H,t,J=6.0 Hz), 9.27(2H,br). Reference Example 50 2-(Methylamino)ethyl N,N-dimethylglycinate dihydrochloride A mixture of tert-butyl 2-hydroxyethyl(methyl)carbamate (3.50 g) obtained in Reference Example 1, N,N-dimethylglycine hydrochloride (5.29 g), 1-ethyl-3-[3-(dimethylamino)propyl]carbodiimide hydrochloride (7.67 g), triethylamine (5.58 mL), 4-dimethylaminopyridine (1.22 g) and N,N-dimethylformamide (50 mL) was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure and a saturated aqueous sodium hydrogen carbonate solution (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (100 mL). The ethyl acetate layer was washed with saturated brine (50 mL), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluted with methanol:ethyl acetate=5:95, then 20:80). 1N Hydrochloric acid (24 mL) was added to the purified product (2.46 g), and the mixture was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure to give the title compound (2.14 g) as a colorless solid. 1H-NMR(DMSO-d6): 2.52(3H,s), 2.85(6H,s), 3.20(2H,m), 4.30(2H,s), 4.43-4.49(2H,m), 9.60(2H,br), 10.81(1H,br). Reference Example 51 S-[2-(Methylamino) ethyl]thioacetate hydrochloride To a solution (50 mL) of tert-butyl 2-hydroxyethyl(methyl)carbamate (3.50 g) obtained in Reference Example 1, thioacetic acid (1.72 mL) and triphenylphosphine (7.87 g) in tetrahydrofuran was dropwise added slowly a solution (10 mL) of diisopropyl azodicarboxylate (5.91 mL) in tetrahydrofuran under ice-cooling. The mixture was stirred under ice-cooling for 1 hr. and at room temperature for 2 hrs. The reaction mixture was again ice-cooled and a solution (10 mL) of triphenylphosphine (7.87 g) and diisopropyl azodicarboxylate (5.91 mL) in tetrahydrofuran was added. The mixture was stirred under ice-cooling for 30 min. Thioacetic acid (1.14 mL) was added and the mixture was stirred under ice-cooling for 30 min. and at room temperature overnight. The reaction mixture was concentrated under reduced pressure and hexane and diisopropyl ether were added to the residue. The precipitate was filtered off and the filtrate was concentrated under reduced pressure. This step was repeated and a saturated aqueous sodium hydrogen carbonate solution (50 mL) was added. The mixture was extracted with ethyl acetate (100 mL). The ethyl acetate layer was washed with saturated brine (50 mL), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=5:95, and then 15:85). A 4N hydrogen chloride—ethyl acetate solution (10 mL) was added to the purified product (4.47 g) and the mixture was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure and ethyl acetate and diethyl ether were added to the residue for crystallization to give the title compound (1.79 g) as a pale-yellow solid. 1H-NMR(DMSO-d6): 2.38(3H,s), 2.52(3H,s), 2.96-3.08(2H,m), 3.12-3.20(2H,m), 9.35(2H,br). Reference Example 52 Ethyl 2-[2-(methylamino)ethoxy]ethyl carbonate hydrochloride To a mixture of 2-(2-aminoethoxy)ethanol (99.52 g) and ethyl acetate (200 mL) was dropwise added a mixture of di-tert-butyl dicarbonate (208.57 g) and ethyl acetate (50 mL) under ice-cooling. After stirring at room temperature for 60 hrs., the mixture was concentrated under reduced pressure. The residue was dissolved in ethyl acetate (500 mL), washed with water (200 mL), 1N hydrochloric acid (200 mL), water (300 mL) and saturated brine (300 mL), and dried over anhydrous sodium sulfate. Concentration under reduced pressure gave tert-butyl [2-(2-hydroxyethoxy)ethyl]carbamate (169.2 g) as a colorless oil. 1H-NMR(CDCl3): 1.45(9H,s), 3.33(2H,q,J=5.1 Hz), 3.54-3.59(4H,m), 3.74(2H,q,J=5.1 Hz), 4.88(2H,bs). To a mixture of tert-butyl [2-(2-hydroxyethoxy)ethyl]carbamate (53.93 g) obtained above and ethyl acetate (350 mL) were added pyridine (53.78 mL) and ethyl chlorocarbonate (70.57 g) under ice-cooling, and the mixture was stirred at room temperature for 96 hrs. Ethyl acetate (500 mL) was added to the reaction mixture, and the mixture was washed with water (500 mL), an aqueous copper sulfate solution (200 mL), water (300 mL) and saturated brine (300 mL) and dried over anhydrous sodium sulfate. Concentration under reduced pressure gave 2-[2-[(tert-butoxycarbonyl)amino]ethoxy]ethyl ethyl carbonate (93.19 g) as a colorless oil. 1H-NMR(CDCl3): 1.32(3H,t,J=7.2 Hz), 1.44(9H,s), 3.32(2H,t, J=5.1 Hz), 3.54(2H,t, J=5.1 Hz), 3.67-3.74(2H,m), 4.21(2H,q, J=7.2 Hz), 4.26-4.31(2H,m), 4.91(1H,bs). To a solution (350 mL) of 2-[2-[(tert-butoxycarbonyl)amino]ethoxy]ethyl ethyl carbonate (93.15 g) obtained above and methyl iodide (83.6 mL) in N,N-dimethylformamide was added sodium hydride (60% in oil, 16.12 g) under ice-cooling. After stirring at room temperature for 24 hrs., the reaction mixture was poured into an ice—aqueous ammonium chloride solution, and extracted with diethyl ether (800 mL). The diethyl ether layer was washed with saturated brine (300 mL), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=1:8). To the purified product was added a 4N hydrogen chloride—ethyl acetate solution (300 mL) was added, and the mixture was stirred at room temperature for 2 hrs. Diethyl ether (300 mL) was added, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to give the title compound (33.21 g) as a white solid. 1H-NMR(DMSO-d6): 1.21(3H,t,J=7.2 Hz), 2.51(3H,s), 3.02-3.09(2H,m), 3.65-3.72(4H,m), 4.12(2H,q,J=7.2 Hz), 4.22(2H,t,J=4.5 Hz), 9.06(2H,br). Reference Example 53 Ethyl 2-[methyl[[2-(methylamino)ethoxy]carbonyl]amino]ethyl carbonate hydrochloride To a solution (100 mL) of bis(trichloromethyl)carbonate (11.87 g) in tetrahydrofuran was dropwise added a solution (20 mL) of pyridine (9.71 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., a solution (20 mL) of tert-butyl 2-hydroxyethyl(methyl)carbamate (17.52 g) obtained in Reference Example 1 in tetrahydrofuran was dropwise added and the mixture was stirred at room temperature for 15 hrs. After concentration under reduced pressure, water (500 mL) and anhydrous sodium sulfate were added to the residue. After filtration, the filtrate was concentrated under reduced pressure. To the obtained residue were added a solution (50 mL) of 2-(methylamino)ethanol (5.00 g) in ethyl acetate and triethylamine (10.0 mL) under ice-cooling and the mixture was stirred at room temperature for 15 hrs. Ethyl acetate (300 mL) was added to the reaction mixture, washed with water (150 mL) and saturated brine (200 mL) and dried over anhydrous sodium sulfate. After concentration under reduced pressure, to a mixture of the residue and ethyl acetate (100 mL) were added pyridine (2.91 mL) and ethyl chlorocarbonate (3.44 g) under ice-cooling, and the mixture was stirred at room temperature for 48 hrs. Ethyl acetate (200 mL) was added to the reaction mixture, washed with water (100 mL), an aqueous copper sulfate solution (50 mL), water (50 mL) and saturated brine (50 mL), and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure and the residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=1:3). To the purified product was added a 4N hydrogen chloride—ethyl acetate solution (30 mL), and the mixture was stirred at room temperature for 3 hrs. Diethyl ether (100 mL) was added, and the precipitated solid was collected by filtration. The solid was dried under reduced pressure to give the title compound (2.90 g) as a white solid. 1H-NMR(DMSO-d6): 1.21(3H,t,J=7.2 Hz), 2.57(3H,bs), 2.86(1.5H,s), 2.93(1.5H,s), 3.16(2H,bs), 3.34(1H,bs), 3.48(1H,t,J=5.1 Hz), 3.58(1H,t,J=5.1 Hz), 4.12(2H,q,J=7.2 Hz), 4.16-4.24(4H,m), 8.94(1H,br). Reference Example 54 2-(Methylamino)ethyl 1-methylpiperidine-4-carboxylate dihydrochloride A mixture of ethyl piperidine-4-carboxylate (4.72 g), methyl iodide (2.24 mL), potassium carbonate (8.29 g) and acetonitrile (50 mL) was stirred at room temperature for 2 hrs. The reaction mixture was concentrated under reduced pressure and water (150 mL) was added. The mixture was extracted with ethyl acetate (150 mL). The ethyl acetate layer was washed with saturated brine (100 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. A 1N aqueous sodium hydroxide solution (20 mL) was added to the residue (2.64 g), and the mixture was stirred overnight at room temperature. The reaction mixture was neutralized by adding 1N hydrochloric acid (20 mL) and the mixture was concentrated under reduced pressure. Ethanol was added to the residue, and the precipitate was filtered off. The filtrate was concentrated under reduced pressure. This step was repeated and ethanol and ethyl acetate were added to the residue for crystallization to give 1-methylpiperidine-4-carboxylic acid (1.79 g) as a colorless solid. 1H-NMR(CD3OD): 1.80-1.98(2H,m), 2.00-2.14(2H,m), 2.28-2.42(1H,m), 2.78(3H,s), 2.88-3.04(2H.m), 3.32-3.44(2H.m). A mixture of 1-methylpiperidine-4-carboxylic acid (1.72 g) obtained above, tert-butyl 2-hydroxyethyl(methyl)carbamate (1.75 g) obtained in Reference Example 1,1-ethyl-3-[3-(dimethylamino)propyl]carbodiimide hydrochloride (2.30 g), 4-dimethylaminopyridine (0.24 g) and acetonitrile (50 mL) was stirred at room temperature for 16 hrs. The reaction mixture was concentrated under reduced pressure and a saturated aqueous sodium hydrogen carbonate solution (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (100 mL). The ethyl acetate layer was washed with saturated brine (50 mL), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=50:50, then 80:20). 1N Hydrochloric acid (25 mL) was added to the purified product (2.73 g), and the mixture was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure and isopropanol was added. The mixture was again concentrated under reduced pressure and the precipitated solid was collected by filtration to give the title compound (1.72 g) as a colorless solid. 1H-NMR(DMSO-d6): 1.70-2.20(4H,m), 2.40-3.50(13H,m), 4.31(2H,m), 9.25(2H,br), 10.77(1H,br). Reference Example 55 2-[[4-(Aminocarbonyl)phenyl]amino]ethyl acetate A mixture of 4-fluorobenzonitrile (6.06 g), 2-aminoethanol (3.71 g), potassium carbonate (8.29 g) and dimethyl sulfoxide (50 mL) was stirred at 100° C. overnight. Water (200 mL) was added to the reaction mixture and the mixture was extracted with ethyl acetate (200 mL×4). The ethyl acetate layer was washed with saturated brine (100 mL), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=30:70, then 50:50, then 80:20, then ethyl acetate) to give 4-[(2-hydroxyethyl)amino]benzonitrile (5.89 g) as a yellow solid. 1H-NMR(CDCl3): 2.04(1H,t,J=4.8 Hz), 3.33(2H,m), 3.86(2H,q,J=4.8 Hz), 4.66(1H,br), 6.58(2H,d,J=8.7 Hz), 7.39(2H,d,J=8.7 Hz). A mixture of 4-[(2-hydroxyethyl)amino]benzonitrile (0.81 g) obtained above, potassium hydroxide (1.12 g) and tert-butanol (20 mL) was stirred at 100° C. for 1 hr. Water (100 mL) was added to the reaction mixture, and extracted with ethyl acetate (100 mL). The ethyl acetate layer was washed with saturated brine (80 mL), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. To a solution (10 mL) of the residue (0.83 g), pyridine (0.49 mL) and 4-dimethylaminopyridine (0.061 g) in tetrahydrofuran was dropwise added a solution (1 mL) of acetic anhydride (0.57 mL) in tetrahydrofuran. The mixture was stirred at room temperature for 1 hr., water (80 mL) was added, and the mixture was extracted with ethyl acetate (100 mL). The ethyl acetate layer was washed with saturated brine (80 mL), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=30:70, then 60:40) to give the title compound (0.68 g) as a colorless solid. 1H-NMR(CDCl3): 2.08(3H,s), 3.44(2H,q,J=5.6 Hz), 4.29(2H,t,J=5.4 Hz), 4.48(1H,br), 6.59(2H,d,J=8.9 Hz), 7.43(2H,d,J=8.9 Hz). Reference Example 56 2-(Methylamino)ethyl 1-methyl-4-piperidinyl carbonate dihydrochloride To a solution (40 mL) of N,N′-carbonyldiimidazole (3.36 g) in tetrahydrofuran was dropwise added slowly a solution (10 mL) of tert-butyl 2-hydroxyethyl(methyl)carbamate (3.30 g) obtained in Reference Example 1 in tetrahydrofuran under ice-cooling. The mixture was stirred under ice-cooling for 40 min. and at room temperature for 2 hrs. N,N′-Carbonyldiimidazole (0.31 g) was added and the mixture was further stirred for 3 days. The reaction mixture was concentrated under reduced pressure and ethyl acetate (150 mL) was added to the residue. The mixture was washed with saturated brine (100 mL×2), water (50 mL×3) and saturated brine (50 mL), dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 2-[(tert-butoxycarbonyl)(methyl)amino]ethyl 1H-imidazole-1-carboxylate (5.24 g) as a colorless oil. 1H-NMR(CDCl3): 1.39(9H×0.5,s), 1.42(9H×0.5,s), 2.94(3H,m), 3.63(2H,m), 4.51(2H,t,J=5.3 Hz), 7.06(1H,m), 7.42(1H,m), 8.13(1H,s). A mixture of 2-[(tert-butoxycarbonyl)(methyl)amino]ethyl 1H-imidazole-1-carboxylate (1.35 g) obtained above, 1-methyl-4-piperidinol (1.38 g) and acetonitrile (20 mL) was stirred overnight at room temperature. 1-Methyl-4-piperidinol (0.92 g) was added and the mixture was stirred overnight. The reaction mixture was concentrated under reduced pressure and a saturated aqueous sodium hydrogen carbonate solution (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (100 mL). The ethyl acetate layer was washed with saturated brine (50 mL), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. 1N Hydrochloric acid (12 mL) was added to the residue (1.60 g), and the mixture was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure, water, isopropanol and ethyl acetate were added, and the precipitated solid was collected by filtration to give the title compound (1.09 g) as a colorless solid. 1H-NMR(DMSO-d6): 1.85-2.20(4H,m), 2.55(3H,s), 2.70(3H×0.5,s), 2.73(3H×0.5,s), 2.90-3.50(6H,m), 4.38(2H,m), 4.65-5.00(1H,m), 9.21(2H,br), 11.10(1H,br). Synthetic Example 1 2-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl acetate To a solution (30 mL) of bis(trichloromethyl)carbonate (0.50 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.40 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., 2-(methylamino)ethyl acetate hydrochloride (0.77 g) obtained in Reference Example 2 was added. A solution (1 mL) of triethylamine (0.70 mL) in tetrahydrofuran was dropwise added and the mixture was stirred at room temperature for 1 hr. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. The mixture was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.11 g), triethylamine (0.84 mL) and 4-dimethylaminopyridine (catalytic amount) were added, and the mixture was stirred at 60° C. overnight. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:1, then ethyl acetate), and further by silica gel column chromatography (eluted with ethyl acetate:hexane=2:1, then ethyl acetate, then acetone:ethyl acetate=1:4, then 1:1) to give the title compound (1.13 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 2.10(3H,s), 2.24(3H,s), 3.09(3H,bs), 3.60-4.00(2H,br), 4.25-4.50(4H,m), 4.89(1H,d,J=13.3 Hz), 5.05(1H,d,J=13.3 Hz), 6.65(1H,d,J=5.5 Hz), 7.35-7.51(3H,m), 7.80-7.90(1H,m), 8.35(1H,d,J=5.5 Hz). Synthetic Example 2 2-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl trimethylacetate To a solution (30 mL) of bis(trichloromethyl)carbonate (0.50 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.40 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 1 hr., 2-(methylamino)ethyl trimethylacetate hydrochloride (0.98 g) obtained in Reference Example 3 was added. A solution (1 mL) of triethylamine (0.70 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred overnight at room temperature. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL), and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.11 g), triethylamine (0.84 mL) and 4-dimethylaminopyridine (0.037 g) were added, and the mixture was stirred overnight at 60° C. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by flash silica gel column chromatography (eluted with acetone:hexane=1:3, then 3:2). Crystallization from acetone-diisopropyl ether and recrystallization from acetone-diisopropyl ether gave the title compound (1.01 g) as a colorless solid. 1H-NMR(CDCl3): 1.23(9H,s), 2.23(3H,s), 3.08(3H,bs), 3.40-4.30(2H,br), 4.30-4.50(4H,m), 4.80-5.20(2H,br), 6.64(1H,d,J=5.7 Hz), 7.35-7.50(3H,m), 7.78-7.88(1H,m), 8.35(1H,d,J=5.7 Hz). Synthetic Example 3 2-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl cyclohexanecarboxylate To a solution (30 mL) of bis(trichloromethyl)carbonate (0.50 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.40 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., 2-(methylamino)ethyl cyclohexane carboxylate hydrochloride (1.11 g) obtained in Reference Example 4 was added. A solution (1 mL) of triethylamine (0.70 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 1 hr. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.11 g), triethylamine (0.84 mL) and 4-dimethylaminopyridine (0.037 g) were added, and the mixture was stirred overnight at 60° C. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by flash silica gel column chromatography (eluted with acetone:hexane=1:3, then 3:2). Crystallization from acetone-diisopropyl ether and recrystallization from acetone-diisopropyl ether gave the title compound (1.11 g) as a colorless solid. 1H-NMR(CDCl3): 1.10-1.55(5H,m), 1.55-1.82(3H,m), 1.84-1.98(2H,m), 2.23(3H,s), 2.27-2.40(1H,m), 3.08(3H,bs), 3.40-4.30(2H,br), 4.30-4.50(4H,m), 4.80-5.15(2H,br), 6.64(1H,d,J=5.4 Hz), 7.35-7.48(3H,m), 7.84(1H,d,J=6.9 Hz), 8.34 (1H,d,J=5.4 Hz) Synthetic Example 4 2-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl benzoate To a solution (30 mL) of bis(trichloromethyl)carbonate (0.50 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.40 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 1 hr., 2-(methylamino)ethyl benzoate hydrochloride (1.08 g) obtained in Reference Example 5 was added. A solution (1 mL) of triethylamine (0.70 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred overnight at room temperature. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.11 g), triethylamine (0.84 mL) and 4-dimethylaminopyridine (0.037 g) were added, and the mixture was stirred overnight at 60° C. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by flash silica gel column chromatography (eluted with acetone:hexane=1:3, then 3:2). Crystallization from acetone-diethyl ether and recrystallization from acetone-diethyl ether gave the title compound (1.09 g) as a colorless solid. 1H-NMR(CDCl3): 2.22(3H,s), 3.12(3H,bs), 3.50-4.30(2H,br), 4.37(2H,q,J=7.8 Hz), 4.68(2H,m), 4.80-5.20(2H,br), 6.63(1H,d,J=5.7 Hz), 7.26-7.48(5H,m), 7.53-7.61(1H,m), 7.82(1H,d,J=8.1 Hz), 8.04(2H,d,J=7.2 Hz), 8.33(1H,d,J=5.7 Hz). Synthetic Example 5 2-[Methyl[[2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl benzoate To a solution (30 mL) of bis(trichloromethyl)carbonate (0.99 g) in tetrahydrofuran was dropwise added a solution (2 mL) of pyridine (0.81 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., 2-(methylamino)ethyl benzoate hydrochloride (2.16 g) obtained in Reference Example 5 was added. After addition of a solution (2 mL) of triethylamine (1.39 mL) in tetrahydrofuran, the mixture was stirred at room temperature for 1 hr. After concentration under reduced pressure, ethyl acetate (100 mL) and water (100 mL) were added to the residue, and the mixture was stirred. The ethyl acetate layer was separated and taken, washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (40 mL). 2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (2.90 g), triethylamine (2.20 mL) and 4-dimethylaminopyridine (0.096 g) were added, and the mixture was stirred at 60° C. for 2 hr. After concentration under reduced pressure, ethyl acetate (150 mL) and water (80 mL) were added to the residue, and the mixture was stirred. The ethyl acetate layer was separated and taken, washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=1:1, then ethyl acetate). Recrystallization from acetone gave the title compound (2.62 g) as a colorless solid. 1H-NMR(CDCl3): 2.22(3H,s), 3.13(3H,bs), 3.68-3.98(2H,bm), 4.38(2H,q,J=7.8 Hz), 4.69(2H,m), 4.80-5.10(2H,bm), 6.64(1H,d,J=5.7 Hz), 7.27-7.48(5H,m), 7.59(1H,m), 7.83(1H,m), 8.06(2H,d,J=6.0 Hz), 8.35(1H,d,J=5.7 Hz). Synthetic Example 6 2-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl 4-methoxybenzoate To a solution (18 mL) of bis(trichloromethyl)carbonate (0.584 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.49 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 40 min., 2-(methylamino)ethyl 4-methoxybenzoate hydrochloride (1.48 g) obtained in Reference Example 6 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was added and the mixture was stirred at room temperature for 80 min. After concentration under reduced pressure, ethyl acetate (80 mL) and water (50 mL) were added to the residue and the mixture was stirred. The ethyl acetate layer was separated and taken, washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (25 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.55 g), triethylamine (1.17 mL) and 4-dimethylaminopyridine (0.051 g) were added, and the mixture was stirred at 60° C. for 3 hrs. After concentration under reduced pressure, ethyl acetate (150 mL) and water (50 mL) were added to the residue, and the mixture was stirred. The ethyl acetate layer was separated and taken, washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=1:1, then ethyl acetate). Recrystallization from ethyl acetate-hexane gave the title compound (1.08 g) as a colorless solid. 1H-NMR(CDCl3): 2.22(3H,s), 3.11(3H,bs), 3.68-3.90(2H,bm), 3.85(3H,s), 4.37(2H,q,J=7.9 Hz), 4.58-4.72(2H,m), 4.82-5.14(2H,bm), 6.63(1H,d,J=5.7 Hz), 6.91(2H,d,J=9.0 Hz), 7.27-7.40(3H,m), 7.82(1H,m), 7.99(2H,d,J=9.0 Hz), 8.33(1H,d,J=5.7 Hz). Synthetic Example 7 2-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl 3-chlorobenzoate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.582 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.49 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., 2-(methylamino)ethyl 3-chlorobenzoate hydrochloride (1.50 g) obtained in Reference Example 7 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was added and the mixture was stirred at room temperature for 2 hrs. After concentration under reduced pressure, ethyl acetate (80 mL) and water (40 mL) were added to the residue and the mixture was stirred. The ethyl acetate layer was separated and taken, washed with saturated brine (25 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.44 g), triethylamine (1.09 mL) and 4-dimethylaminopyridine (0.048 g) were added, and the mixture was stirred at 60° C. for 3 hrs. After concentration under reduced pressure, ethyl acetate (80 mL) and water (40 mL) were added to the residue and the mixture was stirred. The ethyl acetate layer was separated and taken, washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1) to give the title compound (0.84 g) as colorless syrup. 1H-NMR(CDCl3): 2.21(3H,s), 3.12(3H,bs), 3.78-4.08(2H,bm), 4.38(2H,q,J=7.8 Hz), 4.64-5.08(4H,bm), 6.64(1H,d,J=5.2 Hz), 7.34-7.42(4H,m), 7.56(1H,m), 7.82(1H,m), 7.94(1H,d,J=7.6 Hz), 8.02(1H,s), 8.34(1H,d,J=5.2 Hz). Synthetic Example 8 2-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl 3,4-difluorobenzoate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.582 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.49 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., 2-(methylamino)ethyl 3,4-difluorobenzoate hydrochloride (1.51 g) obtained in Reference Example 8 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was added and the mixture was stirred at room temperature for 3 hrs. After concentration under reduced pressure, ethyl acetate (80 mL) and water (50 mL) were added to the residue and the mixture was stirred. The ethyl acetate layer was separated and taken, washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (25 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.71 g), triethylamine (1.29 mL) and 4-dimethylaminopyridine (0.056 g) were added, and the mixture was stirred at 60° C. for 17 hrs. After concentration under reduced pressure, ethyl acetate (100 mL) and water (50 mL) were added to the residue, and the mixture was stirred. The ethyl acetate layer was separated and taken, and the aqueous layer was extracted with ethyl acetate (20 mL). Ethyl acetate layers were combined, washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=1:1, then 2:1), and by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:1). Crystallization from acetone-diisopropyl ether and recrystallization from ethyl acetate-hexane gave the title compound (1.37 g) as a colorless solid. 1H-NMR(CDCl3): 2.21(3H,s), 3.11(3H,bs), 3.82-4.08(2H,bm), 4.38(2H,q,J=7.8 Hz), 4.60-5.14(4H,bm), 6.63(1H,d,J=5.7 Hz), 7.20(1H,m), 7.33-7.41(3H,m), 7.78-7.92(3H,m), 8.33(1H,d,J=5.7 Hz). Synthetic Example 9 2-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl 4-trifluoromethoxybenzoate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.582 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.49 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., 2-(methylamino)ethyl 4-trifluoromethoxybenzoate hydrochloride (1.79 g) obtained in Reference Example 9 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was added and the mixture was stirred at room temperature for 1.5 hrs. After concentration under reduced pressure, ethyl acetate (80 mL) and water (50 mL) were added to the residue and the mixture was stirred. The ethyl acetate layer was separated and taken, washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (25 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.57 g), triethylamine (1.18 mL) and 4-dimethylaminopyridine (0.052 g) were added, and the mixture was stirred at 60° C. for 4.5 hrs. After concentration under reduced pressure, ethyl acetate (100 mL) and water (50 mL) were added to the residue, and the mixture was stirred. The ethyl acetate layer was separated and taken, and the aqueous layer was extracted with ethyl acetate (30 mL). The ethyl acetate layers were combined, washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=1:1), and further by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:1) to give the title compound (1.44 g) as colorless syrup. 1H-NMR(CDCl3): 2.22(3H,s), 3.11(3H,bs), 3.85-4.05(2H,bm), 4.38(2H,q,J=7.8 Hz), 4.60-5.12(4H,bm), 6.64(1H,d,J=5.7 Hz), 7.24(2H,d,J=8.7 Hz), 7.25-7.40(3H,m), 7.82(1H,d,J=7.2 Hz), 8.09(2H,d,J=8.7 Hz), 8.33(1H,d,J=5.7 Hz). Synthetic Example 10 2-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl 4-fluorobenzoate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.582 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.49 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., 2-(methylamino)ethyl 4-fluorobenzoate hydrochloride (1.40 g) obtained in Reference Example 10 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was added and the mixture was stirred at room temperature for 2 hrs. After concentration under reduced pressure, ethyl acetate (80 mL) and water (40 mL) were added to the residue and the mixture was stirred. The ethyl acetate layer was separated and taken, washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.32 g), triethylamine (1.00 mL) and 4-dimethylaminopyridine (0.049 g) were added, and the mixture was stirred at 60° C. for 14.5 hrs. After concentration under reduced pressure, ethyl acetate (150 mL) and water (50 mL) were added to the residue, and the mixture was stirred. The ethyl acetate layer was separated and taken, washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was crystallized from ethyl acetate:hexane=1:1 and collected by filtration. Recrystallization from acetone gave the title compound (1.39 g) as a colorless solid. 1H-NMR(CDCl3): 2.22(3H,s), 3.12(3H,bs), 3.78-4.20(2H,bm), 4.38(2H,q,J=7.8 Hz), 4.58-5.08(4H,bm), 6.65(1H,d,J=5.6 Hz), 7.11(2H,t,J=8.4 Hz), 7.28-7.44(3H,m), 7.81-7.86(1H,m), 8.03-8.11(2H,m), 8.35(1H,d,J=5.6 Hz). Synthetic Example 11 2-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl 3,4,5-trimethoxybenzoate To a solution (30 mL) of bis(trichloromethyl)carbonate (0.60 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.49 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 10 min., 2-(methylamino)ethyl 3,4,5-teimethoxybenzoate hydrochloride (1.22 g) obtained in Reference Example 11 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was dropwise added and the mixture was stirred at room temperature for 1 hr. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with dilute hydrochloric acid (20 mL) and saturated brine (50 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.11 g), triethylamine (0.84 mL) and 4-dimethylaminopyridine (0.037 g) were added, and the mixture was stirred at 60° C. for 3 hrs. and at room temperature for 2 days. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by flash silica gel column chromatography (eluted with acetone:hexane=1:3, then 3:2) to give the title compound (1.56 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 2.21(3H,s), 3.12(3H,bs), 3.50-4.30(2H,br), 3.83(6H,s), 3.90(3H,s), 4.38(2H,q,J=7.8 Hz), 4.67(2H,m), 4.80-5.15(2H,br), 6.64(1H,d,J=5.7 Hz), 7.25-7.40(5H,m), 7.78-7.86(1H,m), 8.33(1H,d,J=5.7 Hz). Synthetic Example 12 2-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl 2-pyridinecarboxylate To a solution (30 mL) of bis(trichloromethyl)carbonate (0.422 g) in tetrahydrofuran was dropwise added pyridine (0.345 mL) under ice-cooling. After stirring under ice-cooling for 30 min., 2-(methylamino)ethyl 2-pyridinecarboxylate dihydrochloride (1.08 g) obtained in Reference Example 12 was added. After dropwise addition of triethylamine (1.19 mL), the mixture was stirred at room temperature for 2 hrs. The precipitated solid was filtered off and the filtrate was concentrated under reduced pressure. The residue was dissolved in tetrahydrofuran (10 mL), and (R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.31 g), triethylamine (0.99 mL) and 4-dimethylaminopyridine (0.043 g) were added. The mixture was stirred at 60° C. for 24 hrs. Ethyl acetate (100 mL) was added to the reaction mixture, and the mixture was washed with water (100 mL) and saturated brine (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=4:1). Crystallization from acetone-diethyl ether gave the title compound (0.9 g) as a white solid. 1H-NMR(CDCl3): 2.22(3H,s), 3.16(3H,s), 3.80-4.20(2H,m), 4.38(2H,q,J=7.8 Hz), 4.60-5.10(4H,m), 6.64(1H,d,J=5.8 Hz), 7.29-7.40(2H,m), 7.47-7.52(2H,m), 7.81-7.89(2H,m), 8.14(1H,d,J=7.8 Hz), 8.34(1H,d,J=5.8 Hz), 8.75-8.79(1H,m). Synthetic Example 13 2-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl methoxyacetate To a solution (15 mL) of bis(trichloromethyl)carbonate (0.652 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.55 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., 2-(methylamino)ethyl methoxyacetate (0.99 g) obtained in Reference Example 13 was added. The mixture was stirred at room temperature for 3 hrs. After concentration under reduced pressure, ethyl acetate (80 mL) and water (50 mL) were added to the residue and the mixture was stirred. The ethyl acetate layer was separated and taken, washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (15 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.13 g), triethylamine (0.86 mL) and 4-dimethylaminopyridine (0.037 g) were added, and the mixture was stirred at 60° C. for 4 days. After concentration under reduced pressure, ethyl acetate (80 mL) and water (30 mL) were added to the residue, and the mixture was stirred. The ethyl acetate layer was separated and taken, and the ethyl acetate layer was washed with a saturated aqueous sodium hydrogen carbonate solution (30 mL) and water (30 mL), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (eluted with ethyl acetate, then acetone:ethyl acetate=1:3), and further by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:1, then 3:1) to give the title compound (0.588 g) as colorless syrup. 1H-NMR(CDCl3): 2.32(3H,s), 2.68(3H,s), 3.48(3H,s), 3.69-4.02(4H,m), 4.38(2H,q,J=7.8 Hz), 4.67(2H,t,J=6.6 Hz), 4.99(1H,d,J=13.9 Hz), 5.12(1H,d,J=13.9 Hz), 6.63(1H,d,J=5.7 Hz), 7.29-7.46(2H,m), 7.62(1H,m), 7.81(1H,m), 8.25(1H,d,J=5.7 Hz). Synthetic Example 14 Ethyl 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate To a solution (40 mL) of bis(trichloromethyl)carbonate (1.31 g) in tetrahydrofuran was dropwise added a solution (2 mL) of pyridine (1.07 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 10 min., ethyl 2-(methylamino)ethyl carbonate hydrochloride (2.02 g) obtained in Reference Example 14 was added. A solution (2 mL) of triethylamine (1.84 mL) in tetrahydrofuran was dropwise added and the mixture was stirred at room temperature for 1 hr. After concentration under reduced pressure, water (100 mL) was added to the residue, and the mixture was extracted with ethyl acetate (100 mL). The ethyl acetate layer was washed with 0.2N hydrochloric acid (50 mL) and saturated brine (100 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (50 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (3.69 g), triethylamine (2.09 mL) and 4-dimethylaminopyridine (0.12 g) were added, and the mixture was stirred at 60° C. for 6 hrs. and at room temperature for 8 hrs. After concentration under reduced pressure, water (100 mL) was added to the residue, and the mixture was extracted with ethyl acetate (100 mL). The ethyl acetate layer was washed with saturated brine (100 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=3:7, then ethyl acetate). Crystallization from diethyl ether and recrystallization from diethyl ether gave the title compound (3.84 g) as a colorless solid. 1H-NMR(CDCl3): 1.32(3H,t,J=7.2 Hz), 2.23(3H,s), 3.10(3H,bs), 3.50-4.20(2H,br), 4.22(2H,q,J=7.2 Hz), 4.39(2H,q,J=7.9 Hz), 4.45(2H,m), 4.80-5.15(2H,br), 6.65(1H,d,J=5.6 Hz), 7.36-7.50(3H,m), 7.84(1H,d,J=7.8 Hz), 8.35(1H,d,J=5.6 Hz). Synthetic Example 15 Isopropyl 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate To a solution (30 mL) of bis(trichloromethyl)carbonate (0.50 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.40 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 1 hr., isopropyl 2-(methylamino)ethyl carbonate hydrochloride (0.99 g) obtained in Reference Example 15 was added. A solution (1 mL) of triethylamine (0.70 mL) in tetrahydrofuran was dropwise added and the mixture was stirred at room temperature for 1 hr. Bis(trichloromethyl)carbonate (0.50 g), a solution (1 mL) of pyridine (0.40 mL) in tetrahydrofuran and a solution (1 mL) of triethylamine (0.70 mL) in tetrahydrofuran were successively added and the mixture was stirred at room temperature for 1 hr. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.11 g), triethylamine (0.84 mL) and 4-dimethylaminopyridine (0.037 g) were added, and the mixture was stirred at 60° C. for 12 hrs. and at room temperature for 3 days. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by flash silica gel column chromatography (eluted with acetone:hexane=1:3, then 3:2), and further by basic silica gel column chromatography (eluted with ethyl acetate:hexane=3:7, then ethyl acetate). Crystallization from diethyl ether and recrystallization from acetone-diisopropyl ether gave the title compound (0.58 g) as a colorless solid. 1H-NMR(CDCl3): 1.31(6H,d,J=6.3 Hz), 2.23(3H,s), 3.08(3H,bs), 3.40-4.30(2H,br), 4.37(2H,q,J=7.9 Hz), 4.32-4.53(2H,m), 4.80-5.20(3H,m), 6.63(1H,d,J=5.7 Hz), 7.35-7.50(3H,m), 7.83(1H,d,J=7.2 Hz), 8.34(1H,d,J=5.7 Hz). Synthetic Example 16 Isopropyl 2-[methyl[[2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.582 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.49 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., isopropyl 2-(methylamino)ethyl carbonate hydrochloride (1.18 g) obtained in Reference Example 15 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was added and the mixture was stirred at room temperature for 2 hrs. After concentration under reduced pressure, ethyl acetate (80 mL) and water (30 mL) were added to the residue, and the mixture was stirred. The ethyl acetate layer was separated and taken, washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (25 mL). 2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.73 g), triethylamine (1.31 mL) and 4-dimethylaminopyridine (0.057 g) were added, and the mixture was stirred at 60° C. for 5 hrs. After concentration under reduced pressure, ethyl acetate (100 mL) and water (50 mL) were added to the residue, and the mixture was stirred. The ethyl acetate layer was separated and taken, washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:1), and further by silica gel column chromatography (eluted with ethyl acetate:hexane=1:1, then 2:1). Crystallization from diisopropyl ether-hexane and recrystallization from diisopropyl ether gave the title compound (1.20 g) as a colorless solid. 1H-NMR(CDCl3): 1.31(6H,d,J=6.6 Hz), 2.23(3H,s), 3.08(3H,bs), 3.50-3.90(2H,bm), 4.38(2H,q,J=7.8 Hz), 4.36-4.58(2H,bm), 4.79-5.15(3H,m), 6.64(1H,d,J=5.7 Hz), 7.35-7.48(3H,m), 7.83(1H,d,J=7.5 Hz), 8.34(1H,d,J=5.7 Hz). Synthetic Example 17 Benzyl 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate To a solution (30 mL) of bis(trichloromethyl)carbonate (0.50 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.40 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 1 hr., benzyl 2-(methylamino)ethyl carbonate hydrochloride (1.08 g) obtained in Reference Example 16 was added. A solution (1 mL) of triethylamine (0.70 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred overnight at room temperature. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.11 g), triethylamine (0.84 mL) and 4-dimethylaminopyridine (0.037 g) were added, and the mixture was stirred overnight at 60° C. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by flash silica gel column chromatography (eluted with acetone:hexane=1:3, then 3:2). Crystallization from acetone-diethyl ether and recrystallization from acetone-diethyl ether gave the title compound (1.17 g) as a colorless solid. 1H-NMR(CDCl3): 2.22(3H,s), 3.05(3H,bs), 3.50-4.20(2H,br), 4.37(2H,q,J=7.8 Hz), 4.46(2H,m), 4.80-5.10(2H,br), 5.17(2H,s), 6.62(1H,d,J=5.6 Hz), 7.26-7.48(8H,m), 7.77-7.88(1H,m), 8.33(1H,d,J=5.6 Hz). Synthetic Example 18 2-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl tetrahydropyran-4-yl carbonate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.48 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.39 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 20 min., 2-(methylamino)ethyl tetrahydropyran-4-yl carbonate hydrochloride (0.96 g) obtained in Reference Example 17 was added. A solution (1 mL) of triethylamine (0.67 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 2 hrs. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with 0.2N hydrochloric acid (20 mL) and saturated brine (50 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.26 g), triethylamine (0.71 mL) and 4-dimethylaminopyridine (0.042 g) were added, and the mixture was stirred at 60° C. for 6 hrs. and at room temperature for 8 hrs. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=3:7, then ethyl acetate). Crystallization from diethyl ether and recrystallization from acetone-diisopropyl ether gave the title compound (1.45 g) as a colorless solid. 1H-NMR(CDCl3): 1.64-1.81(2H,m), 1.92-2.03(2H,m), 2.23(3H,s), 3.09(3H,bs), 3.40-4.30(2H,br), 3.45-3.57(2H,m), 3.87-3.97(2H,m), 4.38(2H,q,J=7.8 Hz), 4.45(2H,m), 4.77-5.15(3H,m), 6.64(1H,d,J=5.7 Hz), 7.35-7.50(3H,m), 7.83(1H,d,J=6.9 Hz), 8.35(1H,d,J=5.7 Hz). Synthetic Example 19 2-Methoxyethyl 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.59 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.49 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 10 min., 2-methoxyethyl 2-(methylamino)ethyl carbonate hydrochloride (1.07 g) obtained in Reference Example 18 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was dropwise added and the mixture was stirred at room temperature for 1 hr. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with 0.2N hydrochloric acid (20 mL) and saturated brine (50 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.85 g), triethylamine (1.05 mL) and 4-dimethylaminopyridine (0.061 g) were added, and the mixture was stirred at 60° C. for 6 hrs. and at room temperature for 8 hrs. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=3:7, then ethyl acetate). Crystallization from ethyl acetate-diethyl ether and recrystallization from ethyl acetate-diisopropyl ether gave the title compound (1.39 g) as a colorless solid. 1H-NMR(CDCl3): 2.23(3H,s), 3.09(3H,bs), 3.37(3H,s), 3.50-4.20(2H,br), 3.59-3.65(2H,m), 4.28-4.33(2H,m), 4.38(2H,q,J=7.8 Hz), 4.46(2H,m), 4.80-5.15(2H,br), 6.64(1H,d,J=5.7 Hz), 7.35-7.47(3H,m), 7.83(1H,d,J=7.8 Hz), 8.34(1H,d,J=5.7 Hz). Synthetic Example 20 2-[Ethyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl acetate To a solution (30 mL) of bis(trichloromethyl)carbonate (0.59 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.49 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 10 min., 2-(ethylamino)ethyl acetate hydrochloride (0.67 g) obtained in Reference Example 20 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was dropwise added and the mixture was stirred at room temperature for 1 hr. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.11 g), triethylamine (0.84 mL) and 4-dimethylaminopyridine (0.037 g) were added, and the mixture was stirred overnight at 60° C. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=3:7, then ethyl acetate) to give the title compound (1.58 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 1.25(3H,m), 2.08(3H,s), 2.23(3H,s), 3.30-4.10(4H,br), 4.23-4.45(2H,m), 4.38(2H,q,J=7.8 Hz), 4.75-5.20(2H,br), 6.64(1H,d,J=5.7 Hz), 7.35-7.46(3H,m), 7.84(1H,d,J=6.9 Hz), 8.36(1H,d,J=5.7 Hz). Synthetic Example 21 2-[Isopropyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl acetate To a solution (10 mL) of bis(trichloromethyl)carbonate (0.543 g) in tetrahydrofuran was dropwise added a solution (5 mL) of pyridine (0.445 mL) in tetrahydrofuran under ice-cooling, and the mixture was stirred at 0° C. for 30 min. 2-(Isopropylamino)ethyl acetate hydrochloride (1.0 g) obtained in Reference Example 22 was added. A solution (5 mL) of triethylamine (0.805 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 30 min. The reaction mixture was concentrated under reduced pressure, water (30 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (30 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained oil was dissolved in tetrahydrofuran (5 mL), and added to a solution (20 mL) of (R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.73 g), triethylamine (1.53 mL) and 4-dimethylaminopyridine (0.134 g) in tetrahydrofuran. The mixture was stirred at 40° C. for 12 hrs. The reaction mixture was concentrated under reduced pressure and water (30 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (30 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=2:1, then ethyl acetate) to give the title compound (1.50 g) as a pale-yellow amorphous solid. 1H-NMR(CDCl3): 1.20-1.40(6H,m), 2.05(3H×0.4,s), 2.11(3H×0.6,s), 2.18(3H×0.6,s), 2.27(3H×0.4,s), 3.40-3.60(1H,m), 3.70-4.60(6H,m), 4.70-5.25(2H,m), 6.65(1H,d,J=5.8 Hz), 7.30-7.50(3H,m), 7.75-7.90(1H,m), 8.37(1H,d,J=5.8 Hz). Synthetic Example 22 Ethyl 2-[isopropyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate To a solution (10 mL) of bis(trichloromethyl)carbonate (0.467 g) in tetrahydrofuran was dropwise added a solution (5 mL) of pyridine (0.381 mL) in tetrahydrofuran under ice-cooling, and the mixture was stirred at 0° C. for 30 min. Ethyl 2-(isopropylamino)ethyl carbonate hydrochloride (1.0 g) obtained in Reference. Example 23 was added to the reaction mixture. A solution (5 mL) of triethylamine (0.69 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at 0° C. for 15 min. and at room temperature for 30 min. The reaction mixture was concentrated under reduced pressure and water (30 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (30 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained oil was dissolved in tetrahydrofuran (5 mL), and added to a solution (20 mL) of (R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.48 g), triethylamine (1.32 mL) and 4-dimethylaminopyridine (0.115 g) in tetrahydrofuran, and the mixture was stirred at 40° C. for 12 hrs. The reaction mixture was concentrated under reduced pressure and water (30 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (30 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=2:1, then ethyl acetate) to give the title compound (1.20 g) as a pale-yellow amorphous solid. 1H-NMR(CDCl3): 1.20-1.40(9H,m), 2.17(3H×0.6,s), 2.27(3H×0.4,s), 3.40-3.70(1H,m), 3.75-4.65(8H,m), 4.70-5.30(2H,m), 6.64(1H,d,J=5.8 Hz), 7.35-7.55(3H,m), 7.75-7.90(1H,m), 8.38(1H,d,J=5.8 Hz). Synthetic Example 23 2-[Cyclohexyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl acetate To a solution (10 mL) of bis(trichloromethyl)carbonate (0.593 g) in tetrahydrofuran was dropwise added pyridine (0.485 mL) under ice-cooling. After stirring under ice-cooling for 30 min., 2-(cyclohexylamino)ethyl acetate hydrochloride (1.33 g) obtained in Reference Example 25 was added. Triethylamine (0.84 mL) was dropwise added, and the mixture was stirred at room temperature for 2 hrs. Ethyl acetate (50 mL) was added to the reaction mixture and the mixture was washed with water (50 mL) and saturated brine (50 mL), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was dissolved in tetrahydrofuran (20 mL), and (R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.61 g), triethylamine (1.21 mL) and 4-dimethylaminopyridine (0.053 g) were added. The mixture was stirred at 60° C. for 24 hrs. Ethyl acetate (50 mL) was added to the reaction mixture, and the mixture was washed with water (20 mL) and saturated brine (50 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by flash silica gel column chromatography (eluted with ethyl acetate:hexane=1:4, then ethyl acetate) to give the title compound (2.12 g) as a pale-yellow amorphous solid. 1H-NMR(CDCl3): 1.00-2.42(16H,m), 3.30-3.70(2H,m), 3.80-4.00(1H,m), 4.27-4.42(2H,m), 4.40(2H,q,J=8.2 Hz), 4.78(1H×0.5,d,J=13.2 Hz), 4.97(2H×0.5,s), 5.20(1H×0.5,d,J=13.2 Hz), 6.67(1H,d,J=5.8 Hz), 7.36-7.46(3H,m), 7.81-7.91(1H,m), 8.39(1H,d,J=5.8 Hz). Synthetic Example 24 2-[Cyclohexyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl ethyl carbonate To a solution (10 mL) of bis(trichloromethyl)carbonate (0.238 g) in tetrahydrofuran was dropwise added pyridine (0.20 mL) under ice-cooling. After stirring under ice-cooling for 30 min., 2-(cyclohexylamino)ethyl ethyl carbonate hydrochloride (0.605 g) obtained in Reference Example 26 was added. Triethylamine (0.335 mL) was dropwise added, and the mixture was stirred at room temperature for 2 hrs. Ethyl acetate (50 mL) was added to the reaction mixture, and the mixture was washed with water (50 mL) and saturated brine (50 mL), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was dissolved in tetrahydrofuran (10 mL), and (R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (0.60 g), triethylamine (0.45 mL) and 4-dimethylaminopyridine (0.02 g) were added. The mixture was stirred at 60° C. for 24 hrs. Ethyl acetate (50 mL) was added to the reaction mixture, and the mixture was washed with water (20 mL) and saturated brine (50 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by flash silica gel column chromatography (eluted with ethyl acetate:hexane=1:4, then ethyl acetate) to give the title compound (0.92 g) as a pale-yellow amorphous solid. 1H-NMR(CDCl3): 1.02-2.27(16H,m), 3.40-4.60(9H,m), 4.78(1H×0.5,d,J=13.2 Hz), 4.97(2H×0.5,s), 5.44(1H×0.5,d,J=13.2 Hz), 6.69(1H,d,J=5.6 Hz), 7.32-7.54(3H,m), 7.80-7.91(1H,m), 8.38(1H,d,J=5.6 Hz). Synthetic Example 25 2-[[[(R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](phenyl)amino]ethyl acetate To a solution (350 mL) of bis(trichloromethyl)carbonate (13.4 g) in tetrahydrofuran was dropwise added pyridine (10.38 mL) under ice-cooling. After stirring under ice-cooling for 30 min., 2-anilinoethyl acetate hydrochloride (25.9 g) obtained in Reference Example 27 was added. Triethylamine (18.4 mL) was dropwise added, and the mixture was stirred at room temperature for 2 hrs. After concentration under reduced pressure, ethyl acetate (500 mL) and water (500 mL) were added to the residue, and the mixture was stirred. The ethyl acetate layer was separated and taken, washed with saturated brine (500 mL), dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give 2-[(chlorocarbonyl)(phenyl)amino]ethyl acetate. This was dissolved in tetrahydrofuran (300 mL), (R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (41.2 g), triethylamine (15.6 mL) and 4-dimethylaminopyridine (1.363 g) were added, and the mixture was stirred at 60° C. for 3 hrs. Ethyl acetate (800 mL) was added to the reaction mixture, and the mixture was washed twice with water (800 mL) and with saturated brine (800 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=3:7, then 1:1). Crystallization from diethyl ether gave the title compound (54.1 g) as a white solid. 1H-NMR(CDCl3): 2.00(3H,s), 2.25(3H,s), 4.15-4.48(6H,m), 4.83(1H,d,J=13.6 Hz), 5.05(1H,d,J=13.6 Hz), 6.67(1H,d,J=5.4 Hz), 7.03-7.45(8H,m), 7.64-7.69(1H,m), 8.40(1H,d,J=5.4 Hz). Synthetic Example 26 2-[[[2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](phenyl)amino]ethyl acetate To a solution (10 mL) of 2-[(chlorocarbonyl)(phenyl)amino]ethyl acetate (0.58 g) prepared in the same manner as in Synthetic Example 25 in tetrahydrofuran were added 2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (0.739 g), triethylamine (0.558 mL) and 4-dimethylaminopyridine (0.024 g), and the mixture was stirred at 60° C. for 15 hrs. Ethyl acetate (30 mL) was added to the reaction mixture, and the mixture was washed with water (50 mL) and saturated brine (50 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by flash silica gel column chromatography (eluted with acetone:hexane=1:4, then 3:2). Crystallization from diethyl ether gave the title compound (0.779 g) as a white solid. 1H-NMR(CDCl3): 1.99(3H,s), 2.25(3H,s), 4.20-4.48(6H,m), 4.83(1H,d,J=13.6 Hz), 5.05(1H,d,J=13.6 Hz), 6.67(1H,d,J=5.8 Hz), 7.03-7.45(8H,m), 7.64-7.69(1H,m), 8.40(1H,d,J=5.8 Hz). Synthetic Example 27 tert-Butyl [2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]-3-pyridyl]methyl carbonate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.30 g) in tetrahydrofuran was dropwise added pyridine (0.24 mL) under ice-cooling. After stirring under ice-cooling for 30 min., tert-butyl [2-(methylamino)-3-pyridyl]methyl carbonate (0.71 g) obtained in Reference Example 28 was added, and the mixture was stirred at room temperature for 2 hrs. The precipitated solid was filtered off and the filtrate was concentrated under reduced pressure. The residue was dissolved in tetrahydrofuran (20 mL), (R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (0.92 g), triethylamine (0.70 mL) and 4-dimethylaminopyridine (0.031 g) were added, and the mixture was stirred at 60° C. for 1 hr. Water (50 mL) was added to the reaction mixture and the mixture was extracted twice with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by flash silica gel column chromatography (eluted with acetone:hexane=1:2), and further by basic silica gel column chromatography (eluted with ethyl acetate) to give the title compound (0.38 g) as a pale-yellow amorphous solid. 1H-NMR(CDCl3): 1.46(9H,s), 2.25(3H,s), 3.54(3H,s), 4.37(2H,q,J=8.0 Hz), 4.95(2H,s), 5.15(1H,d,J=14.0 Hz), 5.27(1H,d,J=14.0 Hz), 6.63(1H,d,J=5.4 Hz), 7.26-7.45(3H,m), 7.69-7.87(3H,m), 8.33(1H,d,J=5.4 Hz), 8.44-8.46(1H,m). Synthetic Example 28 2-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]benzyl acetate To a solution (30 mL) of bis(trichloromethyl)carbonate (1.46 g) in tetrahydrofuran was dropwise added pyridine (1.16 mL) under ice-cooling. After stirring under ice-cooling for 30 min., 2-(methylamino)benzyl acetate (2.57 g) obtained in Reference Example 29 was added. The mixture was stirred at room temperature for 3 hrs. The precipitated solid was filtered off and the filtrate was concentrated under reduced pressure. The residue was dissolved in tetrahydrofuran (40 mL), (R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (4.41 g), triethylamine (3.33 mL) and 4-dimethylaminopyridine (0.15 g) were added, and the mixture was stirred at 60° C. for 18 hrs. Water (100 mL) was added to the reaction mixture, and the mixture was extracted with ethyl acetate (100 mL). The ethyl acetate layer was washed with saturated brine (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by flash silica gel column chromatography (eluted with acetone:hexane=1:4, then 1:2). Crystallization from ethyl acetate-diethyl ether-hexane gave the title compound (2.76 g) as a white solid. 1H-NMR(CDCl3): 2.10(3H,s), 2.00-2.30(3H,br), 3.20-3.50(3H,br), 4.38(2H,q,J=7.6 Hz), 4.70-5.20(2H,m), 5.20-5.50(2H,m), 6.65(1H,d,J=5.4 Hz), 7.10-7.82(8H,m), 8.38(1H,d,J=5.4 Hz). Synthetic Example 29 2-[[2-(Acetyloxy)ethyl][[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl acetate To a solution (30 mL) of bis(trichloromethyl)carbonate (0.50 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.40 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 10 min., 2-[(2-acetyloxyethyl)amino]ethyl acetate hydrochloride (1.13 g) obtained in Reference Example 30 was added. A solution (1 mL) of triethylamine (0.70 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 2 hrs. The precipitated solid was filtered off and the filtrate was concentrated under reduced pressure. Ethyl acetate (20 mL) was added to the residue, the precipitated solid was filtered off and the filtrate was concentrated under reduced pressure. The residue was dissolved in tetrahydrofuran (30 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.48 g), triethylamine (1.12 mL) and 4-dimethylaminopyridine (catalytic amount) were added, and the mixture was stirred at 60° C. overnight. After concentration under reduced pressure, water (50 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=1:1, then ethyl acetate), and further by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:1, then ethyl acetate). The resulting product was dissolved in ethyl acetate (20 mL), activated carbon was added and the mixture was stirred overnight. The activated carbon was filtered off and the filtrate was concentrated under reduced pressure to give the title compound (1.60 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 2.06(3H,s), 2.08(3H, s), 2.24(3H,s), 3.40-4.45(8H,m), 4.39(2H,q,J=7.9 Hz), 4.88(1H,d,J=13.2 Hz), 5.05(1H,d,J=13.2 Hz), 6.66(1H,d,J=5.6 Hz), 7.38-7.50(3H,m), 7.87(1H,d,J=6.9 Hz), 8.36(1H,d,J=5.6 Hz). Synthetic Example 30 [(2S)-1-[[(R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]-2-pyrrolidinyl]methyl acetate To a solution (30 mL) of bis(trichloromethyl)carbonate (0.50 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.40 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 1 hr., (S)-2-pyrrolidinylmethyl acetate hydrochloride (0.90 g) obtained in Reference Example 31 was added. A solution (1 mL) of triethylamine (0.70 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 2 hrs. After concentration under reduced pressure, water (50 mL) was added to the residue, and the mixture was extracted with ethyl acetate (50 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.11 g), triethylamine (0.84 mL) and 4-dimethylaminopyridine (0.037 g) were added, and the mixture was stirred at 60° C. for 1 day and at room temperature for 2 days. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:1, then ethyl acetate) and further by silica gel column chromatography (eluted with ethyl acetate:hexane=3:1, then ethyl acetate, then acetone:ethyl acetate=1:4, then 2:3) to give the title compound (0.80 g) as a pale-yellow amorphous solid. 1H-NMR(CDCl3): 1.80-2.30(4H,m), 2.09(3H,s), 2.30(3H,s), 3.39(1H,m), 3.50-3.62(1H,m), 4.20-4.45(4H,m), 4.58(1H,m), 4.89(1H,d,J=13.5 Hz), 4.96(1H,d,J=13.5 Hz), 6.65(1H,d,J=5.9 Hz), 7.36-7.48(3H,m), 7.89(1H,d,J=8.7 Hz), 8.38(1H,d,J=5.9 Hz) Synthetic Example 31 Ethyl [methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]acetate To a solution (30 mL) of bis(trichloromethyl)carbonate (0.50 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.40 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., sarcosine ethyl ester hydrochloride (0.77 g) was added. A solution (1 mL) of triethylamine (0.70 mL) in tetrahydrofuran was dropwise added and the mixture was stirred at room temperature for 1 hr. The precipitated solid was filtered off and the filtrate was concentrated under reduced pressure. Water (50 mL) was added to the residue, and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (33 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole sodium (1.37 g) and 4-dimethylaminopyridine (catalytic amount) were added, and the mixture was stirred at 60° C. overnight. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:1, then ethyl acetate) to give the title compound (0.40 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 1.33(3H,t,J=7.1 Hz), 2.24(3H,s), 3.10(3H,bs), 3.70-4.30(2H,br), 4.28(2H,q,J=7.1 Hz), 4.38(2H,q,J=7.8 Hz), 4.82-5.10(2H,br), 6.63(1H,d,J=5.5 Hz), 7.34-7.52(2H,m), 7.70-7.90(2H,m), 8.32(1H,d,J=5.5 Hz). Synthetic Example 32 2-[[[5-Methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-benzoimidazol-1-yl]carbonyl](methyl)amino]ethyl benzoate To a solution (10 mL) of bis(trichloromethyl)carbonate (0.344 g) in tetrahydrofuran was dropwise added a solution (5 mL) of pyridine (0.281 mL) in tetrahydrofuran under ice-cooling, and the mixture was stirred at 0° C. for 30 min. 2-(Methylamino)ethyl benzoate hydrochloride (0.750 g) obtained in Reference Example 5 was added. A solution (5 mL) of triethylamine (0.485 mL) in tetrahydrofuran was added, and the mixture was stirred at 0° C. for 1 hr. and at room temperature for 30 min. The reaction mixture was concentrated under reduced pressure and water (30 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (30 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained oil was dissolved in tetrahydrofuran (5 mL), added to a solution (10 mL) of 5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-benzoimidazole (1.0 g), triethylamine (0.808 mL) and 4-dimethylaminopyridine (0.071 g) in tetrahydrofuran, and the mixture was stirred at 40° C. for 18 hrs. The reaction mixture was concentrated under reduced pressure and water (30 mL) was added to the residue. The mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (30 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=1:1, then ethyl acetate) to give a 1:1 mixture (1.50 g) of the title compound and 2-[[[6-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-benzoimidazol-1-yl]carbonyl](methyl)amino]ethyl benzoate as a pale-yellow amorphous solid. 1H-NMR(CDCl3): 2.05-2.35(6H,m), 3.00-3.30(3H,br), 3.60-4.40(8H,m), 4.60-5.10(4H,m), 6.80-7.00(2H,m), 7.20-7.70(4H,m), 7.95-8.25(3H,m). Synthetic Example 33 3-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]propyl benzoate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.582 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.485 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 1 hr., 3-(methylamino)propyl benzoate hydrochloride (1.38 g) obtained in Reference Example 32 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 2 hrs. After concentration under reduced pressure, water (40 mL) was added to the residue, and the mixture was extracted with ethyl acetate (80 mL). The ethyl acetate layer was washed with saturated brine (25 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.63 g), triethylamine (1.23 mL) and 4-dimethylaminopyridine (0.054 g) were added, and the mixture was stirred at 60° C. for 4 hrs. After concentration under reduced pressure, water (40 mL) was added to the residue, and the mixture was extracted with ethyl acetate (80 mL). The ethyl acetate layer was washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1) to give the title compound (1.26 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 2.21(3H,s), 2.20-2.30(2H,bm), 3.06(3H,bs), 3.60-3.75(2H,bm), 4.36(2H,q,J=7.8 Hz), 4.30-4.50(2H,bm), 4.80-5.15(2H,bm), 6.62(1H,d,J=5.7 Hz), 7.26-7.44(5H,m), 7.54(1H,m), 7.81(1H,m), 7.93-8.03(2H,bm), 8.35(1H,d,J=5.7 Hz). Synthetic Example 34 2-[Methyl[[2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl tetrahydropyran-4-yl carbonate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.582 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.485 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 20 min., 2-(methylamino)ethyl tetrahydropyran-4-yl carbonate hydrochloride (1.43 g) obtained in Reference Example 17 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 3 hrs. After concentration under reduced pressure, water (30 mL) was added to the residue, and the mixture was extracted with ethyl acetate (80 mL). The ethyl acetate layer was washed with saturated brine (20 mL), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was dissolved in tetrahydrofuran (20 mL). 2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.63 g), triethylamine (1.23 mL) and 4-dimethylaminopyridine (0.027 g) were added, and the mixture was stirred at 60° C. for 17.5 hrs. After concentration under reduced pressure, water (50 mL) was added to the residue, and the mixture was extracted with ethyl acetate (120 mL). The ethyl acetate layer was washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1), then by silica gel column chromatography (eluted with ethyl acetate:hexane=1:1, then 2:1). Crystallization from diethyl ether gave the title compound (1.23 g) as a colorless solid. 1H-NMR(CDCl3): 1.64-1.81(2H,m), 1.92-2.03(2H,m), 2.23(3H,s), 3.10(3H,bs), 3.40-4.30(2H,br), 3.46-3.59(2H,m), 3.87-3.99(2H,m), 4.39(2H,q,J=7.9 Hz), 4.45(2H,m), 4.77-5.15(3H,m), 6.65(1H,d,J=5.4 Hz), 7.35-7.50(3H,m), 7.85(1H,m), 8.36(1H,d,J=5.4 Hz). Synthetic Example 35 Ethyl 2-[methyl[[2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.582 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.485 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., ethyl 2-(methylamino)ethyl carbonate hydrochloride (1.10 g) obtained in Reference Example 14 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 3 hrs. After concentration under reduced pressure, water (30 mL) was added to the residue, and the mixture was extracted with ethyl acetate (80 mL). The ethyl acetate layer was washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). 2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.63 g), triethylamine (1.23 mL), 4-dimethylaminopyridine (0.054 g) was added, and the mixture was stirred at 60° C. for 14 hrs. After concentration under reduced pressure, water (40 μL) was added to the residue, and the mixture was extracted with ethyl acetate (100 mL). The ethyl acetate layer was washed with saturated brine (30 mL), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1), and then by silica gel column chromatography (eluted with ethyl acetate:hexane=1:1, then 2:1) to give the title compound (1.27 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 1.32(3H,t,J=7.1 Hz), 2.23(3H,s), 3.09(3H,bs), 3.50-4.76(4H,br), 4.21(2H,q,J=7.1 Hz), 4.38(2H,q,J=7.9 Hz), 4.84-5.14(2H,m), 6.64(1H,d,J=5.6 Hz), 7.36-7.46(3H,m), 7.83(1H,d,J=7.2 Hz), 8.34(1H,d,J=5.6 Hz). Synthetic Example 36 Ethyl 2-[methyl[[(S)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.582 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.485 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 1 hr., ethyl 2-(methylamino)ethyl carbonate hydrochloride (1.10 g) obtained in Reference Example 14 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 2 hrs. After concentration under reduced pressure, water (30 mL) was added to the residue, and the mixture was extracted with ethyl acetate (80 mL). The ethyl acetate layer was washed with saturated brine (30 mL), and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (S)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.15 g), triethylamine (0.87 mL) and 4-dimethylaminopyridine (0.035 g) were added, and the mixture was stirred at 60° C. for 12 hrs. After concentration under reduced pressure, water (30 mL) was added to the residue, and the mixture was extracted with ethyl acetate (100 mL). The ethyl acetate layer was washed with saturated brine (30 mL), and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1). Crystallization from diethyl ether gave the title compound (0.40 g) as a colorless solid. 1H-NMR(CDCl3): 1.32(3H,t,J=7.2 Hz), 2.23(3H,s), 3.10(3H,bs), 3.50-4.56(4H,br), 4.22(2H,q,J=7.2 Hz), 4.38(2H,q,J=7.9 Hz), 4.84-5.14(2H,m), 6.65(1H,d,J=5.6 Hz), 7.34-7.50(3H,m), 7.85(1H,m), 8.36(1H,d,J=5.6 Hz). Synthetic Example 37 Ethyl 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-3H-imidazo[4,5-b]pyridin-3-yl]carbonyl](methyl)amino]ethyl carbonate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.582 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.485 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., ethyl 2-(methylamino)ethyl carbonate hydrochloride (1.10 g) obtained in Reference Example 14 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 2.5 hrs. After concentration under reduced pressure, water (30 mL) was added to the residue, and the mixture was extracted with ethyl acetate (80 mL). The ethyl acetate layer was washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). 5-Methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-imidazo[4,5-b]pyridine (1.44 g) synthesized by the method described in JP-A-63-146882, triethylamine (1.16 mL) and 4-dimethylaminopyridine (0.049 g) were added, and the mixture was stirred at 60° C. for 6 hrs. After concentration under reduced pressure, water (30 mL) was added to the residue, and the mixture was extracted with ethyl acetate (100 mL). The ethyl acetate layer was washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1). Crystallization from diethyl ether gave the title compound (0.721 g) as a colorless solid. 1H-NMR(CDCl3): 1.25-1.34(3H,m), 2.23(6H,s), 3.15,3.32(total 3H,s), 3.72(3H,s), 3.90-4.53(9H,m), 4.86(1H,d,J=13.4 Hz), 4.95(1H,d,J=13.4 Hz), 6.79(1H,d,J=8.7 Hz), 7.95(1H,d,J=8.7 Hz), 8.22(1H,s). Synthetic Example 38 2-[[[5-Methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-3H-imidazo[4,5-b]pyridin-3-yl]carbonyl](methyl)amino]ethyl acetate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.582 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.485 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., 2-(methylamino)ethyl acetate hydrochloride (0.922 g) obtained in Reference Example 2 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 2 hrs. After concentration under reduced pressure, water (30 mL) was added to the residue, and the mixture was extracted with ethyl acetate (80 mL). The ethyl acetate layer was washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (10 mL). 5-Methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-imidazo[4,5-b]pyridine (0.85 g) synthesized by the method described in JP-A-63-146882, triethylamine (0.70 mL) and 4-dimethylaminopyridine (0.025 g) were added, and the mixture was stirred at 60° C. for 5 hrs. After concentration under reduced pressure, water (30 mL) was added to the residue, and the mixture was extracted with ethyl acetate (90 mL). The ethyl acetate layer was washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1). Crystallization from diethyl ether gave the title compound (0.173 g) as a colorless solid. 1H-NMR(CDCl3): 2.04,2.09(total 3H,s), 2.24(6H,s), 3.13,3.30(total 3H,s), 3.45-3.97(2H,m), 3.72(3H,s), 3.97(3H,s), 4.15-4.50(2H,m), 4.85(1H,d,J=13.1 Hz), 4.96(1H,d,J=13.1 Hz), 6.80(1H,d,J=8.9 Hz), 7.96(1H,d,J=8.9 Hz), 8.22(1H,s). Synthetic Example 39 2-[[[5-Methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-3H-imidazo[4,5-b]pyridin-3-yl]carbonyl](phenyl)amino]ethyl acetate To a solution (10 mL) of bis(trichloromethyl)carbonate (0.291 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.243 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., 2-anilinoethyl acetate hydrochloride (0.647 g) obtained in Reference Example 27 was added. A solution (1 mL) of triethylamine (0.419 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 3 hrs. After concentration under reduced pressure, water (20 mL) was added to the residue, and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (15 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (10 mL). 5-Methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-imidazo[4,5-b]pyridine (0.867 g) synthesized by the method described in JP-A-63-146882, triethylamine (0.697 mL) and 4-dimethylaminopyridine (0.020 g) was added, and the mixture was stirred at 60° C. for 10 hrs. After concentration under reduced pressure, water (20 mL) was added to the residue, and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (15 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:1). Crystallization from diethyl ether gave the title compound (0.311 g) as a colorless solid. 1H-NMR(CDCl3): 1.96(3H,s), 2.23(3H,s), 2.25(3H,s) 3.72(3H,s), 4.01(3H,s), 4.12-4.52(4H,m), 4.78-5.22(2H,m), 6.62(1H,d,J=8.7 Hz), 7.02-7.18(3H,m), 7.32-7.48(2H,m), 7.73(1H,d,J=8.7 Hz), 8.26(1H,s). Synthetic Example 40 4-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]butyl acetate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.59 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.49 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., 4-(methylamino)butyl acetate hydrochloride (1.08 g) obtained in Reference Example 37 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 3 hrs. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.02 g), triethylamine (0.77 mL) and 4-dimethylaminopyridine (catalytic amount) were added, and the mixture was stirred at 60° C. overnight. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1) to give the title compound (0.93 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 1.65-1.85(4H,m), 2.03(3H,s), 2.23(3H,s), 3.02(3H,bs), 3.45-3.63(2H,m), 4.03-4.13(2H,m), 4.37(2H,q,J=7.8 Hz), 4.85-5.13(2H,m), 6.64(1H,d,J=5.6 Hz), 7.36-7.46(3H,m), 7.84(1H,d,J=8.4 Hz), 8.35(1H,d,J=5.6 Hz). Synthetic Example 41 Ethyl 4-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]butyl carbonate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.59 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.49 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., ethyl 4-(methylamino)butyl carbonate hydrochloride (1.27 g) obtained in Reference Example 39 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 3 hrs. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.26 g), triethylamine (0.95 mL) and 4-dimethylaminopyridine (catalytic amount) were added, and the mixture was stirred at 60° C. overnight. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1) to give the title compound (1.08 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 1.31(3H,t,J=7.2 Hz), 1.73-1.91(4H,m), 2.23(3H,s), 3.01(3H,bs), 3.50-3.62(2H,m), 4.15-4.22(4H,m), 4.38(2H,q,J=7.8 Hz), 4.87-5.13(2H,m), 6.64(1H,d,J=5.4 Hz), 7.35-7.46(3H,m), 7.83(1H,d,J=7.8 Hz), 8.35(1H,d,J=5.4 Hz). Synthetic Example 42 Ethyl 3-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]propyl carbonate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.59 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.49 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., ethyl 3-(methylamino)propyl carbonate hydrochloride (1.18 g) obtained in Reference Example 44 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 3 hrs. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.10 g), triethylamine (0.83 mL) and 4-dimethylaminopyridine (catalytic amount) were added, and the mixture was stirred at 60° C. overnight. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1) to give the title compound (0.88 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 1.29(3H,t,J=7.2 Hz), 2.10-2.20(2H,m), 2.22(3H,s), 3.02(3H,bs), 3.55-3.77(2H,m), 4.14-4.30(4H,m), 4.37(2H,q,J=7.8 Hz), 4.83-5.13(2H,m), 6.64(1H,d,J=5.6 Hz), 7.35-7.46(3H,m), 7.82(1H,d,J=8.1 Hz), 8.35(1H,d,J=5.6 Hz). Synthetic Example 43 3-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]propyl acetate To a solution (40 mL) of bis(trichloromethyl)carbonate (1.19 g) in tetrahydrofuran was dropwise added a solution (2 mL) of pyridine (0.95 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., 3-(methylamino)propyl acetate hydrochloride (1.90 g) obtained in Reference Example 42 was added. A solution (2 mL) of triethylamine (1.68 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 3 hrs. After concentration under reduced pressure, water (100 mL) was added to the residue, and the mixture was extracted with ethyl acetate (100 mL). The ethyl acetate layer was washed with saturated brine (100 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (40 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.99 g), triethylamine (1.50 mL) and 4-dimethylaminopyridine (catalytic amount) were added, and the mixture was stirred at 60° C. overnight. After concentration under reduced pressure, water (100 mL) was added to the residue, and the mixture was extracted with ethyl acetate (100 mL). The ethyl acetate layer was washed with saturated brine (100 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1) to give the title compound (1.22 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 1.97(3H,s), 2.05-2.15(2H,m), 2.22(3H,s), 3.03(3H,bs), 3.42-3.72(2H,m), 4.10-4.22(2H,m), 4.37(2H,q,J=7.8 Hz), 4.85-5.13(2H,m), 6.64(1H,d,J=5.6 Hz), 7.24-7.44(3H,m), 7.83(1H,d,J=7.5 Hz), 8.35(1H,d,J=5.6 Hz). Synthetic Example 44 3-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]propane-1,2-diyl diacetate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.59 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.49 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., 3-(methylamino)propane-1,2-diyl diacetate hydrochloride (1.35 g) obtained in Reference Example 46 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 3 hrs. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.27 g), triethylamine (0.96 mL) and 4-dimethylaminopyridine (catalytic amount) were added, and the mixture was stirred at 60° C. overnight. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1) to give the title compound (0.64 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 2.05(3H,s), 2.13(3H,s), 2.23(3H,s), 3.07(3H,bs), 3.42-3.95(2H,m), 4.06-4.43(2H,m), 4.38(2H,q,J=7.8 Hz), 4.85-5.05(2H,m), 5.42-5.50(1H,m), 6.63-6.66(1H,m), 7.38-7.51(3H,m), 7.78-7.85(1H,m), 8.33-8.36(1H,m). Synthetic Example 45 Diethyl 3-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]propane-1,2-diyl biscarbonate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.59 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.49 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., diethyl 3-(methylamino)propane-1,2-diyl biscarbonate hydrochloride (1.71 g) obtained in Reference Example 47 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 3 hrs. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.53 g), triethylamine (1.16 mL) and 4-dimethylaminopyridine (catalytic amount) were added, and the mixture was stirred at 60° C. overnight. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1) to give the title compound (1.42 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 1.28-1.34(6H,m), 2.22(3H,s), 3.07(3H,bs), 3.42-4.60(10H,m), 4.85-5.08(2H,m), 5.30-5.42(1H,m), 6.62-6.64(1H,m), 7.37-7.42(3H,m), 7.80-7.83(1H,m), 8.32-8.35(1H,m). Synthetic Example 46 2-[[[5-Methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-3H-imidazo[4,5-b]pyridin-3-yl]carbonyl](methyl)amino]ethyl 3-chlorobenzoate To a solution (7 mL) of bis(trichloromethyl)carbonate (0.194 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.162 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., 2-(methylamino)ethyl 3-chlorobenzoate hydrochloride (0.50 g) obtained in Reference Example 7 was added. A solution (1 mL) of triethylamine (0.279 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 2.5 hrs. After concentration under reduced pressure, water (15 mL) was added to the residue, and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (15 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (10 mL). 5-Methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-imidazo[4,5-b]pyridine (0.445 g) synthesized by the method described in JP-A-63-146882, triethylamine (0.357 mL) and 4-dimethylaminopyridine (0.012 g) were added, and the mixture was stirred at 60° C. for 14 hrs. After concentration under reduced pressure, water (30 mL) was added to the residue, and the mixture was extracted with ethyl acetate (70 mL). The ethyl acetate layer was washed with saturated brine (20 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1) to give the title compound (0.360 g) as a colorless amorphous solid. 1H-NMR(CDCl3): 2.21(3H,s), 2.23(3H,s), 3.32,3.38(total 3H,s), 3.72(3H,s), 3.81(3H,s), 3.92-4.09(2H,m), 4.50-4.73(2H,m), 4.87(1H,d,J=13.4 Hz), 4.94(1H,d,J=13.4 Hz), 6.77(1H,d,J=8.8 Hz), 7.36(1H,m), 7.52(1H,m), 7.80-8.03(3H,m), 8.20(1H,s). Synthetic Example 47 2-[Methyl[[2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl acetate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.582 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.485 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 1 hr., 2-(methylamino)ethyl acetate hydrochloride (0.922 g) obtained in Reference Example 2 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 2.5 hrs. After concentration under reduced pressure, water (40 mL) was added to the residue, and the mixture was extracted with ethyl acetate (80 mL). The ethyl acetate layer was washed with saturated brine (25 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (15 mL). 2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.10 g), triethylamine (0.84 mL) and 4-dimethylaminopyridine (0.036 g) were added, and the mixture was stirred at 60° C. for 4.5 hrs. After concentration under reduced pressure, water (40 mL) was added to the residue, and the mixture was extracted with ethyl acetate (80 mL). The ethyl acetate layer was washed with saturated brine (30 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (eluted with ethyl acetate:hexane=1:1, then 2:1) to give the title compound (1.18 g) as a colorless solid. 1H-NMR(CDCl3): 2.10(3H,s), 2.24(3H,s), 3.09(3H,bs), 3.60-4.00(2H,br), 4.25-4.50(2H,m), 4.38(2H, q,J=7.8 Hz), 4.84-5.18(2H,m), 6.64(1H,d,J=5.6 Hz), 7.36-7.48(3H,m), 7.85(1H,d,J=7.8 Hz), 8.35(1H,d,J=5.6 Hz). Synthetic Example 48 Ethyl 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate A solution of (R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (130 g), triethylamine (63.8 mL), 4-dimethylaminopyridine (0.86 g) and 2-[(chlorocarbonyl)(methyl)amino]ethyl ethyl carbonate (84.8 g) obtained in Reference Example 34 in tetrahydrofuran (813 mL) was stirred at 45-50° C. for 18 hrs. The reaction mixture was concentrated under reduced pressure and water (300 mL) was added to the residue, and the mixture was extracted with ethyl acetate (700 mL). The ethyl acetate layer was washed 3 times with saturated brine (300 mL), and anhydrous magnesium sulfate (130 g) and activated carbon (13 g) were added. The mixture was stirred at room temperature for 30 min. and filtrated. The filtrate was concentrated under reduced pressure and the residue was dissolved in diethyl ether (600 mL) containing triethylamine (0.49 mL), and the mixture was concentrated under reduced pressure. This step was further repeated twice. The obtained oily substance was dissolved in ethanol (200 mL) containing triethylamine (2.45 mL) and water (120 mL) was dropwise added under ice-cooling. The precipitated crystals were collected by filtration, washed 3 times with ice-cooled ethanol-water (volume ratio 1:1, 150 mL) and dried to give the title compound (172.2 g) as a colorless solid. 1H-NMR(CDCl3) showed the same chart as with the compound obtained in Synthetic Example 14. Synthetic Example 49 2-Ethoxyethyl 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.43 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.35 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 10 min., 2-ethoxyethyl 2-(methylamino)ethyl carbonate hydrochloride (0.82 g) obtained in Reference Example 48 was added. A solution (1 mL) of triethylamine (0.60 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 3 days. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with 0.2N hydrochloric acid (20 mL) and saturated brine (50 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.11 g), triethylamine (0.63 mL) and 4-dimethylaminopyridine (0.037 g) were added, and the mixture was stirred at 60° C. for 6 hrs. and at room temperature for 11 hrs. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=3:7, then ethyl acetate:hexane=7:3) to give the title compound (1.39 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 1.19(3H,t,J=6.9 Hz), 2.23(3H,s), 3.09(3H,bs), 3.40-4.20(2H,br), 3.53(2H,q,J=6.9 Hz), 3.63-3.69(2H,m), 4.27-4.34(2H,m), 4.39(2H,q,J=7.8 Hz), 4.47(2H,m), 4.80-5.20(2H,m), 6.65(1H,d,J=5.6 Hz), 7.30-7.52(3H,m), 7.84(1H,d,J=7.5 Hz), 8.35(1H,d,J=5.6 Hz). Synthetic Example 50 3-Methoxypropyl 2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl carbonate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.53 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.44 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 5 min., 3-methoxypropyl 2-(methylamino)ethyl carbonate hydrochloride (0.82 g) obtained in Reference Example 49 was added. A solution (1 mL) of triethylamine (0.75 mL) in tetrahydrofuran was dropwise added and the mixture was stirred at room temperature for 1 hr. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with 0.2N hydrochloric acid (20 mL) and saturated brine (50 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.11 g), triethylamine (0.63 mL) and 4-dimethylaminopyridine (0.037 g) were added, and the mixture was stirred at 60° C. for 6 hrs. and at room temperature for 6 hrs. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=3:7, then ethyl acetate:hexane=7:3). Crystallization from diethyl ether gave the title compound (0.70 g) as a colorless solid. 1H-NMR(CDCl3): 1.94(2H,quintet,J=6.2 Hz), 2.23(3H,s), 3.09(3H,bs), 3.31(3H,s), 3.40-4.20(2H,br), 3.44(2H,t,J=6.2 Hz), 4.25(2H,t,J=6.5 Hz), 4.38(2H,q,J=7.8 Hz), 4.44(2H,m), 4.80-5.20(2H,m), 6.64(1H,d,J=5.6 Hz), 7.35-7.48(3H,m), 7.83(1H,d,J=7.8 Hz), 8.34(1H,d,J=5.6 Hz). Synthetic Example 51 2-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl N,N-dimethylglycinate 2-(Methylamino)ethyl N,N-dimethylglycinate dihydrochloride (1.06 g) obtained in Reference Example 50 was added to tetrahydrofuran (40 mL) and the mixture was stirred for a while, to which bis(trichloromethyl)carbonate (0.77 g) was added. After ice-cooling, a solution (5 mL) of triethylamine (2.17 mL) in tetrahydrofuran was dropwise added and the mixture was stirred at room temperature for 3 hrs. The precipitated solid was filtered off and ethyl acetate (80 mL) was added. The mixture was washed with an ice-cooled aqueous sodium hydrogen carbonate solution (50 mL) and saturated brine (50 mL×2) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.11 g), triethylamine (0.63 mL) and 4-dimethylaminopyridine (0.037 g) were added, and the mixture was stirred at 60° C. for 6 hrs. and at room temperature for 3 days. 4-Dimethylaminopyridine (0.037 g) was added, and the mixture was further stirred at 60° C. for 6 hrs. After concentration under reduced pressure, an aqueous sodium hydrogen carbonate solution (50 mL) was added to the residue, and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:1, then ethyl acetate, then methanol:ethyl acetate=1:19). Crystallization from diethyl ether gave the title compound (0.41 g) as a colorless solid. 1H-NMR(CDCl3): 2.23(3H,s), 2.35(6H,s), 3.08(3H,bs), 3.21(2H,s), 3.50-4.20(2H,br), 4.38(2H,q,J=7.8 Hz), 4.44(2H,m), 4.80-5.18(2H,m), 6.64(1H,d,J=5.6 Hz), 7.36-7.48(3H,m), 7.84(1H,d,J=6.9 Hz), 8.35(1H,d,J=5.6 Hz). Synthetic Example 52 S-[2-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl]thioacetate S-[2-(Methylamino)ethyl]thioacetate hydrochloride (0.75 g) obtained in Reference Example 51 was added to tetrahydrofuran (30 mL) and the mixture was stirred for a while, to which bis(trichloromethyl)carbonate (0.66 g) was added. After ice-cooling, a solution (10 mL) of triethylamine (1.85 mL) in tetrahydrofuran was dropwise added and the mixture was stirred under ice-cooling for 30 min. and at room temperature for 30 min. The precipitated solid was filtered off and ethyl acetate (50 mL) was added to the filtrate. The mixture was washed with ice-cooled 0.2N hydrochloric acid (20 mL) and saturated brine (50 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (0.96 g), triethylamine (0.54 mL) and 4-dimethylaminopyridine (0.032 g) were added, and the mixture was stirred at 60° C. for 6 hrs. and at room temperature for 8 hrs. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel column chromatography (eluted with acetone:hexane=3:7, then acetone:hexane=7:3) to give the title compound (1.19 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 2.23(3H,s), 2.34(3H,s), 3.10(3H,bs), 3.22(2H,t,J=6.6 Hz), 3.67(2H,m), 4.38(2H,q,J=7.8 Hz), 4.80-5.20(2H,m), 6.64(1H,d,J=5.7 Hz), 7.35-7.50(3H,m), 7.83(1H,d,J=6.9 Hz), 8.35(1H,d,J=5.7 Hz). Synthetic Example 53 Ethyl 2-[2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethoxy]ethyl carbonate To a solution (40 mL) of bis(trichloromethyl)carbonate (1.19 g) in tetrahydrofuran was dropwise added a solution (2 mL) of pyridine (0.95 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., ethyl 2-[2-(methylamino)ethoxy]ethyl carbonate hydrochloride (2.73 g) obtained in Reference Example 52 was added. A solution (2 mL) of triethylamine (1.68 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 3 hrs. After concentration under reduced pressure, water (100 mL) was added to the residue, and the mixture was extracted with ethyl acetate (100 mL). The ethyl acetate layer was washed with saturated brine (100 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (40 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (2.80 g), triethylamine (2.11 mL) and 4-dimethylaminopyridine (catalytic amount) were added, and the mixture was stirred at 60° C. overnight. After concentration under reduced pressure, water (100 mL) was added to the residue, and the mixture was extracted with ethyl acetate (100 mL). The ethyl acetate layer was washed with saturated brine (100 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1) to give the title compound (2.19 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 1.28(3H,t,J=7.2 Hz), 2.24(3H,s), 3.10(3H,bs), 3.38-3.80(6H,m), 4.18(2H,q,J=7.2 Hz), 4.27-4.34(2H,m), 4.38(2H,q,J=8.4 Hz), 4.83-5.30(2H,m), 6.65(1H,d,J=5.7 Hz), 7.35-7.50(3H,m), 7.84(1H,d,J=7.8 Hz), 8.36(1H,d,J=5.7 Hz). Synthetic Example 54 Ethyl 2-[methyl[[2-[methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethoxy]carbonyl]amino]ethyl carbonate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.59 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.49 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., ethyl 2-[methyl[[2-(methylamino)ethoxy]carbonyl]amino]ethyl carbonate hydrochloride (1.71 g) obtained in Reference Example 53 was added. A solution (1 mL) of triethylamine (0.84 mL) in tetrahydrofuran was dropwise added and the mixture was stirred at room temperature for 3 hrs. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.59 g), triethylamine (1.20 mL) and 4-dimethylaminopyridine (catalytic amount) were added, and the mixture was stirred at 60° C. overnight. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1) to give the title compound (1.62 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 1.24-1.31(3H,m), 2.24(3H,bs), 2.97-2.99(3H,m), 3.10(3H,bs), 3.55-3.58(2H,m), 4.09-4.50(10H,m), 4.88-5.08(2H,m), 6.65(1H,t,J=5.7 Hz), 7.36-7.48(3H,m), 7.85(1H,d,J=6.9 Hz), 8.36(1H,d,J=5.7 Hz). Synthetic Example 55 Ethyl 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](methyl)amino]ethyl carbonate To a solution (10 mL) of bis(trichloromethyl)carbonate (0.291 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.243 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 1 hr., ethyl 2-(methylamino)ethyl carbonate hydrochloride (0.551 g) obtained in Reference Example 14 was added. A solution (1 mL) of triethylamine (0.418 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 2 hrs. After concentration under reduced pressure, water (15 mL) was added to the residue, and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (15 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (10 mL). 5-Methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-benzimidazole (0.817 g), triethylamine (0.661 mL) and 4-dimethylaminopyridine (0.012 g) were added, and the mixture was stirred at 60° C. for 12 hrs. After concentration under reduced pressure, water (20 mL) was added to the residue, and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (15 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1) to give a 3:2 mixture (0.92 g) of the title compound and ethyl 2-[[[6-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](methyl)amino]ethyl carbonate as a pale-yellow amorphous solid. 1H-NMR(CDCl3): 1.27-1.34(3H,m), 2.10-2.30(3H,m), 2.23(3H,s), 2.99-3.23(3H,m), 3.40-3.85(2H,m), 3.69(6/5H,s), 3.71(9/5H,s), 3.86(6/5H,s), 3.88(9/5H,s), 4.14-4.25(2H,m), 4.38-4.60(2H,m), 4.82-5.06(2H,m), 6.92-7.08(7/5H,m), 7.33(3/5H,d,J=9.0 Hz), 7.66(1H,m), 8.21(1H,s). Synthetic Example 56 2-[[[5-Methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](phenyl)amino]ethyl acetate To a solution (10 mL) of bis(trichloromethyl)carbonate (0.291 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.243 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., 2-anilinoethyl acetate hydrochloride (0.647 g) obtained in Reference Example 27 was added. A solution (1 mL) of triethylamine (0.419 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 3 hrs. After concentration under reduced pressure, water (20 mL) was added to the residue, and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (15 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (10 mL). 5-Methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-benzimidazole (0.829 g), triethylamine (0.669 mL) and 4-dimethylaminopyridine (0.012 g) were added, and the mixture was stirred at 60° C. for 14 hrs. After concentration under reduced pressure, water (40 mL) was added to the residue, and the mixture was extracted with ethyl acetate (80 mL). The ethyl acetate layer was washed with saturated brine (15 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2) to give a 1:1 mixture (1.10 g) of the title compound and 2-[[[6-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](phenyl)amino]ethyl acetate as a colorless amorphous solid. 1H-NMR(CDCl3): 1.99(3H,s), 2.19(1.5H.s), 2.21(1.5H,s), 2.25(3H,s), 3.70(1.5H,s), 3.71(3H,s), 3.78(1.5H,s), 3.84(1.5H,s), 4.15-4.56(4H,m), 4.74-4.80(1H,m), 4.91-4.98(1H,m), 6.83-6.91(1.5H,m), 7.04-7.19(3.5H,m), 7.25-7.53(2.5H,m), 7.51(0.5H,d,J=8.7 Hz), 8.25(1H,s). Synthetic Example 57 Ethyl 2-[[[(S)-5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](methyl)amino]ethyl carbonate To a solution (10 mL) of (S)-5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-benzimidazole (1.34 g) synthesized by the method described in Synthetic Example 1 of Japanese Patent Application under PCT laid-open under kohyo No. 10-504290 in tetrahydrofuran were added 2-[(chlorocarbonyl)(methyl)amino]ethyl ethyl carbonate (0.9 mL) obtained in Reference Example 34, triethylamine (1.08 mL) and 4-dimethylaminopyridine (0.010 g), and the mixture was stirred at 60° C. for 6 hrs. After concentration under reduced pressure, water (30 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (15 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1) to give a 3:2 mixture (0.92 g) of the title compound and ethyl 2-[[[(S)-6-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](methyl)amino]ethyl carbonate as a pale-yellow amorphous solid. 1H-NMR(CDCl3): 1.25-1.34(3H,m), 2.10-2.30(3H,m), 2.23(3H,s), 2.99-3.23(3H,m), 3.40-3.85(2H,m), 3.69(6/5H,s), 3.71(9/5H,s), 3.86(6/5H,s), 3.88(9/5H,s), 4.14-4.25(2H,m), 4.38-4.60(2H,m), 4.79-5.05(2H,m), 6.92-7.08(7/5H,m), 7.33(3/5H,d,J=9.3 Hz), 7.65(1H,m), 8.21(1H,s). Synthetic Example 58 Ethyl 2-[[[2-[[[4-(3-methoxypropoxy)-3-methyl-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](methyl)amino]ethyl carbonate To a solution (10 mL) of bis(trichloromethyl)carbonate (0.291 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.243 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., ethyl 2-(methylamino)ethyl carbonate hydrochloride (0.551 g) obtained in Reference Example 14 was added. A solution (1 mL) of triethylamine (0.418 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 2.5 hrs. After concentration under reduced pressure, water (15 mL) was added to the residue, and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (15 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (10 mL). 2-[[[4-(3-Methoxypropoxy)-3-methyl-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (0.723 g), triethylamine (0.528 mL) and 4-dimethylaminopyridine (0.012 g) were added, and the mixture was stirred at 60° C. for 17 hrs. After concentration under reduced pressure, water (40 mL) was added to the residue, and the mixture was extracted with ethyl acetate (80 mL). The ethyl acetate layer was washed with saturated brine (15 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2), then by silica gel column chromatography (eluted with ethyl acetate:hexane=1:1, then ethyl acetate) to give the title compound (0.44 g) as a colorless amorphous solid. 1H-NMR(CDCl3): 1.31(3H,t,J=7.1 Hz), 2.05(2H,m), 2.18(3H,s), 3.08(3H,bs), 3.34(3H,s), 3.54(2H,t,J=6.1 Hz), 3.61-4.01(2H,m), 4.08(2H,t,J=6.3 Hz), 4.21(2H,t,J=7.1 Hz), 4.38-4.54(2H,m), 4.81-5.12(2H,m), 6.68(1H,d,J=5.6 Hz), 7.34-7.48(3H,m), 7.83(1H,d,J=7.8 Hz), 8.27(1H,d,J=5.6 Hz). Synthetic Example 59 2-[[[2-[[[4-(3-Methoxypropoxy)-3-methyl-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](phenyl)amino]ethyl acetate To a solution (10 mL) of bis(trichloromethyl)carbonate (0.291 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.243 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 30 min., 2-anilinoethyl acetate hydrochloride (0.647 g) obtained in Reference Example 27 was added. A solution (1 mL) of triethylamine (0.419 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 3 hrs. After concentration under reduced pressure, water (20 mL) was added to the residue, and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (15 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (10 mL). 2-[[[4-(3-Methoxypropoxy)-3-methyl-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (0.877 g), triethylamine (0.641 mL) and 4-dimethylaminopyridine (0.012 g) were added, and the mixture was stirred at 60° C. for 16 hrs. After concentration under reduced pressure, water (40 mL) was added to the residue, and the mixture was extracted with ethyl acetate (80 mL). The ethyl acetate layer was washed with saturated brine (15 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2), then by silica gel column chromatography (eluted with ethyl acetate) to give the title compound (0.93 g) as a colorless amorphous solid. 1H-NMR(CDCl3): 1.99(3H,s), 2.07(3H.s), 2.19(3H,s), 3.35(3H,s), 3.54(2H,t,J=6.2 Hz), 4.09(2H,t,J=6.2 Hz), 4.14-4.40(4H,m), 4.80(1H,d,J=13.7 Hz), 5.00(1H,d,J=13.7 Hz), 6.71(1H,d,J=5.7 Hz), 7.03-7.34(7H,m), 7.38(1H,m), 7.65(1H,m), 8.32(1H,d,J=5.7 Hz). Synthetic Example 60 2-[[[5-(Difluoromethoxy)-2-[[(3,4-dimethoxy-2-pyridyl)methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl](methyl)amino]ethyl ethyl carbonate To a solution (8 mL) of bis(trichloromethyl)carbonate (0.174 g) in tetrahydrofuran was dropwise added a solution (1 mL) of pyridine (0.146 mL) in tetrahydrofuran under ice-cooling. After stirring under ice-cooling for 1 hr., ethyl 2-(methylamino)ethyl carbonate hydrochloride (0.330 g) obtained in Reference Example 14 was added. A solution (1 mL) of triethylamine (0.250 mL) in tetrahydrofuran was dropwise added, and the mixture was stirred at room temperature for 3 hrs. After concentration under reduced pressure, water (10 mL) was added to the residue, and the mixture was extracted with ethyl acetate (30 mL). The ethyl acetate layer was washed with saturated brine (10 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (8 mL). 5-(Difluoromethoxy)-2-[[(3,4-dimethoxy-2-pyridyl)methyl]sulfinyl]-1H-benzimidazole (0.432 g), triethylamine (0.279 mL) and 4-dimethylaminopyridine (0.008 g) were added, and the mixture was stirred at 60° C. for 17.5 hrs. After concentration under reduced pressure, water (20 mL) was added to the residue, and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (10 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:2, then 1:1), then by silica gel column chromatography (eluted with ethyl acetate:hexane=2:1, then ethyl acetate) to give a 1:1 mixture (0.09 g) of the title compound and 2-[[[6-(difluoromethoxy)-2-[[(3,4-dimethoxy-2-pyridyl)methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]methylamino]ethyl ethyl carbonate as a pale-yellow amorphous solid. 1H-NMR(CDCl3): 1.31(3H,t,J=7.2 Hz), 3.06(3H,s), 3.42-3.98(2H,m), 3.87(3H,s), 3.90(3H,s), 4.21(2H,q,J=7.2 Hz), 4.36-4.54(2H,m), 4.90(1H,d,J=13.2 Hz), 4.98(1H,d,J=13.2 Hz), 6.54(0.5H,t,J=73.5 Hz)., 6.61(0.5H,t,J=73.5 Hz), 6.78(1H,d,J=5.3 Hz), 7.15-7.25(1.5H,m), 7.44(0.5H,d,J=9.0 Hz), 7.59(0.5H,s), 7.80(0.5H,d,J=9.0 Hz), 8.17(1H,d,J=5.3 Hz). Synthetic Example 61 2-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl 1-methylpiperidine-4-carboxylate 2-(Methylamino)ethyl 1-methylpiperidine-4-carboxylate dihydrochloride (0.98 g) obtained in Reference Example 54 was added to tetrahydrofuran (50 mL) and the mixture was stirred for a while, to which bis(trichloromethyl)carbonate (0.53 g) was added. After ice-cooling, a solution (50 mL) of triethylamine (2.01 mL) in tetrahydrofuran was dropwise added and the mixture was stirred at room temperature for 3 hrs. Ethyl acetate (100 mL) was added and the mixture was washed with an aqueous sodium hydrogen carbonate solution (100 mL) and saturated brine (80 mL) and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (0.74 g), triethylamine (0.56 mL) and 4-dimethylaminopyridine (0.049 g) were added, and the mixture was stirred at 60° C. overnight. After concentration under reduced pressure, an aqueous sodium hydrogen carbonate solution (50 mL) was added to the residue, and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=7:3, then ethyl acetate, then methanol:ethyl acetate=1:19) to give the title compound (0.78 g) as a yellow-green amorphous solid. 1H-NMR(CDCl3): 1.65-2.05(6H,m), 2.23(3H,s), 2.25(3H,s), 2.24-2.38(1H,m), 2.75-2.85(2H,m), 3.07(3H,bs), 3.40-4.10(2H,br), 4.38(2H,q,J=7.8 Hz), 4.40(2H,m), 4.80-5.10(2H,br), 6.64(1H,d,J=5.6 Hz), 7.36-7.47(3H,m), 7.84(1H,d,J=7.8 Hz), 8.35(1H,d,J=5.6 Hz). Synthetic Example 62 2-[[4-(Aminocarbonyl)phenyl][[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl acetate To a solution (20 mL) of bis(trichloromethyl)carbonate (0.45 g) in tetrahydrofuran was dropwise added a solution (10 mL) of 2-[[4-(aminocarbonyl)phenyl]amino]ethyl acetate (0.67 g) obtained in Reference Example 55 and triethylamine (0.63 mL) in tetrahydrofuran under ice-cooling, and the mixture was stirred at room temperature for 1 hr. After concentration under reduced pressure, water (50 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with 0.2N hydrochloric acid (20 mL) and saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (30 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.11 g), triethylamine (0.63 mL) and 4-dimethylaminopyridine (0.037 g) were added, and the mixture was stirred at 60° C. for 30 min. and at room temperature overnight. After concentration under reduced pressure, an aqueous sodium hydrogen carbonate solution (50 mL) was added to the residue, and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=4:6, then 6:4, then 8:2) to give the title compound (1.26 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 1.99(3H,s), 2.26(3H,s), 4.15-4.55(4H,m), 4.41(2H,q,J=7.9 Hz), 4.80-5.20(2H,br), 6.69(1H,d,J=5.7 Hz), 7.26-7.38(3H,m), 7.48(2H,d,J=8.9 Hz), 7.54(2H,d,J=8.9 Hz), 7.66-7.73(1H,m), 8.39(1H,d,J=5.7 Hz). Synthetic Example 63 2-[Methyl[[(R)-2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl 1-methyl-4-piperidinyl carbonate 2-(Methylamino)ethyl 1-methyl-4-piperidinyl carbonate dihydrochloride (1.01 g) obtained in Reference Example 56 was added to tetrahydrofuran (30 mL) and, after stirring for a while, ice-cooled. Bis(trichloromethyl)carbonate (0.69 g) was added and a solution (10 mL) of triethylamine (1.95 mL) in tetrahydrofuran was dropwise added. After stirring under ice-cooling for 1 hr. and at room temperature for 1 hr., the precipitated solid was filtered off. After concentration under reduced pressure, ethyl acetate (50 mL) was added, and the mixture was washed with an ice-cooled aqueous sodium hydrogen carbonate solution (50 mL) and saturated brine (50 mL), and dried over anhydrous magnesium sulfate. The layer was concentrated under reduced pressure, and the residue was dissolved in tetrahydrofuran (20 mL). (R)-2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (1.11 g), triethylamine (0.63 mL) and 4-dimethylaminopyridine (0.037 g) were added, and the mixture was stirred at 60° C. overnight. After concentration under reduced pressure, an aqueous sodium hydrogen carbonate solution (50 mL) was added to the residue, and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (50 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=1:1, then ethyl acetate, then methanol:ethyl acetate=1:19) to give the title compound (0.70 g) as a yellow amorphous solid. 1H-NMR(CDCl3): 1.70-1.86(2H,m), 1.90-2.04(2H,m), 2.23(3H,s), 2.28(3H,s), 2.10-2.35(2H,m), 2.60-2.72(2H,m), 3.08(3H,bs), 3.40-4.20(2H,br), 4.39(2H,q,J=7.9 Hz), 4.44(2H,m), 4.60-4.74(1H,m), 4.80-5.15(2H,br), 6.65(1H,d,J=5.9 Hz), 7.35-7.52(3H,m), 7.84(1H,d,J=7.5 Hz), 8.35(1H,d,J=5.9 Hz). Synthetic Example 64 2-[[4-(Aminocarbonyl)phenyl][[2-[[[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazol-1-yl]carbonyl]amino]ethyl acetate To a solution (5 mL) of bis(trichloromethyl)carbonate (0.12 g) in tetrahydrofuran was dropwise added a solution (5 mL) of 2-[[4-(aminocarbonyl)phenyl]amino]ethyl acetate (0.22 g) obtained in Reference Example 55 and triethylamine (0.17 mL) in tetrahydrofuran under ice-cooling, and the mixture was stirred at room temperature for 30 min. Water (20 mL) was added, and the mixture was extracted with ethyl acetate (30 mL). The ethyl acetate layer was washed with saturated brine (20 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was dissolved in tetrahydrofuran (10 mL). 2-[[[3-Methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methyl]sulfinyl]-1H-benzimidazole (0.37 g), triethylamine (0.28 mL) and 4-dimethylaminopyridine (0.012 g) were added, and the mixture was stirred at 60° C. for 1 hr. After concentration under reduced pressure, an aqueous sodium hydrogen carbonate solution (20 mL) was added to the residue, and the mixture was extracted with ethyl acetate (30 mL). The ethyl acetate layer was washed with saturated brine (20 mL) and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=3:7, then 5:5, then 8:2) to give the title compound (0.34 g) as a pale-yellow amorphous solid. 1H-NMR(CDCl3): 1.99(3H,s), 2.26(3H,s), 4.15-4.55(4H,m), 4.41(2H,q,J=7.9 Hz), 4.80-5.20(2H,br), 6.69(1H,d,J=5.9 Hz), 7.26-7.40(3H,m), 7.47(2H,d,J=8.8 Hz), 7.54(2H,d,J=8.8 Hz), 7.65-7.74(1H,m), 8.38(1H,d,J=5.9 Hz). Synthetic Example 65 (−)-Ethyl 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-3H-imidazo[4,5-b]pyridin-3-yl]carbonyl](methyl)amino]ethyl carbonate 5-Methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-imidazo[4,5-b]pyridine synthesized according to the method described in JP-A-63-146882 was subjected to preparative HPLC for optical resolution to give a (−) enantiomeric form (0.10 g) thereof. To a solution (5 mL) of this form in tetrahydrofuran were added 2-[(chlorocarbonyl)(methyl)amino]ethyl ethyl carbonate (0.081 g) obtained in Reference Example 34, triethylamine (0.080 mL) and 4-dimethylaminopyridine (0.007 g) and the mixture was stirred at 50° C. for 18 hrs. After concentration under reduced pressure, water (30 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (30 mL) and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=2:1) to give the title compound (0.053 g) as a colorless oil. 1H-NMR(CDCl3): 1.30(3H,t,J=7.1 Hz), 2.24(6H,s), 3.15,3.32(total 3H,s), 3.73(3H,s), 3.90-4.55(9H,m), 4.85(1H,d,J=13.2 Hz), 4.97(1H,d,J=13.2 Hz), 6.80(1H,d,J=8.8 Hz), 7.96(1H,d,J=8.8 Hz), 8.23(1H,s). Synthetic Example 66 (+)-Ethyl 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-3H-imidazo[4,5-b]pyridin-3-yl]carbonyl](methyl)amino]ethyl carbonate 5-Methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-imidazo[4,5-b]pyridine synthesized according to the method described in JP-A-63-146882 was subjected to preparative HPLC for optical resolution to give a (+) enantiomeric form (0.10 g) thereof. To a solution (5 mL) of this form in tetrahydrofuran were added 2-[(chlorocarbonyl) (methyl)amino]ethyl ethyl carbonate (0.081 g) obtained in Reference Example 34, triethylamine (0.080 mL) and 4-dimethylaminopyridine (0.007 g) and the mixture was stirred at 50° C. for 18 hrs. After concentration under reduced pressure, water (30 mL) was added to the residue and the mixture was extracted with ethyl acetate (50 mL). The ethyl acetate layer was washed with saturated brine (30 mL) and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the residue was purified by basic silica gel column chromatography (eluted with ethyl acetate:hexane=2:1) to give a 2:1 mixture (0.115 g) of the title compound and (+)-ethyl 2-[[[5-methoxy-2-[[(4-methoxy-3,5-dimethyl-2-pyridyl)methyl]sulfinyl]-1H-imidazo[4,5-b]pyridin-1-yl]carbonyl](methyl)amino]ethyl carbonate as a colorless oil. 1H-NMR(CDCl3): 1.20-1.38(3H,m), 2.24(6H,s), 3.08,3.15,3.33(total 3H,s), 3.73(3H,s), 3.88-4.55(9H,m), 4.78-5.05(2H,m), 6.80,6.86(1H,d,J=8.8 Hz), 7.76,7.96(1H,d,J=8.8 Hz), 8.21,8.22(total 1H,s). Example 1 Among the components described below, 247.7 g of lansoprazole R-isomer (hereinafter, referred to as ‘Compound A’), 184.6 g of magnesium carbonate, 492.2 g of purified sucrose, 299.9 g of corn starch and 329.6 g of low substituted hydroxypropyl cellulose were mixed well to obtain a dusting powder. 880 g of sucrose-starch spheres (trade name: Nonpareil-101, produced by Freund Industrial Co., Ltd.) were charged in a centrifugal fluid-bed granulator (CF-360, manufactured by Freund Industrial Co., Ltd.) and the above dusting powder was coated on the sucrose-starch spheres while spraying a hydroxypropyl cellulose solution (2 w/w %), thereby producing spherical granules. The spherical granules were dried at 40° C. for 16 hrs under vacuum and passed through a round sieve to give granules of 710 μm-1400 μm. Composition in 300.0 mg of the granules sucrose·starch spheres 110.0 mg Compound A 30.0 mg magnesium carbonate 22.4 mg purified sucrose 59.8 mg corn starch 36.4 mg low substituted hydroxypropyl cellulose 40.0 mg hydroxypropyl cellulose 1.4 mg total 300.0 mg Example 2 25 g of Macrogol 6000 and 10 g of Polysorbate 80 were dissolved in 1206 g of purified water, and 78 g of talc, 25 g of titanium oxide and 866.7 g of methacrylic acid copolymer LD (260 g as solid content) were dispersed into the resulting solution to obtain an enteric coating solution. The granules obtained in Example 1 were coated with the above enteric coating solution using an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.) under the condition of inlet air temperature: 45° C., rotor revolution speed: 200 rpm, coating solution spray rate: 3.8 g/min. and spray air pressure: 1.0 kg/cm2, followed by drying as it was and passing through a round sieve to give enteric-coated granules of 710 μm-1400 μm having following composition. The obtained spherical granules were dried at 40° C. for 16 hrs under vacuum. Composition in 369.2 mg of the enteric-coated granules granules of Example 1 300.0 mg methacrylic acid copolymer LD 148.7 mg (44.6 mg as solid content) talc 13.8 mg Macrogol 6000 4.4 mg titanium oxide 4.4 mg Polysorbate 80 2.0 mg total 369.2 mg Example 3 36 g of methacrylic acid copolymer S, 12 g of methacrylic acid copolymer L and 4.8 g of triethyl citrate were dissolved in a mixed solution of purified water (69.12 g) and absolute ethanol (622.08 g), and 24 g of talc was dispersed into the resulting solution to obtain a coating solution. 100 g of the enteric-coated granules obtained in Example 2 was coated with the above coating solution using an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.) under the condition of inlet air temperature: 30° C., rotor revolution speed: 150 rpm, coating solution spray rate: 3.3 g/min. and spray air pressure: 1.0 kg/cm2 to give controlled release granules having the following composition which is coated with release-controlled coating-layer being soluble pH-dependently (releasing an active ingredient under the circumstances of more than a certain pH value). The resulting spherical granules were passed through a round sieve to give controlled release granules of 710 μm-1400 μm. Then the obtained spherical granules were dried at 40° C. for 16 hrs under vacuum. Composition in 605.5 mg of the controlled release granules enteric-coated granules of Example 2 369.2 mg methacrylic acid copolymer S 110.8 mg methacrylic acid copolymer L 36.9 mg talc 73.8 mg triethyl citrate 14.8 mg total 605.5 mg Example 4 24 g of methacrylic acid copolymer S, 24 g of methacrylic acid copolymer L and 4.8 g of triethyl citrate were dissolved in a mixed solution of purified water (69.12 g) and absolute ethanol (622.08 g), and 24 g of talc was dispersed into the resulting solution to obtain coating solution. 100 g of the enteric-coated granules obtained in Example 2 was coated with the above coating solution using an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.) under the condition of inlet air temperature: 30° C., rotor revolution speed: 150 rpm, coating solution spray rate: 3.3 g/min. and spray air pressure: 1.0 kg/cm2 to give controlled release granules having the following composition which is coated with release-controlled coating-layer being soluble pH-dependently (releasing an active ingredient under the circumstances of more than a certain pH value). The resulting spherical granules were passed through a round sieve to give controlled release granules of 710 μm-1400 μm. Then the obtained spherical granules were dried at 40° C. for 16 hrs under vacuum. Composition in 605.5 mg of the controlled release granules enteric-coated granules of Example 2 369.2 mg methacrylic acid copolymer S 73.85 mg methacrylic acid copolymer L 73.85 mg talc 73.8 mg triethyl citrate 14.8 mg total 605.5 mg Example 5 104 mg of enteric-coated granules obtained in Example 2 and 500 mg of controlled release granules obtained in Example 3 were mixed and thereto 205 mg of polyethylene oxide (trade name: Polyox WSR Coagulant, produced by Dow Chemical Co., Ltd.) was added to obtain a mixture. Two geratin capsules #0 were filled with the resulting mixture to obtain a capsule. Example 6 104 mg of enteric-coated granules obtained in Example 2 and 500 mg of controlled release granules obtained in Example 4 were mixed and thereto 205 mg of polyethylene oxide (trade name: Polyox WSR Coagulant, produced by Dow Chemical Co., Ltd.) was added to obtain a mixture. Two geratin capsules #0 were filled with the resulting mixture to obtain a capsule. Example 7 300 g of Compound A, 105 g of magnesium carbonate, 195 g of purified sucrose and 75 g of low substituted hydroxypropyl cellulose were mixed well to obtain a dusting powder for active ingredient layer. 75 g of purified sucrose, 48.8 g of titanium oxide and 18.8 g of low substituted hydroxypropyl cellulose were mixed well to obtain a dusting powder for intermediate layer. 375 g of sucrose-starch spheres (trade name: Nonpareil-101, produced by Freund Industrial Co., Ltd.) were charged in a centrifugal fluid-bedgranulator (CF-360, manufactured by Freund Industrial Co., Ltd.) and the sucrose-starch spheres were coated with the above dusting powder for active ingredient layer while spraying a hydroxypropyl cellulose solution (2 w/w %), thereby producing spherical granules. Then, the resulting spherical granules were coated with the above dusting powder for intermediate layer while spraying a hydroxypropyl cellulose solution (2 w/w %) to obtain spherical granules. The obtained spherical granules were dried at 40° C. for 16 hrs under vacuum and passed through a round sieve to give granules of 710 μm-1400 μm. Composition in 120.0 mg of the granules sucrose·starch spheres 37.5 mg hydroxypropyl cellulose 0.75 mg dusting powder for active ingredient layer Compound A 30.0 mg magnesium carbonate 10.5 mg purified sucrose 19.5 mg low substituted hydroxypropyl cellulose 7.5 mg dusting powder for intermediate layer purified sucrose 7.5 mg low substituted hydroxypropyl cellulose 1.875 mg titanium oxide 4.875 mg total 120.0 mg Example 8 25 g of Macrogol 6000 and 10 g of Polysorbate 80 were dissolved in 1206 g of purified water, and 78 g of talc, 25 g of titanium oxide and 866.7 g of methacrylic acid copolymer LD (260 g as solid content) were dispersed into the resulting solution to obtain an enteric coating solution. The granules obtained in Example 7 were coated with the above enteric coating solution using an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.) under the condition of inlet air temperature: 45° C., rotor revolution speed: 200 rpm, coating solution spray rate: 3.8 g/min. and spray air pressure: 1.0 kg/cm2, followed by drying as it was and passing through a round sieve to give enteric-coated granules of 710 μm-1400 μm having the following composition. The obtained spherical granules were dried at 40° C. for 16 hrs under vacuum. Composition in 149.86 mg of the enteric-coated granules granules of Example 7 120.00 mg methacrylic acid copolymer LD 65 mg (19.5 mg as solid content) talc 5.85 mg Macrogol 6000 1.88 mg titanium oxide 1.88 mg Polysorbate 80 0.75 mg total 149.86 mg Example 9 36 g of methacrylic acid copolymer S, 12 g of methacrylic acid copolymer L and 4.8 g of triethyl citrate were dissolved in a mixed solution of purified water (69.12 g) and absolute ethanol (622.08 g), and 24 g of talc was dispersed into the resulting solution to obtain a coating solution. 100 g of the enteric-coated granules obtained in Example 8 was coated with the above coating solution using an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.) under the condition of inlet air temperature: 30° C., rotor revolution speed: 150 rpm, coating solution spray rate: 3.3 g/min. and spray air pressure: 1.0 kg/cm2 to give controlled release granules having the following composition which is coated with a release-controlled coating-layer being soluble pH-dependently (releasing an active ingredient under the circumstances of more than a certain pH value). The resulting spherical granules were passed through a round sieve to give controlled release granules of 710 μm-1400 μm. Then the obtained spherical granules were dried at 40° C. for 16 hrs under vacuum. Composition in 245.86 mg of the controlled release granules enteric-coated granules of Example 8 149.86 mg methacrylic acid copolymer S 45.00 mg methacrylic acid copolymer L 15.00 mg talc 30.00 mg triethyl citrate 6.00 mg total 245.86 mg Example 10 24 g of methacrylic acid copolymer S, 24 g of methacrylic acid copolymer L and 4.8 g of triethyl citrate were dissolved in a mixed solution of purified water (69.12 g) and absolute ethanol (622.08 g), and 24 g of talc was dispersed into the resulting solution to obtain a coating solution. 100 g of the enteric-coated granules obtained in Example 8 was coated with the above coating solution using an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.) under the condition of inlet air temperature: 30° C., rotor revolution speed: 150 rpm, coating solution spray rate: 3.3 g/min. and spray air pressure: 1.0 kg/cm2 to give controlled release granules having the following composition which is coated with a release-controlled coating-layer being soluble pH-dependently (releasing an active ingredient under the circumstances of more than a certain pH value). The resulting spherical granules were passed through a round sieve to give controlled release granules of 710 μm-1400 μm. Then the obtained spherical granules were dried at 40° C. for 16 hrs under vacuum. Composition in 245.86 mg of the controlled release granules enteric-coated granules of Example 8 149.86 mg methacrylic acid copolymer S 30.0 mg methacrylic acid copolymer L 30.0 mg talc 30.0 mg triethyl citrate 6.0 mg total 245.86 mg Example 11 35.5 mg of enteric-coated granules obtained in Example 8 and 175 mg of controlled release granules obtained in Example 9 were mixed and thereto 70.2 mg of polyethylene oxide (trade name: Polyox WSR Coagulant, produced by Dow Chemical Co., Ltd.) was added to obtain a mixture. One capsule #1 was filled with the resulting mixture to obtain a capsule (correspond to 30 mg of Compound A). Example 12 35.5 mg of enteric-coated granules obtained in Example 8 and 175 mg of controlled release granules obtained in Example 10 were mixed and thereto 70.2 mg of polyethylene oxide (trade name: Polyox WSR Coagulant, produced by Dow Chemical Co., Ltd.) was added to obtain a mixture. One capsule #1 was filled with the resulting mixture to obtain a capsule (correspond to 30 mg of Compound A). Experiment Example 1 A capsule obtained in Example 5 was administered orally with 30 ml of water to a fasting beagle dog. Each plasma concentration of Compound A at 1 hr, 2 hrs, 4 hrs, 6 hrs, 7 hrs, 8 hrs and 10 hrs after administration was 186 ng/mL, 132 ng/mL, 107 ng/mL, 303 ng/mL, 355 ng/mL, 216 ng/mL and 113 ng/mL, respectively. Experiment Example 2 A capsule obtained in Example 6 was administered orally with 30 ml of water to a fasting beagle dog. Each plasma concentration of Compound A at 1 hr, 2 hrs, 4 hrs, 6 hrs, 7 hrs, 8 hrs and 10 hrs after administration was 192 ng/mL, 137 ng/mL, 473 ng/mL, 478 ng/mL, 364 ng/mL, 257 ng/mL and 28 ng/mL, respectively. Experiment Example 3 A capsule obtained in Example 11 was administered orally with 30 ml of water to a fasting beagle dog. Each plasma concentration of Compound A at 1 hr, 2 hrs, 4 hrs, 6 hrs, 7 hrs, 8 hrs and 10 hrs after administration was 308 ng/mL, 245 ng/mL, 323 ng/mL, 81 ng/mL, 39 ng/mL, 26 ng/mL and 0 ng/mL, respectively. Experiment Example 4 A capsule obtained in Example 12 was administered orally with 30 ml of water to a fasting beagle dog. Each plasma concentration of Compound A at 1 hr, 2 hrs, 4 hrs, 6 hrs, 7 hrs, 8 hrs and 10 hrs after administration was 160 ng/mL, 319 ng/mL, 631 ng/mL, 371 ng/mL, 230 ng/mL, 144 ng/mL and 25 ng/mL, respectively. Example 13 36 g of methacrylic acid copolymer S, 12 g of methacrylic acid copolymer L and 4.8 g of triethyl citrate were dissolved in a mixed solution of purified water (69.12 g) and absolute ethanol (622.08 g), and 24 g of talc was dispersed into the resulting solution to obtain a coating solution. 100 g of the enteric-coated granules obtained in Example 8 was coated with the above coating solution using an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.) under the condition of inlet air temperature: 30° C., rotor revolution speed: 150 rpm, coating solution spray rate: 3.3 g/min. and spray air pressure: 1.0 kg/cm2 to give controlled release granules having the following composition which is coated with a release-controlled coating-layer being soluble pH-dependently (releasing an active ingredient under the circumstances of more than a certain pH value). The resulting spherical granules were passed through a round sieve to give controlled release granules of 710 μm-1400 μm. Then the obtained spherical granules were dried at 40° C. for 16 hrs under vacuum. Composition in 221.86 mg of the controlled release granules enteric-coated granules of Example 8 149.86 mg methacrylic acid copolymer S 33.75 mg methacrylic acid copolymer L 11.25 mg talc 22.5 mg triethyl citrate 4.5 mg total 221.86 mg Example 14 24 g of methacrylic acid copolymer S, 24 g of methacrylic acid copolymer L and 4.8 g of triethyl citrate were dissolved in a mixed solution of purified water (69.12 g) and absolute ethanol (622.08 g), and 24 g of talc was dispersed into the resulting solution to obtain a coating solution. 100 g of the enteric-coated granules obtained in Example 8 was coated with the above coating solution using an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.) under the condition of inlet air temperature: 30° C., rotor revolution speed: 150 rpm, coating solution spray rate: 3.3 g/min. and spray air pressure: 1.0 kg/cm2 to give controlled release granules having the following composition which is coated with a release-controlled coating-layer being soluble pH-dependently (releasing an active ingredient under the circumstances of more than a certain pH value). The resulting spherical granules were passed through a round sieve to give controlled release granules of 710 μm-1400 μm. Then the obtained spherical granules were dried at 40° C. for 16 hrs under vacuum. Composition in 221.86 mg of the controlled release granules enteric-coated granules of Example 8 149.86 mg methacrylic acid copolymer S 22.5 mg methacrylic acid copolymer L 22.5 mg talc 22.5 mg triethyl citrate 4.5 mg total 221.86 mg Example 15 35.5 mg of enteric-coated granules obtained in Example 8 and 168 mg of controlled release granules obtained in Example 13 were mixed and thereto 68.2 mg of polyethylene oxide (trade name: Polyox WSR Coagulant, produced by Dow Chemical Co., Ltd.) was added to obtain a mixture. One capsule #1 was filled with the resulting mixture to obtain a capsule (correspond to 30 mg of Compound A). Example 16 35.5 mg of enteric-coated granules obtained in Example 8 and 168 mg of controlled release granules obtained in Example 14 were mixed and thereto 68.2 mg of polyethylene oxide (trade name: Polyox WSR Coagulant, produced by Dow Chemical Co., Ltd.) was added to obtain a mixture. One capsule #1 was filled with the resulting mixture to obtain a capsule (correspond to 30 mg of Compound A). Example 17 35.5 mg of enteric-coated granules obtained in Example 8 and 168 mg of controlled release granules obtained in Example 13 were mixed and the resulting mixture was filled in one capsule #3 to give a capsule (correspond to 30 mg of Compound A). Example 18 35.5 mg of enteric-coated granules obtained in Example 8 and 168 mg of controlled release granules obtained in Example 14 were mixed and the resulting mixture was filled in one capsule #3 to give a capsule (correspond to 30 mg of Compound A). Experiment Example 5 A capsule obtained in Example 14 was administered orally with 30 ml of water to a fasting beagle dog. Each plasma concentration of Compound A at 1 hr, 2 hrs, 4 hrs, 6 hrs, 7 hrs, 8 hrs and 10 hrs after administration was 403 ng/mL, 687 ng/mL, 803 ng/mL, 463 ng/mL, 329 ng/mL, 217 ng/mL and 65 ng/mL, respectively. Example 19 100 g of the granules obtained in Example 1 was charged in a centrifugal fluid-bed granulator (CF-mini, manufactured by Freund Industrial Co., Ltd.) and Ac-Di-Sol that is a disintegrant were coated on the granules by a ratio of 32 w/w % based on the granules while spraying a solution of hydroxypropyl cellulose dissolved in isopropyl alcohol (8 w/w %), thereby producing spherical granules. The spherical granules were dried at 40° C. for 16 hrs under vacuum and passed through a round sieve to give granules of 1400 μm or less. Example 20 24 g of aminoalkyl methacrylate copolymer RS was dissolved in acetone (120 g) and isopropyl alcohol (288 g), and 48 g of talc was dispersed into the resulting solution to obtain a coating solution. 100 g of the granules obtained in Example 19 was coated with the above coating solution using an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.) under the condition of inlet air temperature: 30° C., rotor revolution speed: 150 rpm, coating solution spray rate: 3.1 g/min. and spray air pressure: 1.0 kg/cm2 to give controlled release granules having the following composition. The resulting spherical granules were passed through a round sieve to give controlled release granules of 710 μm-1700 μm. Then the obtained spherical granules were dried at 40° C. for 16 hrs under vacuum. Composition in 130.0 mg of the controlled release granules granules of Example 19 100 mg aminoalkyl methacrylate copolymer RS 10.0 mg talc 20.0 mg total 130.0 mg Example 21 104 mg of enteric-coated granules obtained in Example 2 and 420 mg of controlled release granules obtained in Example 20 were mixed and thereto 175 mg of polyethylene oxide (trade name: Polyox WSR Coagulant, produced by Dow Chemical Co., Ltd.) was added to obtain a mixture. Two gelatin capsules #0 were filled with the resulting mixture to obtain a capsule (correspond to 30 mg of Compound A). Example 22 104 mg of enteric-coated granules obtained in Example 2 and 420 mg of controlled release granules obtained in Example 20 were mixed and the resulting mixture was filled in two gelatin capsules #0 to give a capsule (correspond to 30 mg of Compound A). Experiment Example 6 A capsule obtained in Example 21 was administered orally with 30 ml of water to a fasting beagle dog. Each plasma concentration of Compound A at 1 hr, 2 hrs, 4 hrs, 6 hrs, 7 hrs, 8 hrs and 10 hrs after administration was 657 ng/mL, 406 ng/mL, 223 ng/mL, 504 ng/mL, 399 ng/mL, 228 ng/mL and 50 ng/mL, respectively. Example 23 36 g of methacrylic acid copolymer S, 12 g of methacrylic acid copolymer L and 4.8 g of triethyl citrate were dissolved in a mixed solution of purified water (69.12 g) and absolute ethanol (622.08 g), and 24 g of talc was dispersed into the resulting solution to obtain a coating solution. 100 g of the granules obtained in Example 19 was coated with the above coating solution using an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.) under the condition of inlet air temperature: 30° C., rotor revolution speed: 150 rpm, coating solution spray rate: 3.3 g/min. and spray air pressure: 1.0 kg/cm2 to give controlled release granules having the following composition. The resulting spherical granules were passed through a round sieve to give controlled release granules of 710 μm-1700 μm. Then the obtained spherical granules were dried at 40° C. for 16 hrs under vacuum. Composition in 164.0 mg of the controlled release granules granules of Example 19 100 mg methacrylic acid copolymer S 30.0 mg methacrylic acid copolymer L 10.0 mg talc 20.0 mg triethyl citrate 4.0 mg total 164.0 mg Example 24 104 mg of enteric-coated granules obtained in Example 2 and 614 mg of controlled release granules obtained in Example 23 were mixed and thereto 239 mg of polyethylene oxide (trade name: Polyox WSR Coagulant, produced by Dow Chemical Co., Ltd.) was added to obtain a mixture. Two gelatin capsules #0 were filled with the resulting mixture to obtain a capsule (correspond to 30 mg of Compound A). Example 25 104 mg of enteric-coated granules obtained in Example 2 and 614 mg of controlled release granules obtained in Example 23 were mixed and the resulting mixture was filled in two gelatin capsules #0 to obtain a capsule (correspond to 30 mg of Compound A). Experiment Example 7 A capsule obtained in Example 24 was administered orally with 30 ml of water to a fasting beagle dog. Each plasma concentration of Compound A at 1 hr, 2 hrs, 4 hrs, 6 hrs, 7 hrs, 8 hrs and 10 hrs after administration was 106 ng/mL, 135 ng/mL, 639 ng/mL, 129 ng/mL, 49 ng/mL, 16 ng/mL and 0 ng/mL, respectively. Comparison Example 1 One gelatin capsule #0 obtained in Example 2, which was filled with 414 mg of enteric-coated granules, was administered orally with 30 ml of water to a fasting beagle dog. Each plasma concentration of Compound A at 1 hr, 2 hrs, 4 hrs, 6 hrs, 7 hrs, 8 hrs and 10 hrs after administration was 2,068 ng/mL, 689 ng/mL, 70 ng/mL, 0 ng/mL, 0 ng/mL, 0 ng/mL and 0 ng/mL, respectively. Example 26 150 g of Compound A, 50 g of magnesium carbonate, 25 g of low substituted hydroxypropyl cellulose and 25 g of hydroxypropyl cellulose were suspended in 1420 g of purified water to obtain a spraying solution. 200 g of crystalline cellulose (sphere) was charged in an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.) and was sprayed with the above spraying solution under the condition of inlet air temperature: 62° C., rotor revolution speed: 300 rpm, coating solution spray rate: 10 g/min. and spray air pressure: 1.0 kg/cm2 to give spherical granules having the following composition. The resulting spherical granules were dried at 40° C. for 16 hrs under vacuum and passed through a round sieve to give controlled release granules of 500 μm-1400 μm. Composition in 41.24 mg of the granules crystalline cellulose (sphere) 22.5 mg Compound A 11.25 mg magnesium carbonate 3.75 mg low substituted hydroxypropyl cellulose 10.0 mg hydroxypropyl cellulose 1.87 mg total 41.24 mg Example 27 90 g of Compound A, 31.5 g of magnesium carbonate, 58.5 g of purified sucrose and 22.5 g of low substituted hydroxypropyl cellulose were mixed well to obtain a dusting powder of active ingredient layer. 110 g of the granules obtained in Example 26 was charged in a centrifugal fluid-bed granulator (CF-mini, manufactured by Freund Industrial Co., Ltd.) and was coated with the above dusting powder of active ingredient layer while spraying a hydroxypropyl cellulose solution (2 w/w %), thereby producing spherical granules having the following composition. The obtained spherical granules were dried at 40° C. for 16 hrs under vacuum and passed through a round sieve to give granules of 710 μm-1400 μm. Composition in 118.03 mg of the granules granules of Example 26 41.25 mg Compound A 33.75 mg magnesium carbonate 11.81 mg purified sucrose 21.94 mg low substituted hydroxypropyl cellulose 8.44 mg hydroxypropyl cellulose 0.84 mg total 118.03 mg Example 28 The granules obtained in Example 27 were coated with a coating solution for intermediate layer using an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.), and were dried intact to give granules having the following composition. The coating solution for intermediate layer was produced by dissolving 20.09 g of hydroxypropyl methylcellulose 2910 in 361.55 g of purified water and followed by dispersing 8.03 g of titanium oxide and 12.05 g of talc into the obtained solution. The coating operation was carried out under the condition of inlet air temperature: 62° C., rotor revolution speed: 200 rpm, coating solution spray rate: 3.0 g/min. and spray air pressure: 1.0 kg/cm2. The resulting spherical granules were dried at 40° C. for 16 hrs under vacuum and passed through a round sieve to give granules of 710 μm-1400 μm. Composition in 133.03 mg of the granules coated with an intermediate layer granules of Example 27 118.03 mg hydroxypropyl methylcellulose 2910 7.5 mg talc 4.5 mg titanium oxide 3.0 mg total 133.03 mg Example 29 25 g of Macrogol 6000 and 10 g of Polysorbate 80 were dissolved in 1206 g of purified water, and 78 g of talc, 25 g of titanium oxide and 866.7 g of methacrylic acid copolymer LD (260 g as solid content) were dispersed into the resulting solution to obtain an enteric coating solution. The granules obtained in Example 28 were coated with the above enteric coating solution using an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.) under the condition of inlet air temperature: 45° C., rotor revolution speed: 200 rpm, coating solution spray rate: 3.8 g/min. and spray air pressure: 1.0 kg/cm2, followed by drying as it was and passing through a round sieve to give enteric-coated granules of 710 μm-1400 μm having the following composition. The obtained spherical granules were dried at 40° C. for 16 hrs under vacuum. Composition in 165.18 mg of the enteric-coated granules granules of Example 28 133.03 mg methacrylic acid copolymer LD 70 mg (21 mg as solid content) talc 6.30 mg Macrogol 6000 2.02 mg titanium oxide 2.02 mg Polysorbate 80 0.81 mg total 165.18 mg Example 30 36 g of methacrylic acid copolymer S, 12 g of methacrylic acid copolymer L and 4.8 g of triethyl citrate were dissolved in a mixed solution of purified water (69.12 g) and absolute ethanol (622.08 g), and 24 g of talc was dispersed into the resulting solution to obtain a coating solution. 100 g of the granules obtained in Example 28 was coated with the above coating solution using an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.) under the condition of inletair temperature: 30° C., rotor revolution speed: 100 rpm, coating solution spray rate: 3.0 g/min. and spray air pressure: 1.0 kg/cm2 to give controlled release granules having the following composition which is coated with a release-controlled coating-layer being soluble pH-dependently (releasing an active ingredient under the circumstances of more than a certain pH value). The resulting spherical granules were passed through a round sieve to give controlled release granules of 1180 μm-1700 μm. Then the obtained spherical granules were dried at 40° C. for 16 hrs under vacuum. Composition in 196.88 mg of the controlled release granules granules of Example 28 133.03 mg methacrylic acid copolymer S 29.93 mg methacrylic acid copolymer L 9.98 mg talc 19.95 mg triethyl citrate 3.99 mg total 196.88 mg Example 31 24 g of methacrylic acid copolymer S, 24 g of methacrylic acid copolymer L and 4.8 g of triethyl citrate were dissolved in a mixed solution of purified water (69.12 g) and absolute ethanol (622.08 g), and 24 g of talc was dispersed into the resulting solution to obtain a coating solution. 100 g of the granules obtained in Example 28 was coated with the above coating solution using an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.) under the condition of inlet air temperature: 30° C., rotor revolution speed: 100 rpm, coating solution spray rate: 3.0 g/min. and spray air pressure: 1.0 kg/cm2 to give controlled release granules having the following composition which is coated with a release-controlled coating-layer being soluble pH-dependently (releasing an active ingredient under the circumstances of more than a certain pH value). The resulting spherical granules were passed through a round sieve to give controlled release granules of 1180 μm-1700 μm. Then the obtained spherical granules were dried at 40° C. for 16 hrs under vacuum. Composition in 196.88 mg of the controlled release granules granules of Example 28 133.03 mg methacrylic acid copolymer S 19.95 mg methacrylic acid copolymer L 19.95 mg talc 19.95 mg triethyl citrate 3.99 mg total 196.88 mg Example 32 28 mg of enteric-coated granules obtained in Example 29 and 98.7 mg of controlled release granules obtained in Example 30 were mixed and thereto 42.3 mg of polyethylene oxide (trade name: Polyox WSR Coagulant, produced by Dow Chemical Co., Ltd.) was added to obtain a mixture. One capsule #1 was filled with the resulting mixture to obtain a capsule (correspond to 30 mg of Compound A). Example 33 28 mg of enteric-coated granules obtained in Example 29 and 98.7 mg of controlled release granules obtained in Example 31 were mixed and thereto 42.3 mg of polyethylene oxide (trade name: Polyox WSR Coagulant, produced by Dow Chemical Co., Ltd.) was added to obtain a mixture. One capsule #1 was filled with the resulting mixture to obtain a capsule (correspond to 30 mg of Compound A). Example 34 56 mg of enteric-coated granules obtained in Example 29 and 197.4 mg of controlled release granules obtained in Example 30 were mixed and the resulting mixture was filled in one capsule #2 to give a capsule (correspond to 60 mg of Compound A). Example 35 84 mg of enteric-coated granules obtained in Example 29 and 296.1 mg of controlled release granules obtained in Example 30 were mixed and the resulting mixture was filled in one capsule #1 to give a capsule (correspond to 90 mg of Compound A). Example 36 42 mg of enteric-coated granules obtained in Example 29 and 148.05 mg of controlled release granules obtained in Example 30 were mixed and the resulting mixture was filled in one capsule #3 to give a capsule (correspond to 45 mg of Compound A). Example 37 48 g of methacrylic acid copolymer S and 4.8 g of triethyl citrate were dissolved in a mixed solution of purified water (69.12 g) and absolute ethanol (622.08 g), and 24 g of talc was dispersed into the resulting solution to obtain a coating solution. 100 g of the granules obtained in Example 30 was coated with the above coating solution using an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.) under the condition of inlet air temperature: 30° C., rotor revolution speed: 100 rpm, coating solution spray rate: 3.0 g/min. and spray air pressure: 1.0 kg/cm2 to give controlled release granules having the following composition which is coated with a release-controlled coating-layer being soluble pH-dependently (releasing an active ingredient under the circumstances of more than a certain pH value). The resulting spherical granules were passed through a round sieve to give controlled release granules of 1180 μm-1700 μm. Then the obtained spherical granules were dried at 40° C. for 16 hrs under vacuum. Composition in 207.52 mg of the controlled release granules granules of Example 30 196.88 mg methacrylic acid copolymer S 6.65 mg talc 3.32 mg triethyl citrate 0.67 mg total 207.52 mg Example 38 48 g of methacrylic acid copolymer S and 4.8 g of triethyl citrate were dissolved in a mixed solution of purified water (69.12 g) and absolute ethanol (622.08 g), and 24 g of talc was dispersed into the resulting solution to obtain a coating solution. 100 g of the granules obtained in Example 31 was coated with the above coating solution using an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.) under the condition of inlet air temperature: 30° C., rotor revolution speed: 100 rpm, coating solution spray rate: 3.0 g/min. and spray air pressure: 1.0 kg/cm2 to give controlled release granules having the following composition which is coated with a release-controlled coating-layer being soluble pH-dependently (releasing an active ingredient under the circumstances of more than a certain pH value). The resulting spherical granules were passed through a round sieve to give controlled release granules of 1180 μm-1700 μm. Then the obtained spherical granules were dried at 40° C. for 16 hrs under vacuum. Composition in 207.52 mg of the controlled release granules granules of Example 31 196.88 mg methacrylic acid copolymer S 6.65 mg talc 3.32 mg triethyl citrate 0.67 mg total 207.52 mg Example 39 28 mg of enteric-coated granules obtained in Example 29 and 103.8 mg of controlled release granules obtained in Example 37 were mixed and thereto 43.9 mg of polyethylene oxide (trade name: Polyox WSR Coagulant, produced by Dow Chemical Co., Ltd.) was added to obtain a mixture. One capsule #1 was filled with the resulting mixture to obtain a capsule (correspond to 30 mg of Compound A). Example 40 28 mg of enteric-coated granules obtained in Example 29 and 103.8 mg of controlled release granules obtained in Example 38 were mixed and thereto 43.9 mg of polyethylene oxide (trade name: Polyox WSR Coagulant, produced by Dow Chemical Co., Ltd.) was added to obtain a mixture. One capsule #1 was filled with the resulting mixture to obtain a capsule (correspond to 30 mg of Compound A). Example 41 56 mg of enteric-coated granules obtained in Example 29 and 207.5 mg of controlled release granules obtained in Example 37 were mixed and the resulting mixture was filled in one capsule #2 to give a capsule (correspond to 60 mg of Compound A). Example 42 84 mg of enteric-coated granules obtained in Example 29 and 311.3 mg of controlled release granules obtained in Example 37 were mixed and the resulting mixture was filled in one capsule #1 to give a capsule (correspond to 90 mg of Compound A). Example 43 42 mg of enteric-coated granules obtained in Example 29 and 155.6 mg of controlled release granules obtained in Example 37 were mixed and the resulting mixture was filled in one capsule #3 to give a capsule (correspond to 45 mg of Compound A). Example 44 300 g of Compound A, 105 g of magnesium carbonate, 195 g of purified sucrose and 75 g of low substituted hydroxypropyl cellulose were mixed well to obtain a dusting powder for active ingredient layer. 75 g of purified sucrose, 48.8 g of titanium oxide and 18.8 g of low substituted hydroxypropyl cellulose were mixed well to obtain a dusting powder for intermediate layer. 375 g of sucrose-starch spherical granules (trade name: Nonpareil-101, produced by Freund Industrial Co., Ltd.) were charged in a centrifugal fluid-bed granulator (CF-360, manufactured by Freund Industrial Co., Ltd.) and the sucrose-starch spheres were coated with the above dusting powder for active ingredient layer while spraying a hydroxypropyl cellulose solution (2 w/w %), thereby producing spherical granules. The obtained spherical granules were dried at 40° C. for 16 hrs under vacuum and passed through a round sieve to give granules of 710 μm-1400 μm. Composition in 158.07 mg of the granules 56.25 mg sucrose.starch spheres hydroxypropyl cellulose 0.57 mg dusting powder for active 45.00 mg ingredient layer Compound A magnesium carbonate 15.75 mg purified sucrose 29.25 mg low substituted hydroxypropyl 11.25 mg cellulose total 158.07 mg Example 45 The granules obtained in Example 44 were coated with a coating solution for intermediate layer using an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.), and were dried intact to give granules having the following composition. The coating solution for intermediate layer was produced by dissolving 20.09 g of hydroxypropyl methylcellulose 2910 in 361.55 g of purified water and followed by dispersing 8.03 g of titanium oxide and 12.05 g of talc into the obtained solution. The coating operation was carried out under the condition of inlet air temperature: 62° C., rotor revolution speed: 200 rpm, coating solution spray rate: 3.0 g/min. and spray air pressure: 1.0 kg/cm2. The resulting spherical granules were dried at 40° C. for 16 hrs under vacuum and passed through a round sieve to give granules of 710 μm-1400 μm. Composition in 188.07 mg of the granules 158.07 mg coated with an intermediate layer granules of Example 44 hydroxypropyl methylcellulose 2910 15.00 mg talc 9.00 mg titanium oxide 6.00 mg total 188.07 mg Example 46 36 g of methacrylic acid copolymer S, 12 g of methacrylic acid copolymer L and 4.8 g of triethyl citrate were dissolved in a mixed solution of purified water (69.12 g) and absolute ethanol (622.08 g), and 24 g of talc was dispersed into the resulting solution to obtain a coating solution. 100 g of the granules obtained in Example 45 was coated with the above coating solution using an agitation fluidized bed granulator (SPIR-A-FLOW, manufactured by Freund Industrial Co., Ltd.) under the condition of inlet air temperature: 30° C., rotor revolution speed: 100 rpm, coating solution spray rate: 3.0 g/min. and spray air pressure: 1.0 kg/cm2 to give controlled release granules having the following composition which is coated with a release-controlled coating-layer being soluble pH-dependently (releasing an active ingredient under the circumstances of more than a certain pH value). The resulting spherical granules were passed through a round sieve to give controlled release granules of 1180 μm-1700 μm. Then the obtained spherical granules were dried at 40° C. for 16 hrs under vacuum. Composition in 278.35 mg of the controlled 188.07 mg release granules granules of Example 45 methacrylic acid copolymer S 42.32 mg methacrylic acid copolymer L 14.11 mg talc 28.21 mg triethyl citrate 5.64 mg total 278.35 mg Example 47 35.5 mg of enteric-coated granules obtained in Example 8 and 139.2 mg of controlled release granules obtained in Example 46 were mixed and thereto 58.2 mg of polyethylene oxide (trade name: Polyox WSR Coagulant, produced by Dow Chemical Co., Ltd.) was added to obtain a mixture. One capsule #1 was filled with the resulting mixture to obtain a capsule (correspond to 30 mg of Compound A). Example 48 71 mg of enteric-coated granules obtained in Example 8 and 278.35 mg of controlled release granules obtained in Example 46 were mixed and the resulting mixture was filled in one capsule #1 to give a capsule (correspond to 60 mg of Compound A). Example 49 106.5 mg of enteric-coated granules obtained in Example 8 and 417.5 mg of controlled release granules obtained in Example 46 were mixed and the resulting mixture was filled in two capsules #2 to give a capsule (correspond to 90 mg of Compound A). Example 50 53.3 mg of enteric-coated granules obtained in Example 8 and 208.8 mg of controlled release granules obtained in Example 46 were mixed and the resulting mixture was filled in one capsule #2 to give a capsule (correspond to 45 mg of Compound A). Example 51 824.4 g of Compound A, 303.2 g of magnesium carbonate, 1062 g of purified sucrose and 228.2 g of low substituted hydroxypropyl cellulose were mixed well to obtain a dusting powder for active ingredient layer. 722.4 g of sucrose-starch spheres (trade name: Nonpareil-101, produced by Freund Industrial Co., Ltd.) were charged in a centrifugal fluid-bed granulator (CF-360, manufactured by Freund Industrial Co., Ltd.) and the sucrose-starch spheres were coated with the above dusting powder for active ingredient layer while spraying a hydroxypropyl cellulose solution (2 w/w %), thereby producing spherical granules. The obtained spherical granules were dried at 40° C. for 16 hrs under vacuum and passed through a round sieve to give granules of 710 μm-1400 μm. Composition in 86.67 mg of the granules 20.64 mg sucrose.starch spheres hydroxypropyl cellulose 0.24 mg dusting powder for active 22.50 mg ingredient layer Compound A magnesium carbonate 8.25 mg purified sucrose 28.83 mg low substituted hydroxypropyl cellulose 6.21 mg total 86.67 mg Example 52 The granules obtained in Example 51 were coated with a coating solution for intermediate layer using a fluid-bed fluidized bed coating machine (MP-10, manufactured by Powrex Co., Ltd.), and were dried intact to give granules having the following composition. The coating solution for intermediate layer was produced by dissolving 270.0 g of hydroxypropyl methylcellulose 2910 in 4874 g of purified water and followed by dispersing 163.5 g of titanium oxide and 108 g of talc into the obtained solution. The coating operation was carried out under the condition of inlet air temperature: 67° C., inlet air volume: 1.5 m3/min., coating solution spray rate: 12.0 g/min., spray air pressure: 0.28 MPa and spray air volume: 90 Nl/hr. The resulting spherical granules were dried at 40° C. for 16 hrs under vacuum and passed through a round sieve to give granules of 710 μm-1400 μm. Composition in 97.50 mg of the granules 86.67 mg coated with an intermediate layer granules of Example 51 hydroxypropyl methylcellulose 2910 5.40 mg talc 2.16 mg titanium oxide 3.27 mg total 97.50 mg Example 53 57.60 g of Macrogol 6000 and 26.40 g of Polysorbate 80 were dissolved in 2724 g of purified water, and 174 g of talc, 57.6 g of titanium oxide and 19323 g of methacrylic acid copolymer LD (579.6 g as solid content) were dispersed into the resulting solution to obtain an enteric coating solution. The granules obtained in Example 52 were coated with the above enteric coating solution using an agitation fluidized bed granulator (MP-10, manufactured by Powrex Co., Ltd.) under the condition of inlet air temperature: 65° C., inlet air volume: 1.5 m3/min., coating solution spray rate: 15.0 g/min. and spray air pressure: 0.30 MPa, and spray air volume: 90 Nl/hr. The resulting granules were dried as it was and passed through a round sieve to give enteric-coated granules of 710 μm-1400 μm having the following composition. The obtained spherical granules were dried at 40° C. for 16 hrs under vacuum, and to 1918 g of the granules were added 0.96 g of talc and 0.96 g of aerosil to give enteric-coated granules. Composition in 120.0 mg of the enteric-coated 97.5 mg granules granules of Example 52 methacrylic acid copolymer LD 48.3 mg (14.49 mg as solid content) talc 4.35 mg Macrogol 6000 1.44 mg titanium oxide 1.44 mg Polysorbate 80 0.66 mg talc 0.06 mg aerosil 0.06 mg total 120.0 mg Example 54 1131 g of Compound A, 303.2 g of magnesium carbonate, 750.1 g of purified sucrose and 226.8 g of low substituted hydroxypropyl cellulose were mixed well to obtain a dusting powder for active ingredient layer. 720.0 g of sucrose-starch spheres (trade name: Nonpareil-101, produced by Freund Industrial Co., Ltd.) were charged in a centrifugal fluid-bed granulator (CF-360, manufactured by Freund Industrial Co., Ltd.) and the sucrose-starch spheres were coated with the above dusting powder for active ingredient layer while spraying a hydroxypropyl cellulose solution (2 w/w %), thereby producing spherical granules. The obtained spherical granules were dried at 40° C. for 16 hrs under vacuum and passed through a round sieve to give granules of 710 μm-1400 μm. Composition in 189.0 mg of the granules 45.0 mg sucrose.starch spheres hydroxypropyl cellulose 0.54 mg dusting powder for active ingredient layer 67.5 mg Compound A magnesium carbonate 18.0 mg purified sucrose 44.46 mg low substituted hydroxypropyl cellulose 13.5 mg total 189.0 mg Example 55 The granules obtained in Example 54 were coated with a coating solution for intermediate layer using a fluid-bed fluidized bed coating machine (MP-10, manufactured by Powrex Co., Ltd.), and were dried intact to give granules having the following composition. The coating solution for intermediate layer was produced by dissolving 236.4 g of hydroxypropyl methylcellulose 2910 in 4255 g of purified water and followed by dispersing 141.6 g of titanium oxide and 94.8 g of talc into the obtained solution. The coating operation was carried out under the condition of inlet air temperature: 65° C., inlet air volume: 1.5 m3/min., coating solution spray rate: 12.0 g/min., spray air pressure: 0.26 MPa and spray air volume: 90 Nl/hr. The resulting spherical granules were dried at 40° C. for 16 hrs under vacuum and passed through a round sieve to give granules of 710 μm-1400 μm. Composition in 212.64 mg of the granules 189.0 mg coated with an intermediate layer granules of Example 54 hydroxypropyl methylcellulose 2910 11.82 mg talc 4.74 mg titanium oxide 7.08 mg total 212.64 mg Example 56 382.8 g of methacrylic acid copolymer S, 127.7 g of methacrylic acid copolymer L and 50.88 g of triethyl citrate were dissolved in a mixed solution of purified water (734.8 g) and absolute ethanol (6614 g), and 255.1 g of talc was dispersed into the resulting solution to obtain a coating solution. The granules obtained in Example 55 was coated with the above coating solution using an agitation fluidized bed granulator (MP-10, manufactured by Powrex Co., Ltd.) under the condition of inlet air temperature: 65° C., inlet air volume: 1.5 m3/min., coating solution spray rate: 15.0 g/min., spray air pressure: 0.30 MPa and spray air volume: 90 Nl/hr to give controlled release granules having the following composition which is coated with a release-controlled coating-layer being soluble pH-dependently (releasing an active ingredient under the circumstances of more than a certain pH value). The resulting spherical granules were passed through a round sieve to give controlled release granules of 1180 μm-1700 μm. Then the obtained spherical granules were dried at 40° C. for 16 hrs under vacuum, and to 1101 g of the granules were added 0.525 g of talc and 0.525 g of aerosil to give enteric-coated granules. Composition in 315.0 mg of the controlled 212.64 mg release granules granules of Example 55 methacrylic acid copolymer S 47.85 mg methacrylic acid copolymer L 15.96 mg talc 31.89 mg triethyl citrate 6.36 mg talc 0.15 mg aerosil 0.15 mg total 315.0 mg Example 57 120 mg of enteric-coated granules obtained in Example 53 and 315 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #1 to give a capsule (correspond to 90 mg of Compound A). Example 58 80 mg of enteric-coated granules obtained in Example 53 and 210 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #2 to give a capsule (correspond to 60 mg of Compound A). Example 59 40 mg of enteric-coated granules obtained in Example 53 and 105 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #3 to give a capsule (correspond to 30 mg of Compound A). Example 60 240 mg of enteric-coated granules obtained in Example 53 and 210 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #1 to give a capsule (correspond to 90 mg of Compound A). Example 61 160 mg of enteric-coated granules obtained in Example 53 and 280 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #1 to give a capsule (correspond to 90 mg of Compound A). Example 62 192 mg of enteric-coated granules obtained in Example 53 and 252 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #1 to give a capsule (correspond to 90 mg of Compound A). Example 63 160 mg of enteric-coated granules obtained in Example 53 and 210 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #1 to give a capsule (correspond to 75 mg of Compound A). Example 64 100 mg of enteric-coated granules obtained in Example 53 and 262.5 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #1 to give a capsule (correspond to 75 mg of Compound A). Example 65 133.3 mg of enteric-coated granules obtained in Example 53 and 233.3 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #1 to give a capsule (correspond to 75 mg of Compound A). Example 66 200 mg of enteric-coated granules obtained in Example 53 and 175 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #1 to give a capsule (correspond to 75 mg of Compound A). Example 67 106.7 mg of enteric-coated granules obtained in Example 53 and 186.7 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #2 to give a capsule (correspond to 60 mg of Compound A). Example 68 128 mg of enteric-coated granules obtained in Example 53 and 168 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #2 to give a capsule (correspond to 60 mg of Compound A). Example 69 160 mg of enteric-coated granules obtained in Example 53 and 140 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #2 to give a capsule (correspond to 60 mg of Compound A). Example 70 60 mg of enteric-coated granules obtained in Example 53 and 157.5 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #2 to give a capsule (correspond to 45 mg of Compound A). Example 71 120 mg of enteric-coated granules obtained in Example 53 and 105 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #2 to give a capsule (correspond to 45 mg of Compound A). Example 72 80 mg of enteric-coated granules obtained in Example 53 and 140 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #2 to give a capsule (correspond to 45 mg of Compound A). Example 73 96 mg of enteric-coated granules obtained in Example 53 and 126 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #2 to give a capsule (correspond to 45 mg of Compound A). Example 74 53.3 mg of enteric-coated granules obtained in Example 53 and 93.3 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #3 to give a capsule (correspond to 30 mg of Compound A). Example 75 64 mg of enteric-coated granules obtained in Example 53 and 84 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #3 to give a capsule (correspond to 30 mg of Compound A). Example 76 80 mg of enteric-coated granules obtained in Example 53 and 70 mg of controlled release granules obtained in Example 56 were mixed and the resulting mixture was filled in one capsule #3 to give a capsule (correspond to 30 mg of Compound A). INDUSTRIAL APPLICABILITY Since the controlled release preparation of the present invention can extend the therapeutic effective level by controlling the release of active ingredient over a long time, it can provide the effectiveness of treatment with a low dose and the reduction of side effects caused by the rise of blood level, as well as the reduction of administration times.
<SOH> BACKGROUND ART <EOH>An oral formulation is a dosage form which is used most frequently among pharmaceutical agents. Lots of preparations for oral administration wherein the drug efficacy thereof is sustained with the administration of once or twice a day have been developed from the viewpoint of improving QOL in these years. The compound having a kinetics of sustained drug efficacy with the administration of once or twice a day is tried to synthesize in the synthetic stage of compound itself, while quite a lot of attempts to modify the kinetics are made with designing controlled release preparation by contriving formulation. As the dosage form of oral controlled release preparation, various release-controlled systems such as a release control by a release-controlled coating-layer or a diffusion control of compound by a matrix, a release control of compound by erosion of matrix (base material), a pH-dependent release control of compound and a time-dependent release control wherein the compound is released after a certain lag time, are developed and applied. It is considered that a further extension of sustainability becomes possible by combining the above-mentioned release-controlled system with a control of migration speed in the gastrointestinal tract. The preparation containing a medicament having an acid-labile property as an active ingredient such as a benzimidazole compound having a proton pump inhibitor (hereinafter sometimes referred to as PPI) action needs to be enteric-coated. That is, a composition containing a benzimidazole compound having a proton pump inhibitor action is needed to disintegrate rapidly in the small intestine, so the composition is preferred to formulate into a granule or fine granule which has a broader surface area than a tablet and is easy to disintegrate or dissolve rapidly. In the case of a tablet, it is desirable to reduce the size of tablet (for example, see JP-A 62-277322). After administered orally, the tablet, granule or fine granule migrates through gastrointestinal tract with releasing an active ingredient to stomach, duodenum, jejunum, ileum and colon sequentially. And in the meantime, the active ingredient is absorbed at the each absorption site. A controlled release preparation is designed to control the absorption by delaying the release of active ingredient in some way. It is considered that a further extension of sustainability becomes possible by combining a release-controlled system with a function to control the migration speed in gastrointestinal tract such as adherability, floatability etc. These prior arts are disclosed in WO 01/89483, JP-A 2001-526213, U.S. Pat. No. 6,274,173, U.S. Pat. No. 6,093,734, U.S. Pat. No. 4,045,563, U.S. Pat. No. 4,686,230, U.S. Pat. No. 4,873,337, U.S. Pat. No. 4,965,269, U.S. Pat. No. 5,021,433 and the like.
<SOH> SUMMARY OF THE INVENTION <EOH>That is, the present invention provides: (1) A capsule comprising a tablet, granule or fine granule wherein the release of active ingredient is controlled and a gel-forming polymer; (2) The capsule according to the above-mentioned (1), wherein the release of active ingredient is controlled by a release-controlled coating-layer formed on a core particle containing an active ingredient; (3) The capsule according to the above-mentioned (2), wherein the release-controlled coating-layer contains a pH-dependently soluble polymer; (4) The capsule according to the above-mentioned (2), wherein the release-controlled coating-layer is a diffusion-controlled layer; (5) The capsule according to the above-mentioned (1), wherein the release of active ingredient is controlled by dispersing an active ingredient into a release-controlled matrix composing tablet, granule or fine granule; (6) The capsule according to the above-mentioned (3) or (4), wherein the tablet, granule or fine granule in which the release of active ingredient is controlled has a disintegrant layer containing disintegrant formed on the core particle containing an active ingredient and a release-controlled coating-layer formed on said disintegrant layer, and the release of active ingredient is initiated after a certain lag time; (7) The capsule according to any one of the above-mentioned (3) to (6), wherein the tablet, granule or fine granule in which the release of active ingredient is controlled is coated with a gel-forming polymer; (8) The capsule according to the above-mentioned (7) which further contains a gel-forming polymer; (9) The capsule according to any one of the above-mentioned (1) to (7), which comprises two kinds of tablet, granule or fine granule having different release properties of active ingredient; (10) The capsule according to the above-mentioned (9), which comprises a tablet, granule or fine granule having an enteric coat that releases an active ingredient at the pH of about 5.5 and a tablet, granule or fine granule having a release-controlled coating-layer that releases an active ingredient at the pH of about 6.0 or above; (11) The capsule according to the above-mentioned (1), (7) or (8), wherein the gel-forming polymer is a polymer whose viscosity of 5% aqueous solution is about 3,000 mPa·s or more at 25° C.; (12) The capsule according to the above-mentioned (1), (7) or (8), wherein the gel-forming polymer is a polymer having molecular weight of 400,000 to 10,000,000; (13) The capsule according to any one of the above-mentioned (2) to (4) or (6), wherein the release-controlled coating-layer is a layer containing one or more kinds of polymeric substances selected from the group consisting of hydroxypropylmethyl cellulose phthalate, cellulose acetate phthalate, carboxymethylethyl cellulose, methyl methacrylate-methacrylic acid copolymer, methacrylic acid-ethyl acrylate copolymer, ethyl acrylate-methyl methacrylate-trimethylammoniumethyl methacrylate chloride copolymer, methyl methacrylate-ethyl acrylate copolymer, methacrylic acid-methyl acrylate-methyl methacrylate copolymer, hydroxypropyl cellulose acetate succinate and polyvinyl acetate phthalate; (14) The capsule according to the above-mentioned (13), wherein the release-controlled coating-layer is comprised of 2 or more kinds of layers; (15) The capsule according to the above-mentioned (1), wherein the release-controlled granule or fine granule has a particle size of about 100-1,500 μm; (16) The capsule according to the above-mentioned (1), wherein the active ingredient is a proton pump inhibitor (PPI); (17) The capsule according to (16), wherein the PPI is an imidazole compound represented by the formula (I′): wherein ring C′ is an optionally substituted benzene ring or an optionally substituted aromatic monocyclic heterocyclic ring, R 0 is a hydrogen atom, an optionally substituted aralkyl group, acyl group or acyloxy group, R 1 , R 2 and R 3 are the same or different and are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted amino group, and Y represents a nitrogen atom or CH; or a salt thereof or an optically active isomer thereof; (18) The capsule according to the above-mentioned (17), wherein the imidazole compound is lansoprazole; (19) The capsule according to the above-mentioned (17), wherein PPI is an optically active R-isomer of lansoprazole; (20) The capsule according to any one of the above-mentioned (1), (7) or (8), wherein the gel-forming polymer is one or more kinds of substances selected from the group consisting of polyethylene oxide (PEO, molecular weight: 400,000-10,000,000), hydroxypropylmethyl cellulose (HPMC), carboxymethyl cellulose (CMC-Na), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose and carboxyvinyl polymer; (21) The capsule according to any one of the above-mentioned (1), (7) or (8), wherein the gel-forming polymer is polyethylene oxide (molecular weight: 400,000-10,000,000); (22) The capsule according to the above-mentioned (1) or (8), wherein the gel-forming polymer is added as a powder, fine granule or granule; (23) The capsule according to the above-mentioned (3), wherein the pH-dependently soluble polymer is methyl methacrylate-methacrylic acid copolymer; (24) A tablet, granule or fine granule wherein the release of active ingredient is controlled, said tablet, granule or fine granule comprising a core particle containing an imidazole compound represented by the formula (I′): wherein ring C′ is an optionally substituted benzene ring or an optionally substituted aromatic monocyclic heterocyclic ring, R 0 is a hydrogen atom, an optionally substituted aralkyl group, acyl group or acyloxy group, R 1 , R 2 and R 3 are the same or different and are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted amino group, and Y represents a nitrogen atom or CH; or a salt thereof or an optically active isomer thereof as an active ingredient, and a pH-dependently soluble release-controlled coating-layer which comprises one kind of polymeric substance or a mixture of two or more kinds of polymeric substances having different release properties selected from the group consisting of hydroxypropylmethyl cellulose phthalate, cellulose acetate phthalate, carboxymethylethyl cellulose, methyl methacrylate-methacrylic acid copolymer, methacrylic acid-ethyl acrylate copolymer, methacrylic acid-methyl acrylate-methyl methacrylate copolymer, hydroxypropyl cellulose acetate succinate, polyvinyl acetate phthalate and shellac, and said polymeric substance is soluble in the pH range of 6.0 to 7.5; (25) The tablet, granule or fine granule according to the above-mentioned (24), wherein the pH-dependently soluble release-controlled coating-layer is formed on an intermediate layer which is formed on a core particle; (26) The capsule comprising the tablet, granule or fine granule according to the above-mentioned (24); (27) The capsule comprising the tablet, granule or fine granule according to the above-mentioned (24) and an enteric-coated tablet, granule or fine granule containing a compound represented by the formula (II); (28) The tablet, granule or fine granule according to the above-mentioned (24), wherein the active ingredient is lansoprazole; (29) The tablet, granule or fine granule according to the above-mentioned (24), wherein the active ingredient is an optically active R-isomer of lansoprazole; (30) The tablet, granule or fine granule according to the above-mentioned (24), wherein the active ingredient is an optically active S-isomer of lansoprazole; (31) The tablet, granule or fine granule according to the above-mentioned (24), wherein the active ingredient is a derivative of lansoprazole; (32) The tablet, granule or fine granule according to the above-mentioned (24), wherein the active ingredient is a derivative of optically active R-isomer of lansoprazole; (33) The tablet, granule or fine granule according to any one of the above-mentioned (24), (25) or (28) to (32), comprising having an enteric coat on the core particle containing an active ingredient, a disintegrant layer containing disintegrant on said enteric coat and a release-controlled coating-layer on said disintegrant layer; (34) The tablet, granule or fine granule according to any one of the above-mentioned (28) to (33), which is coated with a gel-forming polymer; (35) An extended release capsule comprising the tablet, granule or fine granule according to any one of the above-mentioned (28) to (32) and a gel-forming polymer; (36) A tablet, granule or fine granule according to the above-mentioned (24) wherein the release of active ingredient is controlled by two or more kinds of release-controlled coating-layers, and the outermost release-controlled coating-layer is soluble at higher pH than the inner release-controlled coating-layer; (37) The tablet, granule or fine granule according to the above-mentioned (36), wherein the inner release-controlled coating-layer is soluble in the pH range of 6.0-7.0 and the outermost release-controlled coating-layer is soluble at the pH of 7.0 or above; (38) The tablet, granule or fine granule according to the above-mentioned (36), wherein the inner release-controlled coating-layer is soluble in the pH range of 6.5-7.0 and the outermost release-controlled coating-layer is soluble at the pH of 7.0 or above; (39) The tablet, granule or fine granule according to the above-mentioned (36), wherein the thickness of the outermost release-controlled coating-layer is 100 μm or less; (40) The granule or fine granule according to the above-mentioned (36), wherein the release-controlled granule or fine granule has a particle size of about 100-1,500 μm; (41) A capsule comprising (i) a tablet, granule or fine granule in which the release of active ingredient is controlled; said tablet, granule or fine granule comprises a core particle containing an imidazole compound represented by the formula (I′): wherein ring C′ is an optionally substituted benzene ring or an optionally substituted aromatic monocyclic heterocyclic ring, R 0 is a hydrogen atom, an optionally substituted aralkyl group, acyl group or acyloxy group, R 1 , R 2 and R 3 are the same or different and are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted amino group, and Y represents a nitrogen atom or CH; or a salt thereof or an optically active isomer thereof as an active ingredient, and a pH-dependently soluble release-controlled coating-layer which comprises one kind of polymeric substance or a mixture of two or more kinds of polymeric substances having different release properties selected from the group consisting of hydroxypropylmethyl cellulose phthalate, cellulose acetate phthalate, carboxymethylethyl cellulose, methyl methacrylate-methacrylic acid copolymer, methacrylic acid-ethyl acrylate copolymer, methacrylic acid-methyl acrylate-methyl methacrylate copolymer, hydroxypropyl cellulose acetate succinate, polyvinyl acetate phthalate and shellac; said polymeric substance is soluble in the pH range of 6.0 to 7.5, and (ii) a tablet, granule or fine granule comprising a core particle containing an active ingredient and enteric coat which is dissolved, thereby an active ingredient being released in the pH range of no less than 5.0, nor more than 6.0; (42) The capsule according to the above-mentioned (41), wherein the pH-dependently soluble release-controlled coating-layer is formed on an intermediate layer which is formed on the core particle containing an active ingredient; (43) The capsule according to the above-mentioned (41), wherein the active ingredient is lansoprazole; (44) The capsule according to the above-mentioned (41), wherein the active ingredient is an optically active R-isomer of lansoprazole; (45) The capsule according to the above-mentioned (41), wherein the active ingredient is an optically active S-isomer of lansoprazole; (46) The capsule according to the above-mentioned (41), wherein the core particle containing an active ingredient contains a stabilizer of basic inorganic salt; (47) The capsule according to the above-mentioned (41), wherein the pH-dependently soluble release-controlled coating-layer of the tablet, granule or fine granule in which the release of an active ingredient is controlled is a layer soluble in the pH range of no less than 6.5, nor more than 7.0; (48) The capsule according to the above-mentioned (47), wherein the pH-dependently soluble release-controlled coating-layer contains a mixture of two or more kinds of methyl methacrylate-methacrylic acid copolymers having different release properties; and (49) The capsule according to the above-mentioned (41), which further contains a gel-forming polymer. detailed-description description="Detailed Description" end="lead"?
20050411
20100907
20060119
70428.0
A61K954
8
SHTERENGARTS, SAMANTHA L
CONTROLLED RELEASE PREPARATION
UNDISCOUNTED
0
ACCEPTED
A61K
2,005
10,531,135
ACCEPTED
Double-layer capacitor, use of the same, and method for increasing the maximum charges of double-layer capacitor electrodes
What is proposed is a double-layer capacitor with at least a first and a second electrode, wherein the maximum charges of the two electrodes are matched. In such a double-layer capacitor according to the invention, the amount of material used per maximum storable electric charge and energy is minimal.
1. A double-layer capacitor comprising: a first electrode having a first polarity; a second electrode having a second polarity, the first polarity being different from the second polarity; and an electrolyte that is in contact with the first electrode and the second electrode, wherein the first electrode has a first charge of the first polarity and the second electrode has a second charge of the second polarity, and wherein maximum values of the first charge and the second charge are substantially equal. 2. A double-layer capacitor comprising: a first electrode having a first polarity; a second electrode having a second polarity, the first polarity being different from the second polarity; and an electrolyte that is in contact with the first electrode and the second electrode; wherein the first and second electrodes have first and second surfaces, respectively, the first and second surfaces being different. 3. The double-layer capacitor of claim 2, wherein the first and second surfaces have different sizes. 4. The double-layer capacitor of claim 2, wherein the first and second surfaces comprise a same type of material, and wherein the first and second surfaces have different masses. 5. The double-layer capacitor of claim 2, wherein a product of QV,max+V+=QV,max−V− is approximately equal for the first and second electrodes, where Q corresponds to electrode charge and V corresponds to electrode volume. 6. The double-layer capacitor of claim 2, wherein the first electrode and second electrode comprise a same type of electrode material; wherein a product of QM,max+M+=QM,max−M− is approximately equal for the first and second electrodes, where Q corresponds to electrode charge and M corresponds to electrode mass. 7. The double-layer capacitor of claim 2, wherein at least one of the first and second electrodes comprises carbon. 8. The double-layer capacitor of claim 2, wherein at least one of the first and second electrodes comprises: carbon powder, carbon fabrics, de-metallized metal carbides, carbon aerogels, graphitic carbon, nanostructured carbon, and PVD and/or CVD carbon. 9. The double-layer capacitor of claim 2, wherein at least one of the first and second electrodes comprises a conductive polymer, a conductive ceramic, a metal, and a metal alloy; and wherein the first and second electrodes have differently sized surfaces. 10. The double-layer capacitor of claim 2, wherein the electrolyte comprises at least one of a gel electrolyte, a polymer electrolytes and a liquid gel electrolyte. 11. The double-layer capacitor of claim 2, wherein the electrolyte comprises a solution comprising organic and/or aqueous solvents; and wherein the double-layer capacitor further comprises: a separator between the first and second electrodes. 12. The double-layer capacitor of claim 11, wherein the separator comprises paper, polymer membranes, or glass fibers. 13. The double-layer capacitor of claim 2, wherein the first and second electrodes are stacked, and wherein the double-layer capacitor comprises at least one separator between the first and second electrode layers. 14. The double-layer capacitor of claim 13, wherein the stack defines a coil. 15. A pseudo-capacitor comprising the double-layer capacitor of claim 2; wherein the at least one of the first and second electrodes comprises metal oxide or conductive polymer. 16. A capacitor battery comprising the double-layer capacitor of claim 2. 17. A method of reducing a difference between maximum charges of a first electrode and a second electrode of a double-layer capacitor, the first and second electrodes comprising an electrode material, the method comprising: obtaining a non-corrosion potential range of the electrode material relative to a reference electrode; obtaining maximum charges of the first and second electrodes relative the reference electrode, the maximum charges being within the non-corrosion potential range; and adjusting the maximum charges so that the maximum charges are closer in magnitude. 18. The method of claim 17, wherein obtaining the non-corrosion potential range comprises: obtaining a in potential difference between the first and second electrodes and the reference electrode; and measuring a corrosion current between the first electrode and the second electrode at the potential difference; and wherein obtaining the maximum charges comprises integrating current into the first electrode. 19. The method of claim 17, wherein the adjusting comprises increasing a size of a surface of an electrode having a lowest maximum charge. 20. The method of claim 17, wherein the first and second electrodes comprise a same material and have same dimensions when the non-corrosion potential range is obtained and when the maximum charges are obtained; and wherein adjusting comprises increasing a mass of an electrode having a lowest maximum charge. 21. The method of claim 17, wherein, during adjusting, a product of QV,max+V+=QV,max−V− or QM,max+M+=QM,max−M− is approximately equal for the first and second electrodes, where Q corresponds to electrode charge, V corresponds to electrode volume, and M corresponds to electrode mass.
Capacitors, such as double-layer capacitors, are also used in applications with high output requirements, because they can be implemented with high capacitances with simultaneously very low ESR. When used as temporary energy storage, for example, double-layer capacitors must emit or absorb, within relatively short periods of time of a few seconds or less, high currents and, associated with this, high energy. The operating voltages of double-layer capacitors generally amount to only a few volts. However, because applications usually require significantly higher voltages, multiple double-layer capacitors are frequently connected in series to form a capacitor battery. Because of the large number of individual capacitors, this means that constructing a capacitor battery is often very cost-intensive. For this reason, capacitors with the highest possible operating voltages are in demand. The later that critical corrosion currents are reached during charging of the capacitor, the higher its operating voltage. A high operating voltage requires a higher output density and energy density of the capacitor. The rated voltage of a capacitor is upwardly limited by the difference between the corrosion potentials of the capacitor electrodes and the electrolyte. If an electrode is at a potential within the corrosion range, electrochemical reactions can disadvantageously lead to corrosion of the electrodes or to disintegration of the electrodes, a process in which gas development can occur, significantly reducing the serviceable life of the capacitor. To avoid this, capacitors are generally used only at operating voltages at which the resulting individual electrode potentials remain outside the corrosion potential. The goal of the present invention, therefore, is to provide a double-layer capacitor with increased output density and energy density that can be operated at higher voltages. This goal is achieved with a double-layer capacitor according to claim 1. Advantageous embodiments of the capacitor as well as its use and a method for increasing the maximum, potential-dependent charges of the capacitor electrodes are the object of additional claims. It is known from the prior art that the maximum charge of a capacitor, which, advantageously, should be as large as possible, depends on its maximum operating voltage, that is, on the difference in the maximum potential that can be applied between the two electrodes of the capacitor. The inventors have found that, depending on the electrode system used, the individual double-layer capacitor electrodes, in the case of opposite polarity, that is, when connected as positively or negatively charged electrodes, can surprisingly absorb different maximum charge amounts. In this connection, the maximum absorbable charge is any charge amount that can be supplied to the electrode until the critical potential is reached. This electric characteristic of the electrode is referred to in the following as the maximum charge. This effect, newly discovered here, is apparently attributable, on the one hand, to the different distances between the corrosion potentials of the electrodes and their resting potentials and, on the other hand, to the different behaviors of the anions and cations of the electrolyte solution in the electrochemical double layer. In this connection, the different volumes of the solvated, positively and negatively charged ions play as important a role as their mobility in the electrolyte solution and the charge number (valence) of the respective ions. The effect of different maximum charges of the electrodes also occurs with oppositely charged electrodes that consist of the same electrode material and have the same dimensions (see FIG. 2C). This surprising discovery of differences in the dependencies of the capacitance of the two oppositely charged electrodes on the applied potential means that the electrodes in a double-layer capacitor, in their charged state, have different potential distances from their resting potential. The reversibly exchangeable maximum charge of a double-layer capacitor depends solely on the difference in electrode potential in the charged state at which an electrode first reaches the corrosion potential. The second electrode, in this connection, is still removed from its corrosion potential, meaning that it could still absorb additional charge. As a result, the volume of material used for this second electrode does not have to be used entirely for energy storage. Because conventional, commercially obtainable double-layer capacitors usually contain electrodes that are made of the same electrode material and have the same dimensions, the energy densities of conventional double-layer capacitors and the amount of material required for each stored electric charge are therefore not optimal. The inventors have found that the different maximum charges of the electrode are not only affected by the polarity and the electrolyte, but also by the dimensions, the design, the mass as well as the surface area and surface structures of the electrodes. This leads to the possibility of matching the maximum charges of the electrode, which differ at the respective corrosion potential, which is not the case in conventional double-layer capacitors. For this reason, the invention describes a double-layer capacitor in which at least a first and second electrode are present, both electrodes being in contact with an electrolyte. In the double-layer capacitor, the maximum charges, which are dependent on the polarity of the electrodes and determined relative to a reference electrode, are matched to one another. Electrodes, within the meaning of the invention, are defined as electron-conducting materials that are in contact with an electrolyte, electrolytes being defined as media that exclusively conduct ions. The advantage of a double-layer capacitor according to the invention over a conventional double-layer capacitor is that the amount of material used per stored electric charge is reduced. In a conventional double-layer capacitor, the maximum charges of the individual electrodes, which are determined relative to a reference electrode, are not matched, because it was previously not known that the individual electrodes have different maximum charges that depend on the polarity of the electrode, the electrode material and the design. Thus, for example, conventional double-layer capacitor electrodes differ in terms of their charge, by 10% at a difference in potential of +1 V relative to the resting potential and by 12% at a difference in potential of ±0.5 V. This effect results, for example, in a difference of at least 39% in the amounts of the individual potentials of the electrodes relative to the resting potential, at a capacitor voltage of 2.4 V. The electrodes of a double-layer capacitor according to the invention have different capacitance-forming surface areas. This means that the maximum charges of the electrodes are matched to one another by using different electrode surface areas or different surface structures. The structure of the inner surface of an electrode determines the electrochemical double layer that forms in electrochemical double-layer capacitors during charging of the capacitor. In addition, in a variant of a double-layer capacitor according to the invention, in which the electrodes are made of the same electrode material, the masses of the respective electrodes can be different. This means that in the case of the same electrode materials but different masses, such as in the case of electrodes with different layer thicknesses, the sizes of the inner surfaces of the electrodes are also different, resulting in maximum charges matched to one another. In an advantageous embodiment of a double-layer capacitor according to the invention, both electrodes of the capacitor have a charge Q, in the maximum charged state, which is indicated by the following equation: wherein Q = V + ⁢ Q V ⁢ ⁢ max + = V - ⁢ Q V ⁢ ⁢ max - ⁢ ⁢ where Q V ⁢ ⁢ max + = ∫ 0 φ + max ⁢ c V ⁡ ( φ ) ⁢ ⁢ ⅆ φ ⁢ ⁢ and ⁢ Q V ⁢ ⁢ max - = ∫ 0 φ - max ⁢ - c V ⁡ ( φ ) ⁢ ⁢ ⅆ φ = Q V ⁢ ⁢ max - wherein Q+Vmax and Q−Vmax are the respective maximum, volume-specific charge densities of the positive and negative electrodes, V+ and V− the respective volumes of the positive and negative electrodes, φ is the electric potential, φ−min and φ+max are the electric potentials at which corrosion of the electrodes does not yet take place, and cv is the volume-specific, differential capacitance in the potential range valid for the respective electrode. The products of the respective maximum volume-specific charge densities and the respective electrode volumes, that is, the maximum charges of both electrodes, are approximately equal, so that the material volume of both electrodes can essentially be used entirely for energy storage. The maximum, volume-specific charge densities Q+Vmax and Q−Vmax of the electrodes, within the meaning of the invention, are also material-specific and indicate the same maximum charge per unit of volume of the electrode that can be supplied to the electrode without it reaching the corrosion potential. The critical charge densities and/or potentials can be determined by a person skilled in the art using leakage current measurements (see FIGS. 2A and 2B), for example. In another variant of the double-layer capacitor according to the invention, the two electrodes can be made of the same electrode material, wherein, in the maximum charged state of the capacitor, the product of the mass M+ or M− of the electrode and its critical, mass-specific charge density Q+M,max and Q−M,max is approximately equal for both electrodes: Q = Q max + = M + ⁢ Q M , max + M - ⁢ Q M , max - = Q max - ⁢ ⁢ with Q M , max + = ∫ 0 φ + ⁢ c M ⁡ ( φ + ) ⁢ ⁢ ⅆ φ + ⁢ ⁢ and Q M , max - = ∫ 0 φ - ⁢ c M ⁡ ( φ - ) ⁢ ⁢ ⅆ φ - This means, as already described above, that the maximum charges of the two electrodes are approximately equal, so that the volume of material used for the electrodes can be used almost entirely for energy storage. The term matching, as it is used in the invention, advantageously refers to adjusting the different maximum charges of the electrodes of a double-layer capacitor until the respective corrosion potentials are reached, in such a way that their difference is smaller than in conventional double-layer capacitors, that is, is less than about 10% for standard operating voltages of about 2V, for example, and is less than about 12% for operating voltages of 3V. The term matching, in this connection, can mean that, following determination of the maximum charges in the potential range that is negative relative to the reference electrode, using the measuring arrangement shown in FIGS. 1A and 1B, for example, the maximum charge of those electrodes whose maximum charge was lower in the measurements is increased. As already described, increasing the charge can be achieved, for example, by increasing the mass or the volume, or by modifying the chemical composition of the electrode. Double-layer capacitors according to the invention, which contain such matched electrodes, have higher charge densities and elevated operating voltages when compared with conventional double-layer capacitors. In principle, however, it is also possible to reduce the maximum charge of those electrodes with the higher maximum charge, thereby matching them to the electrode with the lower maximum charge. This can be achieved by reducing the size of the surface of this electrode. If the electrode materials are the same, a reduction in the mass and/or volume of this electrode is also possible. Double-layer capacitors according to the invention that contain such matched electrodes have higher operating voltages than conventional double-layer capacitors. Furthermore, because less electrode material is needed for one of the electrodes, these double-layer capacitors according to the invention are less expensive than conventional capacitors, while nonetheless providing the same capacitor capacitance. In electrodes according to the invention with approximate equal maximum, potential-dependent charges, the changes can diverge from one another by up to 5%. This divergence is attributable, among other things, to measuring errors during determination of the maximum charge, which generally do not permit an exact determination of this variable. In double-layer capacitors according to the invention, one of the electrodes can comprise carbon. Carbon electrodes bring about charge storage primarily through their large inner surface. The electrode material can be selected from a group of the following materials: a) carbon powder, b) carbon fibers, e.g., fabric, nonwoven fabric, paper or strands, c) de-metallized metal carbides, d) carbon aerogels, e) graphitic carbon, f) nanostructured carbon, g) carbon applied by means of physical vapor deposition (PVD) and/or chemical vapor deposition (CVD). Carbon powder electrodes, which consist, for example, of carbon powder applied to aluminum foil, are especially advantageous, because it is especially easy to vary their layer thickness on the aluminum foil. In this manner, it is especially easy to implement electrodes according to the invention which, due to different thickness, for example, have approximately the same maximum charges. A large range of fabrics, for example, having, for example, different weaving structures, material thickness and material density, can be used as carbon fibers. Nonwoven fabrics or papers can also be used. Depending on their structure, carbon fibers have different volume-specific capacitances, different voltage stabilities and gassing tendencies. Carbon electrodes with a large surface can also be produced by removing metallic components from metal carbides (de-metallized metal carbides), for example. SiC or TiC, for example, may be used as metal carbides. Carbon aerogels are monolithic, open-pore solid bodies with a large inner surface (more than 1500 m2/g, determined using the BET method), whose structural parameters during production in a sol-gel process can be varied within a wide range. Also in the case of carbon electrodes consisting of graphitic carbon, very high volume-specific capacitances can be achieved in that, for example, the graphitic carbon, coke, for example, which can be derived from tar or petroleum, is baked with a base, such as potassium hydroxide, at high temperatures of approximately 700 to 850°. During this process, the structure of the carbon is opened, also resulting in a very large surface, which can be used for electrostatic charge storage. Nanostructured carbon exists in the form of so-called nanofilaments, which typically have a diameter in the nanometer range and lengths in the micrometer range. Carbon electrodes with large surfaces can also be produced by precipitating carbon out of the gas phase by means, for example, of Chemical Vapor Deposition (CVD). Ionized carbon particles can be applied in an electric field by means of Physical Vapor Deposition (PVD). It is also possible that at least one of the electrodes of a double-layer capacitor according to the invention is selected from a group consisting of conductive polymers, such as polyaniline, conductive ceramics, such as titanium nitride, and metals or metal alloys, and has a large surface. The electrolyte of a double-layer capacitor according to the invention can comprise a gel electrolyte and/or polymer electrolyte. It is also possible that the electrolyte is an electrolyte solution comprising organic and/or aqueous solvents, in which case a separator is additionally arranged between the electrodes, said separator comprising, for example, paper, a polymer membrane or glass fibers. Double-layer capacitors according to the invention that encompass different electrodes can also be implemented as a stack layer. In this case, both electrodes are structured as layers, the layered stack encompassing alternating first and second electrode layers with separators disposed between the layers. The separators and the electrodes are soaked in an electrolyte solution. It is also possible to roll the first and second electrode, which are structured as a layer, along with separators disposed between them, into a capacitor coil. In the case, for example, of carbon electrodes applied to an aluminum foil, the electrodes are contacted by protruding sections of the aluminum foil. Instead of circular coils, flat coils with rectangular shapes are also possible. In another variant, the double-layer capacitors according to the invention can also comprise pseudo-capacitors, in which case both electrodes comprise either metal oxides or conductive polymers. The metal oxide can, for example, comprise ruthenium oxide, iridium oxide or nickel oxide, and the electrically conductive polymer can, for example, comprise polypyrrol, polythiophene or polyaniline, or derivatives of these conductive polymers. In the case of pseudo-capacitors, pseudo-capacitances develop on the surface of the electrodes as a result of the movement of electric charges generated by oxidation and reduction processes at the electrodes. Double-layer capacitors according to the invention can also be used in capacitor batteries. The advantage of capacitor batteries consisting of the capacitors according to the invention is that they are made of significantly fewer individual capacitors, because capacitors according to the invention have higher operating voltages than conventional capacitors. The object of the invention is also a method for reducing the difference between the different maximum charges of a first and a second double-layer capacitor electrode with opposite charge. The method consists of the following steps: A) the corrosion-free potential window of the electrode material, as measured against a reference electrode, is determined; B) the maximum charges, as measured against a reference electrode, of the electrode materials of the first and second electrode are determined and then, in step C) the maximum charges of the two electrodes are matched. In step A), a difference in potential between the first electrode and the reference electrode can be set, followed by measurement of the corrosion current. The allowable potential range is exceeded where this current exceeds a critical limit value, such as 10 μA/cm2. Then, in step B), the electrode is brought to the critical potential within a short period of time, such as 1 minute, and the charge needed for this purpose is determined by integration of the current. This process is then repeated on the other end of the allowable potential range. This measurement can be performed either with the same electrodes or with electrodes made of a different material. In step C), the surface area of the electrode that is to operate later on in the double-layer capacitor on the side of the allowable potential window that has the lower maximum, potential-dependent charge density is elevated, for example. This has the result that the maximum voltage and the total capacitance of a double-layer capacitor containing electrodes matched to one another by means of this method are higher than in a conventional double-layer capacitor. The charge densities of the first and second electrode determined at the positive and at the negative edge of the corrosion-free potential window are used to calculate the volume or mass ratio of both electrode according to the following equation and, by modifying the mass and/or volume, matching them to one another: M + M - = Q M , max - Q M , max + ⁢ ⁢ and ⁢ / ⁢ or ⁢ ⁢ V + V - = Q V , max - Q V , max + In another advantageous variant of the method, the same electrode material and the same design and dimensions are used for the first and second electrode in steps A) and B). Then, in step C), the mass or the volume of those electrodes with the lower critical charge is increased. An increase in the mass or volume means that, while the electrode materials and the dimensions remain the same, the surface area of the electrode increases, thereby raising the critical charge. In another advantageous variant of the method according to the invention, in step C), the product QV,max+V+=QV,max−V− and/or QM,max+M+=QM,max−M− is set to be approximately equal for both electrodes. If this product is approximately equal, the maximum charges of the two electrodes are also approximately equal. In this case, the total capacitance and the operating voltage of a double-layer capacitor containing these electrodes are at a maximum. In the following, the invention will be explained in greater detail on the basis of exemplary embodiments and figures. FIG. 1 shows, in model form, the dependency of the potential on the charge. FIGS. 2A to 2C schematically show measurement arrangements for determining the potential-dependent charge of an electrode and the test curves obtained with the measurements, respectively. FIGS. 3A and 3B show a schematic test setup for leakage current measurement and a measurement curve obtained by means of the test setup. FIG. 4 shows a possible variant of a double-layer capacitor according to the invention. FIG. 5 shows a capacitor coil as an additional exemplary embodiment of a double-layer capacitor according to the invention. FIG. 1 shows, in model form, the dependency of the potential φ on the charge Q. In the case of a classic plate capacitor, in which, for example, two flat printed circuit boards, as electrodes, are separated by a dielectric, such as air, both positive potentials, i.e., for the positive electrode, and negative potentials, i.e., for the negative electrode, result in a linear progression 2A or 2B, the capacitance being constant in each case. In a double-layer capacitor, electron-conducting materials (electrodes) are in contact with ion-conducting materials (electrolytes), which, in reality, results in the schematic dependencies of the potential φ on the charge Q identified as 4A and 4B, for example. It is evident that the respective dependency of the charge on the potential for positive and negative potentials has different and, in particular, non-linear progressions, so that the capacitance is dependent on the potential. In the double-layer capacitor, the contact between the electron conductor and the electrolyte furthermore leads to corrosion phenomena, which are dependent on potential and can result in destruction of the components. The different magnitudes of the positive and negative critical corrosion potentials 6A and 6B, respectively, in FIG. 1 result in different projections 7A and 7B on the Q axis. These represent the respectively different maximum charges of the electrode at their critical corrosion potentials. A double-layer capacitor should be operated in such a way that charging ends as soon as one of the two electrodes has reached its corrosion potential (that is, the negative electrode has reached the negative corrosion potential and the positive electrode the positive corrosion potential). The charges of both electrode are always oppositely equal and, with respect to magnitude, exactly equal to the charge supplied to the capacitor by the external current circuit. Because of the potential dependency of the electrode capacitance described above and the non-oppositely equal distances of the corrosion potentials from the potential of the as yet uncharged electrode, one of the electrodes will usually reach its corrosion potential earlier than the other, so that the charging process must be terminated to prevent corrosion. The second electrode is then still at a distance from its corrosion potential and could thus absorb an additional charge. As a result, the volume of material used for this electrode cannot be fully used for energy storage. Thus, the energy density of the double-layer capacitor and the amount of material used per stored electric charge are not optimal. The fact that, therefore, the maximum potential difference between the electrodes, which is usable in principle, cannot be utilized leads to another disadvantage. The maximum charge voltage of the double-layer capacitor is smaller than the maximum possible value determined by the difference between the critical electrode potentials. Because the operating voltage of a double-layer capacitor cell lies at only a few volts, whereas the applications generally require higher voltages, it is of interest to choose the highest possible voltage for the individual cell, so that the smallest possible number of cells have to be connected in series to achieve the target voltage. Important parameters that can be modified to match the maximum charges of the electrodes are the surface characteristics of the electrodes, such as their capacitive active surface, which is determined by, among other things, the porosity and the particle size of the material, the corrosion stability of the electrodes and the charge eliminator, and the chemical composition of the electrolyte, e.g., valence and ion radii. FIG. 2A shows, in schematic form, a test setup for determining the potential-dependent charge. It is evident that a reference electrode 10, consisting, for example, of a coiled carbon fabric electrode, is introduced into a measuring cell 15 that contains an electrolyte solution 20. In this connection, aluminum is applied, by means of a spray process, for example, to the carbon fabrics. The first electrode 1 and the second electrode 5, the maximum charges of which are to be determined, are separated from one another by a separator 3. The voltage between the first and the second electrode was set to 0 V. Subsequently, a difference in potential is set between the electrode 1 and the reference electrode 10. Using the circuit array shown in FIG. 2B, and with the aid of a voltage divider 25, it was possible to set the difference in potential to any value within a range of 0 to 3 V, for example. A battery, for example, was used as a DC voltage source 30. The reference electrode 10 and the electrode 1 are integrated into the circuit array of FIG. 1B at the test points 39 or 35. Using a frequency response analyzer 60, an AC voltage of 5 mV, for example, is applied between the first electrode 1 and the second electrode 5, which is connected at 41 in FIG. 2B. The voltage multiplier 40 in the circuit array of FIG. 2B ensures that the resulting current response flows through the cell formed by electrodes 1 and 5 and does not escape through the voltage divider 25 and the battery. Following stabilization of the difference in potential between the reference electrode and the electrode 1 after 1 to 2 hours, an impedance measurement between electrodes 1 and 5 was performed at a small amplitude of about 5 mV, in order to measure the differential capacitance of the cell formed by electrodes 1 and 5. Electrode 5 apparently has the same potential relative to the reference electrode as electrode 1, because electrodes 1 and 5 only differ by the small AC voltage of 5 mV applied for the purpose of measuring impedance. Using different settings on the voltage divider 25, it was possible to determine the potential-dependent capacitance of the electrode 1 at various negative differences in potential between the electrode and the reference electrode. After the polarity of the battery had been reversed, it was possible to use the same approach to measure the capacitance of the electrode in the case of a positive difference in potential relative to the reference electrode. In this connection, the reference electrode 10 remains at resting potential, because it has a significantly larger surface area than the two other electrodes 1 or 5 (1.2 cm2 for the first and second electrode, for example, and about 100 cm2 for the reference electrode, for example). The electrolyte was stirred during the measurements using a floating stirrer, so that the concentration gradient possibly forming in the electrolyte could equalize more quickly. The distance between the first and second electrode was, for example, about 28 μm, and the amount of electrolyte was, for example, about 30 ml. In the measurements, a solution of 0.5 to 1.5 M tetraethylammonium tetrafluoroborate (C2H5)4NBF4 in 100% acetonitrile was used as the electrolyte. The two first and second electrodes 1, 5 were dried prior to measurement. FIG. 2C shows a measurement curve obtained by means of the measurement arrangement outlined in FIGS. 2A and 2B. The differential, potential-dependent capacitance, in F/cm3, is plotted against the difference in potential between the cell formed by electrodes 1 and 5 and the reference electrode 10. The positive differences in potential between this cell and the reference electrode are plotted to the right of the origin on the x axis and the negative differences in potential to the left of the origin on the x axis. It is evident that the capacitance progressions differ between positive and negative potential. This property was surprisingly discovered by the inventors and is attributable to the different behaviors of the anions and cations of the electrolyte in the electric field. The different volumes of the solvated positively and negatively charged ions, i.e., tetraethylammonium cations and tetrafluoroborate anions, in the case of the electrolyte solution described above, play as important a role as their mobility in the electrolyte solution and in the pores of the electrodes, as do the charges of the ions. In the case of FIG. 2C, the electrodes 1 and 5, as well as 10, consist of an aluminum foil with a thickness of about 30 μm, for example, to which the activated charcoal powder was applied in a thickness of about 100 μm. The density of the carbon layers of the electrodes 1 and 5 was approximately 0.71 g/cm3. Thus, FIG. 2C clearly shows that even electrodes made of the same electrode material and having the same design and dimensions exhibit different differential, potential-dependent capacitances when they have opposite polarity. A carbon fabric electrode with a larger surface area than the working electrodes was used as the reference electrode. FIG. 3A shows, schematically, a test setup for determining the leakage current that flows through the electrolyte between electrodes 1 and 5 when a specific difference in potential is set between the reference electrode 10 and the first electrode 1, as the working electrode. The purpose of the leakage current measurements is to discover the positive and/or negative limits in potential, up to which an electrode can be maximally charged. They are also used to determine the critical charge density already described earlier. This is defined as the maximum charge, per volume or mass of the electrode that can be supplied to the electrode without it reaching the corrosion potential. At the corrosion potential, electrochemical processes occur at the electrode that impair the serviceable life of the electrode and, for example, can lead to decomposition of the electrolyte, along with gas formation. Thus, the critical charge density indicates, in a manner of speaking, the maximum charge that can be supplied per volume or mass of the electrode. Between the working electrode 1 and the reference electrode 10, such as the carbon fabric electrode mentioned above, the voltage, beginning at 0 V, is increased incrementally and kept constant for a period of approximately 3 hours at each increment. The leakage current flowing through the electrolyte, between the working electrode 1 and the counter-electrode 5, is determined. To obtain a noise-free test signal, a voltage multiplier 40 (approximately 500 Ω) is connected ahead of the test setup 15. The potential of the counter-electrode relative to the reference electrode was recorded using an additional digital voltmeter. The surface area of both the working electrode and the counter-electrode was about 1 cm2, while that of the reference electrode was, once again, about 100 cm2. The distance between the working electrode and counter-electrode was about 1 cm. The measurement was performed in the above-mentioned electrolyte at room temperature. The electrolyte volume was approximately 30 ml. The working electrode, the counter-electrode and the reference electrode was heated in a vacuum at 90° C. prior to the measurement. FIG. 3B shows a measurement curve obtained by means of the leakage current measurement mentioned above. In this connection, the leakage current is plotted as a factor of the difference in potential between the working electrode 1 and the reference electrode 10. FIG. 4 shows a possible variant of a double-layer capacitor according to the invention, which comprises a layer stack consisting of alternating first electrode layers 1 and second electrode layers 5, with separators 3 disposed between the layers. In a double-layer capacitor according to the invention, the maximum charges of the first and the second electrode layer, given the same electrode materials, are adjusted by using different thicknesses of the electrode layers 1, 5. Electrode terminals 55 located on the housing 45 of the double-layer capacitor can be contacted by way of protruding small metal bands 50. FIG. 5 shows another possible embodiment of a double-layer capacitor according to the invention, in the form of a capacitor coil. In this case, a first electrode layer 1, a separator 3 as well as the second electrode layer 5 are coiled around a core tube or mandrel, which, after being removed, leaves the hole 55. In this embodiment of the double-layer capacitor, the respective electrode layers can also be contacted by way of protruding small metal bands 50 and, for adjustment of the maximum charges, have, for example, different thicknesses with identical electrode material. The invention is not limited to the exemplary embodiments described here. Other variations are possible, both with respect to the design of the electrodes and with respect to the structural shape of the capacitor. In this case, a matching of the maximum charges always occurs for a specific electrolyte, because different electrolytes cause different maximum charges and can thus require different measures for matching.
20051114
20081021
20060511
65133.0
H01G900
0
THOMAS, ERIC W
DOUBLE-LAYER CAPACITOR, USE OF THE SAME, AND METHOD FOR INCREASING THE MAXIMUM CHARGES OF DOUBLE-LAYER CAPACITOR ELECTRODES
UNDISCOUNTED
0
ACCEPTED
H01G
2,005
10,531,237
ACCEPTED
Quinolinyl-pyrrolopyrazoles
A compound according to formula II and the pharmaceutically acceptable salts thereof and the method of treating cancer in a patient in need thereof by administration of said compound.
1. A compound according to formula II and the pharmaceutically acceptable salts thereof. 2. The compound which is 2-(6-methyl-pyridin-2-yl)-3-[6-amido-quinolin-4-yl)-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazole and the pharmaceutically acceptable salts thereof. 3. A pharmaceutical formulation comprising a compound according to claim 1 or the pharmaceutically acceptable salt, ester or prodrug thereof together with a pharmaceutically acceptable diluent, excipient, or carrier. 4. A method of treating cancer which comprises administering to a patient in need thereof a therapeutically effective amount of a compound according to claim 1 or a pharmaceutically acceptable salt, ester or prodrug thereof.
The invention relates to new quionolinyl-pyrazole compounds and their use as pharmaceutical agents, in particular their use as TGF-beta signal transduction inhibitors. BACKGROUND OF THE INVENTION The transforming growth factor-beta (TGF-beta) (“TGF-β”) polypeptides influence growth, differentiation, and gene expression in many cell types. The first polypeptide of this family that was characterized, TGF-β1, has two identical 112 amino acid subunits that are covalently linked. TGF-β1 is a highly conserved protein with only a single amino acid difference distinguishing humans from mice. There are two other members of the TGF-β gene family that are expressed in mammals. TGF-β2 is 71% homologous to TGF-β1 (de Martin, et al. (1987) EMBO J. 6:3673-3677), whereas TGF-β3 is 80% homologous to TGF-β1 (Derynck, et al. (1988) EMBO J 7:3737-3743). The structural characteristics of TGF-β1 as determined by nuclear magnetic resonance (Archer, et al. (1993) Biochemistry 32:1164-1171) agree with the crystal structure of TGF-β2 (Daopin, et al. (1992) Science 257:369-374; Schlunegger and Grutter (1992) Nature 358:430-434). There are at least three different extracellular TGF-β receptors, Type I, II and III that are involved in the biological functions of TGF-β1, -β2 and -β3 (For reviews, see Derynck (1994) TIBS 19:548-553 and Massague (1990) Ann. Rev. Cell Biol. 6:597-641). The Type I and Type II receptors are transmembrane serine/threonine kinases, which in the presence of TGF-β form a heteromeric signaling complex (Wrana, et al (1992) Cell 71: 1003-1014). The mechanism of activation of the heteromeric signaling complex at the cell surface has been elucidated (Wrana, et al. (1994) Nature 370: 341-347). TGF-β first binds the type II receptor that is a constitutively active transmembrane serine/threonine kinase. The type I receptor is subsequently recruited into the complex, phoshorylated at the GS domain and activated to phosphorylate downstream signaling components (e.g. Smad proteins) to initiate the intracellular signaling cascade. A constitutively active type I receptor (T204D mutant) has-been shown to effectively transduce TGF-β responses, thus bypassing the requirement for TGF-β and the type II receptor (Wieser, et al. (1995) EMBO J 14: 2199-2208). Although no signaling function has been discovered for the type III receptor, it does increase TGF-β2's affinity for the type II receptor making it essentially equipotent with TGF-β1 and TGF-β3 (Lopez-Casillas, et al. (1993) Cell 73:1435-1444). Vascular endothelial cells lack the Type III receptor. Instead endothelial cells express a structurally related protein called endoglin (Cheifetz, et al. (1992) J. Biol. Chem. 267:19027-19030), which only binds TGF-β1 and TGF-β3 with high affinity. Thus, the relative potency of the TGF-β's reflects the type of receptors expressed in a cell and organ system. In addition to the regulation of the components in the multi-factorial signaling pathway, the distribution of the synthesis of TGF-β polypeptides also affects physiological function. The distribution of TGF-β2 and TGF-β3 is more limited Derynck, et al. (1988) EMBO J 7:3737-3743) than TGF-β1, e.g., TGF-β3 is limited to tissues of mesenchymal origin, whereas TGF-β1 is present in both tissues of mesenchymal and epithelial origin. TGF-β1 is a multifunctional cytokine critical for tissue repair. High concentrations of TGF-β1 are delivered to the site of injury by platelet granules (Assoian and Sporn (1986) J. Cell Biol. 102:1217-1223). TGF-β1 initiates a series of events that promote healing including chemo taxis of cells such as leukocytes, monocytes and fibroblasts, and regulation of growth factors and cytokines involved in angiogenesis, cell division associated with tissue repair and inflammatory responses. TGF-β1 also stimulates the synthesis of extracellular matrix components (Roberts, et al. (1986) Proc. Natl. Acad. Sci. USA 83:4167-4171; Sporn, et al. (1983) Science 219:1329-1330; Massague (1987) Cell 49:437-438) and most importantly for understanding the pathophysiology of TGF-β1, TGF-β1 autoregulates its own synthesis (Kim, et al. (1989) J. Biol. Chem. 264:7041-7045). The compounds disclosed herein may also exhibit other kinase activity, such as p38 kinase inhibition and/or KDR (VEGFR2) kinase inhibition. Assays to determine such kinase activity are known in the art and one skilled in the art would be able to test the disclosed compounds for such activity. SUMMARY OF THE INVENTION The disclosed invention also relates to the select compound of Formula II: 2-(6-methyl-pyridin-2-yl)-3-[6-amido-quinolin-4-yl)-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazole and the pharmaceutically acceptable salts thereof. The compound above is generically disclosed and claimed in PCT patent application PCT/US02/11884, filed 13 May 2002, which claims priority from U.S. patent application U.S. Ser. No. 60/293,464, filed 24 May 2001, and incorporated herein by reference. The above compound has been selected for having a surprisingly superior toxicology profile over the compounds specifically disclosed in application cited above. DETAILED DESCRIPTION OF THE INVENTION The term “effective amount” as used in “an effective amount of a compound of Formula I,” for example, refers to an amount of a compound of the present invention that is capable of inhibiting TGF-beta. The term μM refers to micromolar. The general chemical terms used herein have their usual meanings. The following abbreviations are used throughout the synthesis Schemes and Examples: DMF refers to dimethyl formamide THF refers to tetrahydrofuran Ms refers to mesyl which is methylsulfonyl THP refers to tetrahydropyran The compounds disclosed herein can be made according to the following schemes and examples. The examples should in no way be understood to be limiting in any way as to how the compounds may be made. The following scheme illustrates the preparation of the compound of Formula I. The following scheme illustrates the preparation of the compound of Formula II. The following examples further illustrate the preparation of the compounds of this invention as shown schematically in Schemes I and II. EXAMPLE 1 Preparation of 7-(2-morpholin-4-yl-ethoxy)-4-(2-pyridin-2-yl-5,6-dihydro-4H-pyrrolo[[1,2-b]pyrazol-3-yl)-quinoline A. Preparation of 4-(2-pyridin-2-yl-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-3-yl)-7-[2-(tetrahydropyran-2-yloxy)ethoxy]quinoline Heat 4-(2-pyridin-2-yl-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-3-yl)-quinolin-7-ol (376 mg, 1.146 mmol), cesium carbonate (826 mg, 2.54 mmol), and 2-(2-bromoethoxy)tetrahydro-2H-pyran (380 μL, 2.52 mmol) in DMF (5 mL) at 120° C. for 4 hours. Quench the reaction with saturated sodium chloride and then extract with chloroform. Dry the organic layer over sodium sulfate and concentrate in vacuo. Purify the reaction mixture on a silica gel column eluting with dichloromethane to 10% methanol in dichloromethane to give the desired subtitled intermediate as a yellow oil (424 mg, 81%). MS ES+ m/e 457.0 (M+1). B. Preparation of 2-[4-(2-pyridin-2-yl-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-3-yl)-quinolin-7-yloxy]-ethanol Heat a solution of 4-(2-pyridin-2-yl-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-3-yl)-7-[2-(tetrahydropyran-2-yloxy)ethoxy]quinoline (421 mg, 0.92 mmol) in acetic acid: tetrahydrofuran: water (4:2:1) (20 mL). Remove the solvent in vacuo and recover the residue with chloroform:isopropyl (3:1). Wash the organic layer with saturated sodium bicarbonate and dry over sodium sulfate. Concentrate in vacuo. The residue will be pure enough for the next step in the scheme (425 mg, 100%). MS ES+ m/e 373.1 (M+1). C. Preparation of Methanesulfonic Acid 2-[4-(2-pyridin-2-yl-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-3-yl)-quinolin-7-yloxy]-ethyl Ester Stir a solution of 2-[4-(2-pyridin-2-yl-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-3-yl)-quinolin-7-yloxy]-ethanol (293 mg, 0.78 mmol) and methane sulfonyl chloride (68μL, 0.81 ml) in dried pyridine (5 mL) for 2 hours. Remove the pyridine in vacuo and recover the residue with chloroform. Wash the organic layer with saturated sodium bicarbonate and dry over sodium sulfate to give the desired subtitled intermediate as a white foam (425 mg, 100%). MS ES+ m/e 451.1 (M+1). D. Preparation of 7-(2-morpholin-4-yl-ethoxy)-4-(2-pyridin-2-yl-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-3-yl)-quinoline Heat methanesulfonic acid 2-[4-(2-pyridin-2-yl-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-3-yl)-quinolin-7-yloxy]-ethyl ester (87 mg, 0.19 mmol) with morpholine (1 mL) at 50° C. for 4 hours. Remove the morpholine in vacuo and then extract the product with isopropyl alcohol:chloroform (1:3). Wash the organic layer with sodium chloride and dry over sodium sulfate. Concentrate in vacuo to give the desired title product as a slight yellow solid (83 mg, 100%). MS ES+ m/e 442.0 (M+1). EXAMPLE 2 Preparation of 2-(6-methyl-pyridin-2-yl)-3-[6-amido-quinolin-4-yl)-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazole A. Preparation of 6-bromo-4-methyl-quinoline Stir a solution of 4-bromo-phenylamine (1 eq), in 1,4-dioxane and cool to approximately 12° C. Slowly-add sulfuric acid (2 eq) and heat at reflux. Add methylvinyl ketone (1.5 eq) dropwise into the refluxing solution. Heat the solution for 1 hour after addition is complete. Evaporate the reaction solution to dryness and dissolve in methylene chloride. Adjust the solution to pH 8 with 1 M sodium carbonate and extract three times with water. Chromatograph the residue on SiO2 (70/30 hexane/ethyl acetate) to obtain the desired subtitled intermediate. MS ES+ m/e =158.2 (M+1). B. Preparation of 6-methyl-pyridine-2-carboxylic Acid Methyl Ester Suspend 6-methyl-pyridine-2-carboxylic acid (10 g, 72.9 mmol) in methylene chloride (200 mL). Cool to 0° C. Add methanol (10 mL), 4-dimethylaminopyridine (11.6 g, 94.8 mmol), and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) (18.2 g, 94.8 mmol). Stir the mixture at room temperature for 6 hours, wash with water and brine, and dry over sodium sulfate. Filter the mixture and concentrate in vacuo. Chromatograph the residue on SiO2 (50% ethyl acetate/hexanes) to obtain the desired subtitled intermediate, 9.66 g (92%), as a colorless liquid. 1H NMR (CDCl3) δ 7.93-7.88 (m, 1H), 7.75-7.7 (m, 1H), 7.35-7.3 (m, 1H), 4.00 (s, 3H), 2.60 (s, 3H). C. Preparation of 2-(6-bromo-quinolin-4-yl)-1-(6-methyl-pyridin-2-yl)-ethanone Dissolve 6-bromo-4-methyl-quinoline (38.5 g, 153 mmol) in 600 mL dry THF. Cool to −70° C. and treat with the dropwise addition of 0.5 M potassium hexamethyldisilazane (KN(SiMe3)2 (400 mL, 200 mmol) over 2 hours while keeping the temperature below −65 ° C. Stir the resultant solution at −70° C. for 1 hour and add a solution of 6-methylpyridine-2-carboxylic acid methyl ester (27.2, 180 mmol) in 100 mL dry THF dropwise over 15 minutes. During the addition, the mixture will turn from dark red to pea-green and form a precipitate. Stir the mixture at −70° C. over 2 hours then allow it to warm to ambient temperature with stirring for 5 hours. Cool the mixture then quench with 12 N HCl to pH=1. Raise the pH to 9 with solid potassium carbonate. Decant the solution from the solids and extract twice with 200 mL ethyl acetate. Combine the organic extracts, wash with water and dry over potassium carbonate. Stir the solids in 200 mL water and 200 mL ethyl acetate and treat with additional potassium carbonate. Separate the organic portion and dry with the previous ethyl acetate extracts. Concentrate the solution in vacuo to a dark oil. Pass the oil through a 300 mL silica plug with methylene chloride then ethyl acetate. Combine the appropriate fractions and concentrate in vacuo to yield an amber oil. Rinse the oil down the sides of the flask with methylene chloride then dilute with hexane while swirling the flask to yield 38.5 g (73.8%) of the desired subtitled intermediate as a yellow solid. MS ES+=341 (M+1). D. Preparation of 1-[2-(6-bromo-quinolin-4-yl)-1-(6-methyl-pyridin-2-yl)-ethylideneamino]-pyrrolidin-2-one Stir a mixture of 2-(6-bromo-quinolin-4-yl)-1-(6-methyl-pyridin-2-yl)-ethanone (38.5 g, 113 mmol) and 1-aminopyrrolidinone hydrochloride (20 g, 147 mmol) in 115 mL pyridine at ambient temperature for 10 hours. Add about 50 g 4 Å unactivated sieves. Continue stirring an additional 13 h and add 10-15 g silica and filter the mixture through a 50 g silica plug. Elute the silica plug with 3 L ethyl acetate. Combine the filtrates and concentrate in vacuo. Collect the hydrazone precipitate by filtration and suction dry to yield 33.3 g (69.7%) of the desired subtitled intermediate as an off-white solid. MS ES+=423 (M+1). E. Preparation of 6-bromo-4-[2-(6-methyl-pyridin-2-yl)-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-3-yl]-quinoline To a mixture of (1.2 eq.) cesium carbonate and 1-[2-(6-bromo-quinolin-4-yl)-1-(6-methyl-pyridin-2-yl)-ethylideneamino]-pyrrolidin-2-one (33.3 g, 78.7 mmol) add 300 mL dry N,N-dimethylformamide. Stir the mixture 20 hours at 100° C. The mixture may turn dark during the reaction. Remove the N,N-dimethylformamide in vacuo. Partition the residue between water and methylene chloride. Extract the aqueous portion with additional methylene chloride. Filter the organic solutions through a 300 mL silica plug, eluting with 1.5 L methylene chloride, 1.5 L ethyl acetate and 1.5 L acetone. Combine the appropriate fractions and concentrate in vacuo. Collect the resulting precipitate by filtration to yield 22.7 g (71.2%) of the desired subtitled intermediate as an off-white solid. MS ES+=405 (M+1). F. Preparation of 4-[2-(6-methyl-pyridin-2-yl)-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-3-yl]-quinoline-6-carboxylic Acid Methyl Ester Add 6-bromo-4-[2-(6-methyl-pyridin-2-yl)-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-3-yl]-quinoline (22.7 g, 45 mmol) to a mixture of sodium acetate (19 g, 230 mmol) and the palladium catalyst [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(I), complex with dichloromethane (1:1) (850 mg, 1.04 mmol) in 130 mL methanol. Place the mixture under 50 psi carbon monoxide atmosphere and stir while warming to 90° C. over 1 hour and with constant charging with additional carbon monoxide. Allow the mixture to cool over 8 hours, recharge again with carbon monoxide and heat to 90° C. The pressure may rise to about 75 PSI. The reaction is complete in about an hour when the pressure is stable and tic (1:1 toluene/acetone) shows no remaining bromide. Partition the mixture between methylene chloride (600 mL) and water (1 L). Extract the aqueous portion with an additional portion of methylene chloride (400 mL.) Filter the organic solution through a 300 mL silica plug and wash with 500 mL methylene chloride, 1200 mL ethyl acetate and 1500 mL acetone. Discard, the acetone portion. Combine appropriate fractions and concentrate to yield 18.8 g (87.4%) of the desired subtitled intermediate as a pink powder. MS ES+=385 (M+1). G. Preparation of 2-(6-methyl-pyridin-2-yl)-3-[6-amido-quinolin-4-yl)-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazole Warm a mixture of 4-[2-(6-methyl-pyridin-2-yl)-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-3-yl]-quinoline-6-carboxylic acid methyl ester in 60 mL 7 N ammonia in methanol to 90° C. in a stainless steel pressure vessel for 66 hours. The pressure will rise to about 80 PSI. Maintain the pressure for the duration of the reaction. Cool the vessel and concentrate the brown mixture in vacuo. Purify the residual solid on two 12 g Redi-Pak cartridges coupled in series eluting with acetone. Combine appropriate fractions and concentrate in vacuo. Suspend the resulting nearly white solid in methylene chloride, dilute with hexane, and filter. The collected off-white solid yields 1.104 g (63.8%) of the desired title product. MS ES+=370 (M+1). The compounds disclosed herein were tested by the following protocols for TGF-β inhibition, as described below in the protocol description. TGF-β Receptor I Purification and In Vitro Kinase Reactions For TGF-β Type I (RIT204D) Receptors: The 6×-HIS tagged cytoplasmic kinase domain of each receptor was expressed and purified from Sf9 insect cell lysates as briefly described below: Cell pellets after 48-72 hours of infection were lysed in lysis buffer (LB: 50 mM Tris pH 7.5, 150 mM NaCl, 50 mM NaF, 0.5% NP40 with freshly added 20 mM β-mercaptoethanol, 10 mM imidazole, 1 mM PMSF, 1× EDTA-free Complete Protease Inhibitor(Boehringer Mannheim). Cell lysates were clarified by centrifugation and 0.45 uM filtered prior to purification by Ni/NTA affinity chromatography (Qiagen). Chromatography Protocol: Equilibrate with 10 CV of LB, load sample, wash with 10 CV RIPA buffer (50 mM Tris pH 7.5, 150 mM NaCl, 1% NP40, 1 mM EDTA, 0.25% sodium deoxycholate, added fresh 20 mM β-mercaptoethanol, 1 mM PMSF), wash with 10 CV LB, wash with 10 CV 1× KB (50 mM Tris pH 7.5, 150 mM NaCl, 4 mM MgCl2, 1 mM NaF, 2 mM β-mercaptoethanol), elute with a linear gradient of 1× KB containing 200 mM Imidazole. Both enzymes were approximately 90% pure and had autophosphorylation activity. Reactions: 170-200 nM enzyme in 1× KB, compound dilution series in 1× KB/16% DMSO (20 μM to 1 nM final concentration with 4% DMSO final concentration), reactions started by adding ATP mix (4 μM ATP/1 μCi 33P-γ-ATP final concentrations) in 1× KB. Reactions were incubated at 30° C. for 1 hour. Reactions were stopped and quantitated using standard TCA/BSA precipitation onto Millipore FB glass fiber filter plates and by liquid scintillation counting on a MicroBeta JET. The compounds disclosed herein inhibit the TGF-β Type I (RIT204D) receptor kinase domain with IC50 values <20 μM, while exhibiting less toxicity in vivo than structurally related compounds as disclosed in PCT patent application PCT/US02/11884 identified above. Conditions “characterized by enhanced TGF-β activity” include those wherein TGF-β synthesis is stimulated so that TGF-β is present at increased levels or wherein TGF-β latent protein is undesirably activated or converted to active TGF-β protein or wherein TGF-β receptors are upregulated or wherein the TGF-β protein shows enhanced binding to cells or extracellular matrix in the location of the disease. Thus, in either case “enhanced activity” refers to any condition wherein the biological activity of TGF-β is undesirably high, regardless of the cause. A number of diseases have been associated with TGF-β1 over production. Inhibitors of TGF-β intracellular signaling pathway are useful treatments for fibroproliferative diseases. Specifically, fibroproliferative diseases include kidney disorders associated with unregulated TGF-β activity and excessive fibrosis including glomerulonephritis (GN), such as mesangial proliferative GN, immune GN, and crescentic GN. Other renal conditions include diabetic nephropathy, renal interstitial fibrosis, renal fibrosis in transplant patients receiving cyclosporin, and HIV-associated nephropathy. Collagen vascular disorders include progressive systemic sclerosis, polymyositis, scleroderma, dermatomyositis, eosinophilic fascitis, morphea, or those associated with the occurrence of Raynaud's syndrome. Lung fibroses resulting from excessive TGF-β activity include adult respiratory distress syndrome, idiopathic pulmonary fibrosis, and interstitial pulmonary fibrosis often associated with autoimmune disorders, such as systemic lupus erythematosus and scleroderma, chemical contact, or allergies. Another autoimmune disorder associated with fibroproliferative characteristics is rheumatoid arthritis. Eye diseases associated with a fibroproliferative condition include retinal reattachment surgery accompanying proliferative vitreoretinopathy, cataract extraction with intraocular lens implantation, and post glaucoma drainage surgery are associated with TGF-β1 overproduction. Fibrotic diseases associated with TGF-β1 overproduction can be divided into chronic conditions such as fibrosis of the kidney, lung and liver and more acute conditions such as dermal scarring and restenosis (Chamberlain, J. Cardiovascular Drug Reviews, 19(4):329-344). Synthesis and secretion of TGF-β1 by tumor cells can also lead to immune suppression such as seen in patients with aggressive brain or breast tumors (Arteaga, et al. (1993) J. Clin. Invest. 92:2569-2576). The course of Leishmanial infection in mice is drastically altered by TGF-β1 (Barral-Netto, et al. (1992) Science 257:545-547). TGF-β1 exacerbated the disease, whereas TGF-β1 antibodies halted the progression of the disease in genetically susceptible mice. Genetically resistant mice became susceptible to Leishmanial infection upon administration of TGF-β1. The profound effects of TGF-β1 on extracellular matrix deposition have been reviewed (Rocco and Ziyadeh (1991) in Contemporary Issues in Nephrology v.23, Hormones, autocoids and the kidney. ed. Jay Stein, Churchill Livingston, New York pp.391-410; Roberts, et al. (1988) Rec. Prog. Hormone Res. 44:157-191) and include the stimulation of the synthesis and the inhibition of degradation of extracellular matrix components. Since the structure and filtration properties of the glomerulus are largely determined by the extracellular matrix composition of the mesangium and glomerular membrane, it is not surprising that TGF-β1 has profound effects on the kidney. The accumulation of mesangial matrix in proliferative glomerulonephritis (Border, et al. (1990) Kidney Int. 37:689-695) and diabetic nephropathy (Mauer, et al. (1984) J. Clin. Invest. 74:1143-1155) are clear and dominant pathological features of the diseases. TGF-β1 levels are elevated in human diabetic glomerulosclerosis (advanced neuropathy) (Yamamoto, et al. (1993) Proc. Natl. Acad. Sci. 90:1814-1818). TGF-β1 is an important mediator in the genesis of renal fibrosis in a number of animal models (Phan, et al. (1990) Kidney Int. 37:426; Okuda, et al. (1990) J. Clin. Invest. 86:453). Suppression of experimentally induced glomerulonephritis in rats has been demonstrated by antiserum against TGF-β1 (Border, et al. (1990) Nature 346:371) and by an extracellular matrix protein, decorin, which can bind TGF-β1 (Border, et al. (1992) Nature 360:361-363). Too much TGF-β1 leads to dermal scar-tissue formation. Neutralizing TGF-β1 antibodies injected into the margins of healing wounds in rats have been shown to inhibit scarring without interfering with the rate of wound healing or the tensile strength of the wound (Shah, et al. (1992) Lancet 339:213-214). At the same time there was reduced angiogenesis, reduced number of macrophages and monocytes in the wound, and a reduced amount of disorganized collagen fiber deposition in the scar tissue. TGF-β1 may be a factor in the progressive thickening of the arterial wall which results from the proliferation of smooth muscle cells and deposition of extracellular matrix in the artery after balloon angioplasty. The diameter of the restenosed artery may be reduced 90% by this thickening, and since most of the reduction in diameter is due to extracellular matrix rather than smooth muscle cell bodies, it may be possible to open these vessels to 50% simply by reducing extensive extracellular matrix deposition. In uninjured pig arteries transfected in vivo with a TGF-β1 gene, TGF-β1 gene expression was associated with both extracellular matrix synthesis and hyperplasia (Nabel, et al. (1993) Proc. Natl. Acad. Sci. USA 90:10759-10763). The TGF-β1 induced hyperplasia was not as extensive as that induced with PDGF-BB, but the extracellular matrix was more extensive with TGF-β1transfectants. No extracellular matrix deposition was associated with FGF-1 (a secreted form of FGF) induced hyperplasia in this gene transfer pig model (Nabel (1993) Nature 362:844-846). There are several types of cancer where TGF-β1 produced by the tumor may be deleterious. MATLyLu rat prostate cancer cells (Steiner and Barrack (1992) Mol. Endocrinol 6:15-25) and MCF-7 human breast cancer cells (Arteaga, et al. (1993) Cell Growth and Differ. 4:193-201) became more tumorigenic and metastatic after transfection with a vector expressing the mouse TGF-β1. TGF-β1 has been associated with angiogenesis, metastasis and poor prognosis in human prostate and advanced gastric cancer (Wikstrom, P., et al. (1998) Prostate 37: 19-29; Saito, H. et al. (1999) Cancer 86: 1455-1462). In breast cancer, poor prognosis is associated with elevated TGF-β (Dickson, et al. (1987) Proc. Natl. Acad. Sci. USA 84:837-841; Kasid, et al. (1987) Cancer Res. 47:5733-5738; Daly, et al. (1990) J. Cell Biochem. 43:199-211; Barrett-Lee, et al. (1990) Br. J Cancer 61:612-617; King, et al. (1989) J. Steroid Biochem. 34:133-138; Welch, et al. (1990) Proc. Natl. Acad. Sci. USA 87:7678-7682; Walker, et al. (1992) Eur. J. Cancer 238:641-644) and induction of TGF-β1 by tamoxifen treatment (Butta, et al. (1992) Cancer Res. 52:4261-4264) has been associated with failure of tamoxifen treatment for breast cancer (Thompson, et al. (1991) Br. J. Cancer 63:609-614). Anti TGF-β1 antibodies inhibit the growth of MDA-231 human breast cancer cells in athymic mice (Arteaga, et al. (1993) J. Clin. Invest. 92:2569-2576), a treatment which is correlated with an increase in spleen natural killer cell activity. CHO cells transfected with latent TGF-β1 also showed decreased NK activity and increased tumor growth in nude mice (Wallick, et al. (1990) J. Exp. Med. 172:1777-1784). Thus, TGF-β secreted by breast tumors may cause an endocrine immune suppression. High plasma concentrations of TGF-β1 have been shown to indicate poor prognosis for advanced breast cancer patients (Anscher, et al. (1993) N. Engl. J. Med. 328-1592-1598). Patients with high circulating TGF-β before high dose chemotherapy and autologous bone marrow transplantation are at high risk for hepatic veno-occlusive disease (15-50% of all patients with a mortality rate up to 50%) and idiopathic interstitial pneumonitis (40-60% of all patients). The implication of these findings is 1) that elevated plasma levels of TGF-β1 can be used to identify at risk patients and 2) that reduction of TGF-β1 could decrease the morbidity and mortality of these common treatments for breast cancer patients. Many malignant cells secrete transforming growth factor-β (TGF-β), a potent imunosuppressant, suggesting that TGF-β production may represent a significant tumor escape mechanism from host immunosurveillance. Establishment of a leukocyte sub-population with disrupted TGF-β signaling in the tumor-bearing host offers a potential means for immunotherapy of cancer. A transgenic animal model with disrupted TGF-β signaling in T cells is capable of eradicating a normally lethal TGF-β over expressing lymphoma tumor, EL4 (Gorelik and Flavell, (2001) Nature Medicine 7(10): 1118-1122). Down regulation of TGF-β secretion in tumor cells results in restoration of immunogenicity in the host, while T-cell insensitivity to TGF-β results in accelerated differentiation and autoimmunity, elements of which may be required in order to combat self-antigen-expressing tumors in a tolerized host. The immunosuppressive effects of TGF-β have also been implicated in a subpopulation of HIV patients with lower than predicted immune response based on their CD4/CD8 T cell counts (Garba, et al. J. Immunology (2002) 168: 2247-2254). A TGF-β neutralizing antibody was capable of reversing the effect in culture, indicating that TGF-β signaling inhibitors may have utility in reversing the immune suppression present in this subset of HIV patients. During the earliest stages of carcinogenesis, TGF-β1 can act as a potent tumor suppressor and may mediate the actions of some chemopreventive agents. However, at some point during the development and progression of malignant neoplasms, tumor cells appear to escape from TGF-β-dependent growth inhibition in parallel with the appearance of bioactive TGF-β in the microenvironment. The dual tumor suppression/tumor promotion roles of TGF-β have been most clearly elucidated in a transgenic system over expressing TGF-β in keratinocytes. While the transgenics were more resistant to formation of benign skin lesions, the rate of metastatic conversion in the transgenics was dramatically increased (Cui, et al (1996) Cell 86(4):531-42). The production of TGF-β1 by malignant cells in primary tumors appears to increase with advancing stages of tumor progression. Studies in many of the major epithelial cancers suggest that the increased production of TGF-β by human cancers occurs as a relatively late event during tumor progression. Further, this tumor-associated TGF-β provides the tumor cells with a selective advantage and promotes tumor progression. The effects of TGF-β on cell/cell and cell/stroma interactions result in a greater propensity for invasion and metastasis. Tumor-associated TGF-β may allow tumor cells to escape from immune surveillance since it is a potent inhibitor of the clonal expansion of activated lymphocytes. TGF-β has also been shown to inhibit the production of angiostatin. Cancer therapeutic modalities such as radiation therapy and chemotherapy induce the production of activated TGF-β in the tumor, thereby selecting outgrowth of malignant cells that are resistant to TGF-β growth inhibitory effects. Thus, these anticancer treatments increase the risk and hasten the development of tumors with enhanced growth and invasiveness. In this situation, agents targeting TGF-β-mediated signal transduction might be a very effective therapeutic strategy. The resistance of tumor cells to TGF-β has been shown to negate much of the cytotoxic effects of radiation therapy and chemotherapy and the treatment-dependent activation of TGF-β in the stroma may even be detrimental as it can make the microenvironment more conducive to tumor progression and contributes to tissue damage leading to fibrosis. The development of a TGF-β signal transduction inhibitors is likely to benefit the treatment of progressed cancer alone and in combination with other therapies. The compounds are useful for the treatment of cancer and other disease states influenced by TGF-β by inhibiting TGF-β in a patient in need thereof by administering said compound(s) to said patient. TGF-β would also be useful against atherosclerosis (T. A. McCaffrey: TGF-βs and TGF-β Receptors in Atherosclerosis: Cytokine and Growth Factor Reviews 2000, 11, 103-114) and Alzheimer's (Masliah, E.; Ho, G.; Wyss-Coray, T.: Functional Role of TGF-β in Alzheimer's Disease Microvascular Injury: Lessons from Transgenic Mice: Neurochemistry International 2001, 39, 393-400) diseases. Pharmaceutical Compositions The compositions of the present invention are therapeutically effective amounts of the TGF-β antagonists, noted above. The composition may be formulated with common excipients, diluents or carriers, and compressed into tablets, or formulated elixirs or solutions for convenient oral administration or administered by intramuscular intravenous routes. The compounds can be administered transdermally and maybe formulated as sustained release dosage forms and the like. The method of treating a human patient according to the present invention includes administration of the TGF-β antagonists. The TGF-β antagonists are formulated into formulations which may be administered by the oral and rectal routes, topically, parenterally, e.g., by injection and by continuous or discontinuous intra-arterial infusion, in the form of, for example, tablets, lozenges, sublingual tablets, sachets, cachets, elixirs, gels, suspensions, aerosols, ointments, for example, containing from 1 to 10% by weight of the active compound in a suitable base, soft and hard gelatin capsules, suppositories, injectable solutions and suspensions in physiologically acceptable media, and sterile packaged powders adsorbed onto a support material for making injectable solutions. Advantageously for this purpose, compositions may be provided in dosage unit form, preferably each dosage unit containing from about 5 to about 500 mg (from about 5 to 50 mg in the case of parenteral or inhalation administration, and from about 25 to 500 mg in the case of oral or rectal administration) the compounds. Dosages from about 0.5 to about 300 mg/kg per day, preferably 0.5 to 20 mg/kg, of active ingredient may be administered although it will, of course, readily be understood that the amount of the compound actually to be administered will be determined by a physician, in the light of all the relevant circumstances including the condition to be treated, the choice of compound to be administered and the choice of route of administration and therefore the above preferred dosage range is not intended to limit the scope of the present invention in any way. The formulations useful for separate administration of the TGF-β antagonists will normally consist of at least one compound selected from the compounds specified herein mixed with a carrier, or diluted by a carrier, or enclosed or encapsulated by an ingestible carrier in the form of a capsule, sachet, cachet, paper or other container or by a disposable container such as an ampoule. A carrier or diluent may be a solid, semi-solid or liquid material which serves as a vehicle, excipient or medium for the active therapeutic substance. Some examples of the diluents or carrier which may be employed in the pharmaceutical compositions of the present invention are lactose, dextrose, sucrose, sorbitol, mannitol, propylene glycol, liquid paraffin, white soft paraffin, kaolin, fumed silicon dioxide, microcrystalline cellulose, calcium silicate, silica, polyvinylpyrrolidone, cetostearyl alcohol, starch, modified starches, gum acacia, calcium phosphate, cocoa butter, ethoxylated esters, oil of theobroma, arachis oil, alginates, tragacanth, gelatin, syrup, methyl cellulose, polyoxyethylene sorbitan monolaurate, ethyl lactate, methyl and propyl hydroxybenzoate, sorbitan trioleate, sorbitan sesquioleate and oleyl alcohol and propellants such as trichloromonofluoromethane, dichlorodifluoromethane and dichlorotetrafluoroethane. In the case of tablets, a lubricant may be incorporated to prevent sticking and binding of the powdered ingredients in the dies and on the punch of the tableting machine. For such purpose there may be employed for instance aluminum, magnesium or calcium stearates, talc or mineral oil. Preferred pharmaceutical, forms of the present invention are capsules, tablets, suppositories, injectable solutions, creams and ointments. Especially preferred are formulations for inhalation application, such as an aerosol, for injection, and for oral ingestion.
<SOH> BACKGROUND OF THE INVENTION <EOH>The transforming growth factor-beta (TGF-beta) (“TGF-β”) polypeptides influence growth, differentiation, and gene expression in many cell types. The first polypeptide of this family that was characterized, TGF-β1, has two identical 112 amino acid subunits that are covalently linked. TGF-β1 is a highly conserved protein with only a single amino acid difference distinguishing humans from mice. There are two other members of the TGF-β gene family that are expressed in mammals. TGF-β2 is 71% homologous to TGF-β1 (de Martin, et al. (1987) EMBO J. 6:3673-3677), whereas TGF-β3 is 80% homologous to TGF-β1 (Derynck, et al. (1988) EMBO J 7:3737-3743). The structural characteristics of TGF-β1 as determined by nuclear magnetic resonance (Archer, et al. (1993) Biochemistry 32:1164-1171) agree with the crystal structure of TGF-β2 (Daopin, et al. (1992) Science 257:369-374; Schlunegger and Grutter (1992) Nature 358:430-434). There are at least three different extracellular TGF-β receptors, Type I, II and III that are involved in the biological functions of TGF-β1, -β2 and -β3 (For reviews, see Derynck (1994) TIBS 19:548-553 and Massague (1990) Ann. Rev. Cell Biol. 6:597-641). The Type I and Type II receptors are transmembrane serine/threonine kinases, which in the presence of TGF-β form a heteromeric signaling complex (Wrana, et al (1992) Cell 71: 1003-1014). The mechanism of activation of the heteromeric signaling complex at the cell surface has been elucidated (Wrana, et al. (1994) Nature 370: 341-347). TGF-β first binds the type II receptor that is a constitutively active transmembrane serine/threonine kinase. The type I receptor is subsequently recruited into the complex, phoshorylated at the GS domain and activated to phosphorylate downstream signaling components (e.g. Smad proteins) to initiate the intracellular signaling cascade. A constitutively active type I receptor (T204D mutant) has-been shown to effectively transduce TGF-β responses, thus bypassing the requirement for TGF-β and the type II receptor (Wieser, et al. (1995) EMBO J 14: 2199-2208). Although no signaling function has been discovered for the type III receptor, it does increase TGF-β2's affinity for the type II receptor making it essentially equipotent with TGF-β1 and TGF-β3 (Lopez-Casillas, et al. (1993) Cell 73:1435-1444). Vascular endothelial cells lack the Type III receptor. Instead endothelial cells express a structurally related protein called endoglin (Cheifetz, et al. (1992) J. Biol. Chem. 267:19027-19030), which only binds TGF-β1 and TGF-β3 with high affinity. Thus, the relative potency of the TGF-β's reflects the type of receptors expressed in a cell and organ system. In addition to the regulation of the components in the multi-factorial signaling pathway, the distribution of the synthesis of TGF-β polypeptides also affects physiological function. The distribution of TGF-β2 and TGF-β3 is more limited Derynck, et al. (1988) EMBO J 7:3737-3743) than TGF-β1, e.g., TGF-β3 is limited to tissues of mesenchymal origin, whereas TGF-β1 is present in both tissues of mesenchymal and epithelial origin. TGF-β1 is a multifunctional cytokine critical for tissue repair. High concentrations of TGF-β1 are delivered to the site of injury by platelet granules (Assoian and Sporn (1986) J. Cell Biol. 102:1217-1223). TGF-β1 initiates a series of events that promote healing including chemo taxis of cells such as leukocytes, monocytes and fibroblasts, and regulation of growth factors and cytokines involved in angiogenesis, cell division associated with tissue repair and inflammatory responses. TGF-β1 also stimulates the synthesis of extracellular matrix components (Roberts, et al. (1986) Proc. Natl. Acad. Sci. USA 83:4167-4171; Sporn, et al. (1983) Science 219:1329-1330; Massague (1987) Cell 49:437-438) and most importantly for understanding the pathophysiology of TGF-β1, TGF-β1 autoregulates its own synthesis (Kim, et al. (1989) J. Biol. Chem. 264:7041-7045). The compounds disclosed herein may also exhibit other kinase activity, such as p38 kinase inhibition and/or KDR (VEGFR2) kinase inhibition. Assays to determine such kinase activity are known in the art and one skilled in the art would be able to test the disclosed compounds for such activity.
<SOH> SUMMARY OF THE INVENTION <EOH>The disclosed invention also relates to the select compound of Formula II: 2-(6-methyl-pyridin-2-yl)-3-[6-amido-quinolin-4-yl)-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazole and the pharmaceutically acceptable salts thereof. The compound above is generically disclosed and claimed in PCT patent application PCT/US02/11884, filed 13 May 2002, which claims priority from U.S. patent application U.S. Ser. No. 60/293,464, filed 24 May 2001, and incorporated herein by reference. The above compound has been selected for having a surprisingly superior toxicology profile over the compounds specifically disclosed in application cited above. detailed-description description="Detailed Description" end="lead"?
20050413
20070904
20060223
94591.0
A61K314709
0
SEAMAN, D MARGARET M
QUINOLINYL-PYRROLOPYRAZOLES
UNDISCOUNTED
0
ACCEPTED
A61K
2,005
10,531,369
ACCEPTED
Liquid crystal display and backlight adjusting method
A liquid crystal display apparatus and backlight adjustment method are provided. Backlight luminance sensors 111A to 111D are disposed in the vicinity of four outer corners of an effective screen of an LCD panel 121. Each of the backlight luminance sensors 111A to 111D detects the luminance of each of three primary colors. A backlight unit is composed of a three-primary LED array and a light diffusion unit. Transistors of the backlight luminance sensors and transistors of a pixel portion are formed on the same substrate in the same process. When a transistor is irradiated with backlight in its sufficient off region, an off current occurs due to light excitation. Since the value of the off current corresponds to the luminance of the rays of backlight that irradiates the transistor, the luminance of the backlight is detected with an output voltage into which the off current is converted. As a result, the luminance of the backlight is kept constant.
1. A liquid crystal display apparatus having a liquid crystal interposed between two substrates and a backlight as a light source for the liquid crystal, comprising: a luminance sensor formed on one of the substrates (this substrate is referred to as the first substrate), the luminance sensor and thin film devices as pixels being formed on the first substrate in the same process, the luminance sensor that detects the luminance of the backlight; and a control circuit that generates a drive signal that keeps the luminance of the backlight almost constant on the basis of a detection signal detected by the luminance sensor. 2. The liquid crystal display apparatus as set forth in claim 1, wherein the backlight includes a light emitting device array and a diffusion portion, the light emitting device array being an arrangement of repetition of at least three color light emitting devices, the diffusing portion that diffuses color rays emitted from the light emitting device array and generates white light. 3. The liquid crystal display apparatus as set forth in claim 1, wherein the backlight includes a light emitting device array, a diffusion portion, and a light guide portion, the light emitting device array that is an arrangement of repetition of at least three color light emitting devices in a line shape, the diffusion portion that diffuses color rays emitted from the light emitting device array and generates white light, the light guide portion that equally guides the color rays emitted from the light emitting device array to the entire surface of the diffusion portion. 4. The liquid crystal display apparatus as set forth in claim 1, wherein the substrate on which the thin film devices are formed when viewed from the liquid crystal side is disposed on the backlight side, at least one luminance sensor being disposed in a screen on which the pixels are formed, a light shield portion being disposed on the other substrate (this substrate is referred to as the second substrate) so that the light shield portion is opposite to the luminance sensor. 5. The liquid crystal display apparatus as set forth in claim 1, wherein the second substrate opposite to the first substrate on which the thin film devices are formed is disposed on the backlight side when viewed from the liquid crystal, at least one luminance sensor being disposed outside a screen on which the pixels of the thin film devices are formed, and wherein the liquid crystal display apparatus further comprises: a housing that houses the first substrate, the second substrate, the backlight, and the control circuit and that covers the luminance sensor. 6. The liquid crystal display apparatus, wherein the second substrate opposite to the first substrate on which the thin film devices are formed is disposed on the backlight side when viewed from the liquid crystal, wherein the luminance sensor detects an output voltage into which an off current due to light excitation corresponding to luminance of light emitted from the backlight is converted in the state that a thin film device that composes the luminance sensor is sufficiently turned off, and wherein the liquid crystal display apparatus further comprises: an input signal generation portion that generates an input signal having a repetitive period that is shorter than a period for which the liquid crystal transmits light and that the user does not recognize as flickering, the input signal generation portion that supplies the input signal to the thin film device that compose the luminance sensor; a sample hold portion that sample-holds a detection signal of the luminance sensor; and a control circuit that generates a drive signal that keeps the luminance of the backlight almost constant on the basis of a signal sample-held by the sample hold portion. 7. The liquid crystal display apparatus as set forth in claim 6, wherein the sample hold portion is formed on the first substrate on which thin film devices are formed. 8. The liquid crystal display apparatus as set forth in claim 1, wherein color filters corresponding to at least three color light emitting devices are disposed on one of the two substrate, wherein the luminance sensors are disposed corresponding to the light emitting devices and detect the luminance of each of the colors, and wherein the control circuit generates drive signals for the light emitting devices corresponding to the luminance of each of the colors. 9. A luminance adjustment method for backlight as a light source of white light that is a mixture of rays emitted from an arrangement of repetition of at least three-color light emitting devices disposed on a liquid crystal display panel, thin film devices being formed as a screen on the liquid crystal display panel, a luminance sensor being disposed on the liquid crystal display panel, comprising the steps of: detecting luminance of the backlight; generating a drive signal on the basis of the detected result at the first step; and driving at least three-color light emitting devices with the drive signal generated at the second step and keeping the luminance of the backlight almost constant. 10. A liquid crystal display method for the luminance adjustment method for backlight as a light source of white light that is a mixture of rays emitted from an arrangement of repetition of at least three-color light emitting devices disposed on a liquid crystal display panel, thin film devices being formed as a screen on the liquid crystal display panel, a luminance sensor being disposed on the liquid crystal display panel of claim 9, comprising the steps of: generates an input signal having a repetitive period that is shorter than a period for which the liquid crystal transmits light and that the user does not recognize as flickering and supplying the input signal to the thin film device that composes the luminance sensor; sample-holding the detected signal of the luminance sensor on the basis of the input signal supplied at the first step; generating a drive signal on the basis of the signal sample-held at the second step; and driving at least three-color light emitting devices with the drive signal generated at the third step so as to keep the luminance of the backlight almost constant.
CROSS REFERENCE TO RELATED APPLICATION The present application claims priority to Japanese Patent Document No. P2003-408735 filed on Dec. 8, 2003, the disclosure of which is herein incorporated by reference. BACKGROUND OF THE INVENTION The present invention relates to a liquid crystal display apparatus and a backlight adjustment method. A liquid crystal display (hereinafter abbreviated as an LCD), which is of non-self emitting type, needs backlight as a light source. Examples of the backlight are a cold cathode ray tube and a light emitting diode (hereinafter abbreviated as an LED). When an LED is used, a white diode can be used. However, in a liquid crystal television monitor, three-primary color LEDs of R (red), G (green), and B (blue) are often used to improve color reproducibility. By mixing these colors of these LEDs, white backlight is formed. When a white LED is used for backlight, since the luminance and chromaticity of the backlight depend on the current that flows in the LED, the duty of on time and off time of the current that flows in the LED is controlled as disclosed in related art (Japanese Patent Laid-Open Publication No. 2002-324685). In the related art as shown in FIG. 16, the luminance of backlight for an LCD module is adjusted by controlling current, duty, and so forth. In other words, an output current value of an LED drive current source 11 is controlled by a current value control circuit 12. A switch circuit 14 is disposed between the LED drive current source 11 and a white LED 15. The switch circuit 14 is turned on/off with a PWM signal of a PWM generation circuit 13. The duty ratio of the PWM signal is controlled with a control signal supplied from a duty ratio control circuit 16. However, the luminance of the backlight of the LCD module described in the document deteriorates by aged deterioration or the like. In the past, when an LCD module was shipped, the luminance of the backlight was adjusted. The luminance of the backlight was controlled by a thermistor as a temperature detection device. Alternatively, the end user needed to adjust the luminance of the backlight. Thus, after the liquid crystal display had been shipped, the aged deterioration of the luminance of the backlight could not be handled or it was improperly adjusted. Thus, the user needed to adjust the luminance of the backlight. SUMMARY OF THE INVENTION The present invention provides in an embodiment a thin type liquid crystal display apparatus and a backlight adjustment method that do not need the user to adjust the luminance of the backlight and that can be adjusted with high accuracy. The present invention provides in an embodiment a liquid crystal display apparatus having a liquid crystal interposed between two substrates and a backlight as a light source for the liquid crystal, comprising: a luminance sensor formed on one of the substrates (this substrate is referred to as the first substrate), the luminance sensor and thin film devices as pixels being formed on the first substrate in the same process, the luminance sensor that detects the luminance of the backlight; and a control circuit that generates a drive signal that keeps the luminance of the backlight almost constant on the basis of a detection signal detected by the luminance sensor. The backlight includes in an embodiment a light emitting device array and a diffusion portion, the light emitting device array being an arrangement of repetition of at least three color light emitting devices, the diffusing portion that diffuses color rays emitted from the light emitting device array and generates white light. Alternatively, the backlight includes in an embodiment a light emitting device array, a diffusion portion, and a light guide portion, the light emitting device array that is an arrangement of repetition of at least three color light emitting devices in a line shape, the diffusion portion that diffuses color rays emitted from the light emitting device array and generates white light, the light guide portion that equally guides the color rays emitted from the light emitting device array to the entire surface of the diffusion portion. Alternatively, the present invention includes in an embodiment a luminance adjustment method for backlight as a light source of white light that is a mixture of rays emitted from an arrangement of repetition of at least three-color light emitting devices disposed on a liquid crystal display panel, thin film devices being formed as a screen on the liquid crystal display panel, a luminance sensor being disposed on the liquid crystal display panel, comprising the steps of: detecting luminance of the backlight; generating a drive signal on the basis of the detected result at the first step; and driving at least three-color light emitting devices with the drive signal generated at the second step and keeping the luminance of the backlight almost constant. According to this aspect in an embodiment, since luminance sensors and pixel transistors of the LCD are formed in the same process, a thin type LCD panel unit can be produced. In addition, the luminance of the backlight can be kept constant. The luminance sensor detects an output voltage into which an off current due to light excitation corresponding to luminance of light emitted from the backlight is converted in the state that a thin film device that composes the luminance sensor is sufficiently turned off. The liquid crystal display apparatus further comprises an input signal generation portion that generates an input signal having a repetitive period that is shorter than a period for which the liquid crystal transmits light and that the user does not recognize as flickering, the input signal generation portion that supplies the input signal to the thin film device that compose the luminance sensor; a sample hold portion that sample-holds a detection signal of the luminance sensor; and a control circuit that generates a drive signal that keeps the luminance of the backlight almost constant on the basis of a signal sample-held by the sample hold portion. The sample hold portion is formed on the first substrate on which thin film devices are formed. According to this aspect in an embodiment, when a light insulation portion can not be disposed in a substrate opposite to a substrate on which thin film devices are formed or when a frame portion that shields luminance sensors cannot be disposed, since a potential that causes the sensor portion to sense the luminance of the backlight for a short time that the observer cannot recognize and that causes it to appear to be black in the rest of the time is applied to the sensor portion, even if the substrate on which the thin film devices are formed is disposed on the backlight side, the luminance of the backlight can be detected so that the observer does not recognize the sensor portion. The liquid crystal display apparatus according to an embodiment the present invention can keep the luminance of the backlight constant even if the aged deterioration takes place in the liquid crystal display apparatus. According to the present invention in an embodiment, the luminance detection means of the backlight can be disposed on the substrate for the pixel transistors of the LCD. In addition, the luminance detection means can be formed in the process for the pixel transistors. Thus, the cost of the sensors can be decreased. In addition, since the sensors can be formed in the LCD module, it can be thinned. Additional features and advantages of the present invention are described in, and will be apparent from, the following Detailed Description of the Invention and the figures. BRIEF DESCRIPTION OF THE FIGURES FIG. 1A is a sectional view showing an outlined structure of an LCD display apparatus, FIG. 1B being a plan view showing an outlined structure of the LCD display apparatus. FIG. 2 is a perspective view showing an outlined structure of an LCD panel unit. FIG. 3 is a perspective view showing an outlined structure of an example of the LCD panel unit. FIG. 4 is a perspective view showing an outlined structure of another example of the backlight unit. FIG. 5 is a schematic diagram showing connections of an equivalent circuit of one pixel in a write mode. FIG. 6 is a schematic diagram showing connections of an equivalent circuit of one pixel in a hold state. FIG. 7 is a schematic diagram showing connections of an equivalent circuit of a backlight luminance sensor according to an embodiment of the present invention. FIG. 8 is a schematic diagram showing characteristics of the backlight luminance sensor according to the embodiment of the present invention. FIG. 9 is a schematic diagram showing an example of the positions of the backlight luminance sensors according to the embodiment of the present invention. FIG. 10 is a perspective view showing a structure of a backlight luminance sensor portion according to the embodiment of the present invention. FIG. 11 is a perspective view showing a structure of a backlight luminance sensor portion according to another embodiment of the present invention. FIG. 12 is a schematic diagram showing connections of an equivalent circuit of a backlight luminance sensor according to the other embodiment of the present invention. FIG. 13 is a timing chart describing the operation of the other embodiment of the present invention. FIG. 14 is a block diagram showing a structure for a process for an output voltage of the backlight luminance sensor according to the present invention. FIG. 15 is a block diagram showing details of a part of the structure for the process for the output voltage of the backlight luminance sensor according to the present invention. FIG. 16 is a block diagram showing an example of a backlight luminance adjustment apparatus according to related art. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a liquid crystal display apparatus and a backlight adjustment method. Next, with reference to the accompanying drawings, an embodiments of the present invention will be described. Before that, a typical structure of a liquid crystal display apparatus will be described. As shown in FIG. 1A and FIG. 1B, a liquid crystal display apparatus 100 is composed of an LCD panel unit 101 and a backlight unit 102. In addition, a circuit for a control system is also disposed in the liquid crystal display apparatus 100. These units are housed in a housing 200. Reference numeral 200A represents a frame portion that surrounds a screen of the housing 200. As shown in FIG. 2, the LCD panel unit 101 is composed of two substrates 103A and 103B that are layered. The LCD panel unit 101 is a thin film transistor (TFT) liquid crystal. The TFT is categorized as an amorphous silicon type and a polysilicon type. The amorphous silicon type uses an amorphous material for a substrate. The polysilicon type uses a polysilicon material for a substrate. In FIG. 2, reference numeral 103A represents a backlight side substrate. Reference numeral 103B represents a screen side substrate. In the TFT liquid crystal, two substrates are oppositely disposed and a liquid crystal material is interposed therebetween. One substrate is a TFT side substrate on which TFTs and so forth are formed on a glass substrate. The other substrate is an opposite side substrate on which a color filter and so forth are disposed. A backlight luminance sensor, which will be described later, is formed on the TFT side substrate. As the substrate 103A shown in FIG. 2, an opposite side substrate is disposed. As the substrate 103B, a TFT side substrate is disposed. The relationship of this arrangement is referred to as pattern A. Alternatively, as the substrate 103A, a TFT side substrate may be disposed. As the substrate 103B, an opposite side substrate may be disposed. The relationship of this arrangement is referred to as pattern B. The present invention can be applied to any one of these arrangements. FIG. 3 shows an example of the backlight unit 102. Reference numeral 104 represents a three-primary color LED array. Reference numeral 105 represents an optical diffusion unit. The LED array 104 is composed of a repetition of a horizontal array of blue LEDs 106B, a horizontal array of green LEDs 106G, and a horizontal array of red LEDs 106R. The three-primary colors of the LEDs 106B, 106G, and 106R are diffused by the optical diffusion unit 105. As a result, the optical diffusion unit 105 generates white color backlight. FIG. 4 shows another example of the backlight unit 102. An LED array 107 is composed of red LEDs 106R, green LEDs 106G, and blue LEDs 106B that are alternately arranged in a line shape. The LED array 107 is disposed on the lower end side of a light guide plate 108. The light guide plate 108 equally transmits light of each LED of the LED array 107 to the entire surface of the optical diffusion unit 105. The optical diffusion unit 105 mixes the colors of the light guide plate 108. As a result, the optical diffusion unit 105 generates white color backlight. In addition to the light emitting devices of three-primary colors, light emitting devices of another color may be used to improve the color reproducibility. The backlight adjustment method according to the present invention is performed by controlling drive signals of light emitting devices of individual colors. To keep the luminance of the backlight constant, a sensor that measures the luminance of the backlight is needed. When the sensor that measures the luminance of the backlight is disposed in the structure shown in FIG. 3 or FIG. 4, the sensor needs to be disposed in the vicinity of the optical diffusion unit 105. When the luminance of the backlight is actually detected, it is preferred to dispose the sensor on the screen side. However, when the sensor is disposed on the screen side, the sensor shadows the screen. Thus, the sensor cannot be disposed on the screen side. As a practical arrangement method for the sensor, it may be disposed on a side surface of the optical diffusion unit 105 shown in FIG. 4 or in the space of the backlight unit 102 shown in FIG. 3 and FIG. 4 rather than on the LCD panel unit side. However, when the sensor is disposed on the side surface of the optical diffusion unit 105, the depth of the housing 200 increases by the thickness of the sensor. In the LCD module that is composed of LEDs of three primary colors shown in FIG. 3 and FIG. 4, unless the sensor receives the completely mixed light, the sensor will recognize incorrect luminance. In other words, when the sensor is disposed on the side surface of the optical diffusion unit 105 or in the space of the backlight unit 102, the sensor needs to receive the mixed light. According to the present invention, in consideration of the above-described point of view, white light which the backlight unit 102 emits to the LCD panel is detected. In other words, the sensor that detects the luminance of the backlight is disposed in the LCD panel. The sensor detects light with which the inside of the LCD panel is irradiated. Since the LCD panel is irradiated with designed white light of mixed colors, the sensor can receive white right of mixed colors. According to the embodiment of the present invention, the LCD panel unit 101 has a sensor that detects the luminance of the backlight. In addition, according to the embodiment of the present invention, the backlight luminance sensor and the pixel portion, namely TFTs, of the LCD panel unit 101 shown in FIG. 5 and FIG. 6 are formed in the same process. In FIG. 5 and FIG. 6, reference numeral 110 represents a structure of one pixel of the LCD panel unit 101. Tr represents a pixel transistor that has the same structure as an MOS-FET. G represents a gate line. S represents a source line (also called a data line). Cs represents a capacitor. C represents a Cs line. A gate of the transistor Tr is connected to the gate line G. A source of the transistor Tr is connected to the source line S. The capacitor Cs is connected between a drain of the transistor Tr and the Cs line C. A pixel electrode is connected in parallel with the capacitor Cs. A liquid crystal capacity Cd exists between the drain of the transistor Tr and an opposite electrode A. In FIG. 5 and FIG. 6, the transistor Tr is composed of an N channel type transistor. Alternatively, the transistor Tr may be composed of a P channel type transistor. Next, in the following description, it is assumed that the transistor Tr is composed of an N channel type transistor. FIG. 5 shows an equivalent circuit of the pixel 110 in a write state. Since signals are supplied to both the gate line G and the source line S, the pixel becomes active. A potential of the signal supplied through the source line S is written to the pixel through the pixel transistor Tr. When the pixel transistor Tr is turned on and a current flows between the drain and the source of the transistor Tr, the liquid crystal capacitor Cd and the capacitor Cs are charged. FIG. 6 shows an equivalent circuit of the pixel 110 in the state that a minus potential is supplied to the gate line of the transistor Tr and the transistor Tr is turned off (hold state). When an off current flows in the pixel transistor Tr through the gate line G, the pixel transistor Tr is turned off. The capacitor Cs, which is an auxiliary capacitor, holds the written signal potential until the next signal is written. FIG. 7 shows a structure of a backlight luminance sensor 111. Q represents a transistor of the backlight luminance sensor 111. A gate of the transistor Q is connected to a gate line G. A source of the transistor Q is connected to a terminal 112. A voltage VIN is supplied to the terminal 112. A drain of the transistor Q is connected to a terminal 113. An output voltage VOUT is obtained from the terminal 113. The transistor Q is an N channel MOS type transistor like the pixel transistor Tr. The transistor Q and the transistor Tr of the pixel portion are formed in the same process on the same substrate. The transistor Q has characteristics as shown in FIG. 8. The horizontal axis and the vertical axis of FIG. 8 represent a gate potential and a drain current, respectively. In this case, the relationship of (gate potential=potential of gate line G−potential of VIN) is satisfied. The drain current is a current that flows in the transistor Q, namely a current that flow between the terminals 112 and 113. With the gate potential, the transistor Q always has a sufficient off region. In the sufficient off region, when rays of backlight irradiate the transistor Q, an off current Ik (also called a leak current) occurs due to light excitation. The value of the off current Ik corresponds to the luminance of the rays of backlight that irradiate the transistor Q. Thus, with the output voltage VOUT into which the off current Ik is converted, the luminance of the backlight can be detected. The channel width and so forth of the transistor Q are different from those of the pixel transistor so that the off current of the transistor Q can be dynamically varied. For example, as shown in FIG. 9, backlight luminance sensors 111A, 111B, 111C, and 111D are disposed in the vicinity of four outer corners of the effective screen of an LCD panel 121. The backlight luminance sensors 111A to 111D detect the luminance of each of the three primary colors. As shown in FIG. 3, the backlight unit is composed of the three-primary color LED array 104 and the optical diffusion unit 105. Alternatively, the backlight luminance sensors may be disposed at four inner corners of the effective screen. The effective screen is a region in which pixels are disposed. Alternatively, backlight luminance sensors may be disposed at more positions than the four corners. When the integration of LCD panel 121 can be increased using for example low temperature polysilicon process, the backlight luminance sensors can be disposed to individual pixels. In this case, the luminance of the backlight can be measured from the entire region of the effective screen. FIG. 10 shows a green light detection sensor of one backlight luminance sensor, for example, 111A. In FIG. 10, a TFT substrate 131 is disposed on the backlight side. A TFT and a backlight luminance sensor are formed on the TFT substrate 131. An opposite substrate 132 is disposed opposite to the TFT substrate 131 with a liquid crystal material (not shown) interposed therebetween. The relationship of this arrangement is pattern B shown in FIG. 2. The size of each of the substrates 131 and 132 is the same as the size of one screen. However, for easy understanding, only one backlight luminance sensor is illustrated. White light Lw emitted from the backlight unit passes through a color (for example a green) filter film 133. The color filter film 133 transmits green light Lg. In FIG. 10, the color filter film 133 is spaced apart from the TFT substrate 131. Actually, the color filter film 133 adheres to the TFT substrate 131. The color filter film 133 adheres to a light transmission portion of the backlight luminance sensor that detects the luminance of green light with which the TFT substrate 131 is irradiated. In addition, backlight luminance sensors (transistors) (not shown in FIG. 10) that detect the luminance of red light and blue light of the white light Lw are disposed. As shown in FIG. 9, the backlight luminance sensors 111A to 111D are disposed around or inside the effective screen. In this case, these backlight luminance sensors 111A to 111d need to appear to be a black image so that the person who watches the screen, namely, the observer, does not feel that the picture quality deteriorates. If the backlight luminance sensor portions always appear to be white or with three primary colors, the observer recognizes them to be bright dots. Thus, the observer seems that the picture quality deteriorates. Thus, in FIG. 10, at least the opposite substrate 132 that is opposite to the light transmission portion of the backlight luminance sensor 111A is a light shield region. In this case, the backlight luminance sensor portion may be shielded with a member made of resin such as a frame of the housing of the LCD display apparatus instead of the opposite substrate 132. When the backlight luminance sensor portion is permitted to always appear to be white, it is not necessary to light shield it. FIG. 11 shows another embodiment of the present invention. According to the other embodiment, an opposite substrate 132 is disposed on the backlight side. A TFT substrate 131 is disposed on the screen side with a liquid crystal material (not shown) interposed therebetween. The relationship of the arrangement of the opposite substrate 132 and the TFT substrate 131 is pattern A shown in FIG. 2. The size of each of the TFT substrate 131 and the opposite substrate 132 is the same as the size of one screen. However, for easy understanding, only one backlight luminance sensor is illustrated. A green filter 134 is disposed in a region corresponding to a green light detection transistor of the backlight luminance sensor 111A of the opposite substrate 132. White light Lw emitted from the backlight unit passes through the green filter 134. The green filter 134 transmits green light Lg. The green light Lg passes through a liquid crystal material (not shown) and irradiates a transistor Q of the backlight luminance sensor 111A. Alternatively, light that passes through a color filter disposed on the opposite substrate 132 may irradiate the backlight luminance sensor 111A. FIG. 12 shows a structure of the backlight luminance sensor 111 according to another embodiment. Q represents a transistor of the backlight luminance sensor 111. A gate of the transistor Q is connected to a gate line G. A source of the transistor Q is connected to a terminal 112. A voltage VIN is supplied to the terminal 112. A drain of the transistor Q is connected to a terminal 113. An output voltage VOUT is obtained from the terminal 113. A liquid crystal capacitor Cd exists between the source of the transistor Q and an opposite electrode A. Like the pixel transistor Tr, the transistor Q is an N channel MOS type transistor. The transistor Q and the transistor Tr of the pixel portion are formed in the same process. As described above, with a gate voltage, the transistor Q always has a sufficient off region. In the sufficient off region, when rays of the backlight irradiate the transistor Q, an off current Ik occurs due to light excitement. The value of the off current Ik corresponds to the luminance of the rays of backlight that irradiate the transistor Q. Thus, with the output voltage VOUT into which the off current Ik is converted, the backlight luminance can be detected. In FIG. 12, reference numeral 135 represents an opening portion. The opening portion 135 of the opposite substrate 132 cannot be light shielded. When the opening portion 135 is light shielded in the arrangement shown in FIG. 11, the rays of backlight do not irradiate the transistor Q of the backlight luminance sensor. Thus, a sense time that the observer cannot recognize is set. FIG. 13 shows an example of timing at which the luminance of backlight is detected. FIG. 13 shows an input voltage VIN, an output voltage VOUT, and a gate line potential in the order. The gate line potential is a minus potential Voff that is lower than the threshold voltage of the transistor Q. The gate line potential is a level at which the transistor Q is sufficiently turned off. In the structure of the connections shown in FIG. 12, the input voltage VIN is applied to the liquid crystal interposed between the TFT substrate 131 and the opposite substrate 132. The input voltage VIN sets a white signal (a signal that causes the liquid crystal to transmit light) and a black signal (a signal that causes the liquid crystal to shield light) on the basis of the potential of the opposite electrode A. Assuming that the sum of the period Tb of the black signal and the period Tw of the white signal is a measurement interval, the period Tw is sufficiently short in the measurement interval. The measurement interval depends on the drive method of the LCD and the performance of the transistor. In the LCD composed of amorphous transistors, the measurement interval is preferably in the range from several microseconds to ten several milliseconds. The period Tw of the white signal is selected so that the observer is not bothered by a white image (flickering). When the level of the white signal is applied as the input voltage VIN in the period Tw, the liquid crystal transmits light. As a result, the green light Lg that passes through the color filter 134 irradiates the transistor Q of the backlight luminance sensor 111A. The transistor Q generates the detected voltage Vs as the output voltage VOUT. With the level of the detection voltage Vs, the luminance level of the backlight can be detected. The output voltage VOUT contains the offset voltage Vf. As shown in the timing chart shown in FIG. 13, the short time Tw that the observer cannot recognize is set as a sense time. In the other period, a potential for black is applied to the backlight luminance sensor. According to the embodiment shown in FIG. 11, not only the optical characteristics of the backlight, but the luminance of the backlight including the optical characteristics of the LCD color filter disposed on the opposite substrate 132 can be detected. In the arrangement shown in FIG. 11, a frame may be disposed around the screen of the liquid crystal display apparatus on the screen side of the TFT substrate 131 so that the frame shields light. FIG. 14 shows an example of a structure of a system that processes an output signal of a backlight luminance sensor. This system can be applied to both the foregoing embodiments. For example, detection voltages of the backlight luminance sensors disposed at four corners of the screen shown in FIG. 9 are supplied to amplifiers 142A, 142B, 142C, and 142D. Output voltages of the amplifiers 142A, 142B, 142C, and 142D are supplied to latches 143A, 143B, 143C, and 143D. The latches 143A to 143D are circuits that latch levels of detection voltages at predetermined timing defined with latch pulses. The latches 143A to 143D are composed of for example sample hold circuits. Output signals of the latches 143A to 143D are supplied to a microcomputer 144. The microcomputer 144 generates a compensation signal that keeps the luminance of the backlight constant. The compensation signal is supplied to an LED controller 145. The LED controller 145 generates a drive current to drive a red LED group 146R, a green LED group 146G, and a blue LED group 146B. The amplifier 142A and the latch 143A have signal paths corresponding to rays of three primary colors. Likewise, the amplifiers 142B, 142C, and 142D and the latches 143B, 143C, and 143D have signal paths corresponding to rays of three primary colors. FIG. 15 shows an example of one signal path of the system shown in FIG. 14. The off current of the transistor Q of the backlight luminance sensor varies with light as a variable resistor 147. The backlight luminance sensor is for example a red light sensor. The output voltage VOUT of the backlight luminance sensor is supplied to the latch 143A through the amplifier 142a. The value of the detection voltage of the output voltage VOUT is latched by the latch 143A. An output of the latch 143A is converted into a digital detection signal of for example six bits by an A/D converter 148. The digital detection signal of six bits is supplied to a compensation portion 149. A default value 150 of a luminance level held in a hold portion 150 is supplied to the compensation portion 149. The default value of the luminance level can be freely set. The compensation portion 149 compares the value of the digital detection signal with the default value and repeats an addition or a subtraction until they become equal. The compensation portion 149 detects the difference between the digital detection signal and the default value and outputs a digital difference signal of six bits. A D/A converter 151 outputs the digital difference signal as an analog compensation signal. The A/D converter 148, the hold portion 150, the compensation portion 149, and the D/A converter 151 represent functions as blocks, the functions being accomplished by the microcomputer 144 shown in FIG. 14. The analog difference signal is supplied from the D/A converter 151 to a drive current decision portion 152. The drive current decision portion 152 detects a drive current. The drive current decision portion 152 corresponds to the LED controller 145 shown in FIG. 14. The drive current decision portion 152 decides a drive current of the red LED group 146R. The red LED group 146R lights with the drive current. In the structure shown in FIG. 15, a drive current of the red LED group 146R is decided with the luminance detected by one backlight luminance sensor. In this case, the luminance of an LED in the vicinity of the backlight luminance sensor is controlled. When the duty ratio control circuit 16 and the PWM generation circuit 13 are disposed as shown in FIG. 16, the output of the D/A converter 151 may be directly input to the duty ratio control circuit 16. In this case, the drive current decision portion 152 is omitted. In the arrangement shown in FIG. 9, by dividing the length and breadth of the screen are divided by two each, four divided regions are obtained. The LED groups of the LED unit are divided so that they correspond to the four divided regions. Drive currents formed with the detection signals of the backlight luminance sensors are supplied to LEDs of the groups. When the output voltage VOUT shown in FIG. 15 is the output of the backlight luminance sensor 111A (see FIG. 9), the red LED group 146R is an LED group corresponding to the upper right region of the four divided regions. The process that correlates the positions of the backlight luminance sensors and the positions of the LED groups is an example. Alternatively, optimum drive currents may be generated by combining output signals of the backlight luminance sensors. For example, compensation signals formed of two luminance sensors may be linearly interpolated so as to generate compensation signals of individual portions of the screen. In the structure shown in FIG. 14, in a device such as a low temperature polysilicon, when peripheral circuits such as the amplifiers 142A to 142D and the latches 143A to 143D and the TFTs are formed on the same substrate, the peripheral circuits may be integrated with an LCD panel. It should be understood by those skilled in the art that various modifications, combinations, sub-combinations and alternations may occur depending on design requirements and other factors insofar as they are within the scope of the appended claims or the equivalents thereof. For example, when a white fluorescent lamp is used instead of three color LEDs, an AC pulse voltage supplied to the fluorescent lamp may be varied corresponding to the analog difference signal. It should be understood that various changes and modifications to the presently preferred embodiments described herein will be apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the present invention and without diminishing its intended advantages. It is therefore intended that such changes and modifications be covered by the appended claims.
<SOH> BACKGROUND OF THE INVENTION <EOH>The present invention relates to a liquid crystal display apparatus and a backlight adjustment method. A liquid crystal display (hereinafter abbreviated as an LCD), which is of non-self emitting type, needs backlight as a light source. Examples of the backlight are a cold cathode ray tube and a light emitting diode (hereinafter abbreviated as an LED). When an LED is used, a white diode can be used. However, in a liquid crystal television monitor, three-primary color LEDs of R (red), G (green), and B (blue) are often used to improve color reproducibility. By mixing these colors of these LEDs, white backlight is formed. When a white LED is used for backlight, since the luminance and chromaticity of the backlight depend on the current that flows in the LED, the duty of on time and off time of the current that flows in the LED is controlled as disclosed in related art (Japanese Patent Laid-Open Publication No. 2002-324685). In the related art as shown in FIG. 16 , the luminance of backlight for an LCD module is adjusted by controlling current, duty, and so forth. In other words, an output current value of an LED drive current source 11 is controlled by a current value control circuit 12 . A switch circuit 14 is disposed between the LED drive current source 11 and a white LED 15 . The switch circuit 14 is turned on/off with a PWM signal of a PWM generation circuit 13 . The duty ratio of the PWM signal is controlled with a control signal supplied from a duty ratio control circuit 16 . However, the luminance of the backlight of the LCD module described in the document deteriorates by aged deterioration or the like. In the past, when an LCD module was shipped, the luminance of the backlight was adjusted. The luminance of the backlight was controlled by a thermistor as a temperature detection device. Alternatively, the end user needed to adjust the luminance of the backlight. Thus, after the liquid crystal display had been shipped, the aged deterioration of the luminance of the backlight could not be handled or it was improperly adjusted. Thus, the user needed to adjust the luminance of the backlight.
<SOH> SUMMARY OF THE INVENTION <EOH>The present invention provides in an embodiment a thin type liquid crystal display apparatus and a backlight adjustment method that do not need the user to adjust the luminance of the backlight and that can be adjusted with high accuracy. The present invention provides in an embodiment a liquid crystal display apparatus having a liquid crystal interposed between two substrates and a backlight as a light source for the liquid crystal, comprising: a luminance sensor formed on one of the substrates (this substrate is referred to as the first substrate), the luminance sensor and thin film devices as pixels being formed on the first substrate in the same process, the luminance sensor that detects the luminance of the backlight; and a control circuit that generates a drive signal that keeps the luminance of the backlight almost constant on the basis of a detection signal detected by the luminance sensor. The backlight includes in an embodiment a light emitting device array and a diffusion portion, the light emitting device array being an arrangement of repetition of at least three color light emitting devices, the diffusing portion that diffuses color rays emitted from the light emitting device array and generates white light. Alternatively, the backlight includes in an embodiment a light emitting device array, a diffusion portion, and a light guide portion, the light emitting device array that is an arrangement of repetition of at least three color light emitting devices in a line shape, the diffusion portion that diffuses color rays emitted from the light emitting device array and generates white light, the light guide portion that equally guides the color rays emitted from the light emitting device array to the entire surface of the diffusion portion. Alternatively, the present invention includes in an embodiment a luminance adjustment method for backlight as a light source of white light that is a mixture of rays emitted from an arrangement of repetition of at least three-color light emitting devices disposed on a liquid crystal display panel, thin film devices being formed as a screen on the liquid crystal display panel, a luminance sensor being disposed on the liquid crystal display panel, comprising the steps of: detecting luminance of the backlight; generating a drive signal on the basis of the detected result at the first step; and driving at least three-color light emitting devices with the drive signal generated at the second step and keeping the luminance of the backlight almost constant. According to this aspect in an embodiment, since luminance sensors and pixel transistors of the LCD are formed in the same process, a thin type LCD panel unit can be produced. In addition, the luminance of the backlight can be kept constant. The luminance sensor detects an output voltage into which an off current due to light excitation corresponding to luminance of light emitted from the backlight is converted in the state that a thin film device that composes the luminance sensor is sufficiently turned off. The liquid crystal display apparatus further comprises an input signal generation portion that generates an input signal having a repetitive period that is shorter than a period for which the liquid crystal transmits light and that the user does not recognize as flickering, the input signal generation portion that supplies the input signal to the thin film device that compose the luminance sensor; a sample hold portion that sample-holds a detection signal of the luminance sensor; and a control circuit that generates a drive signal that keeps the luminance of the backlight almost constant on the basis of a signal sample-held by the sample hold portion. The sample hold portion is formed on the first substrate on which thin film devices are formed. According to this aspect in an embodiment, when a light insulation portion can not be disposed in a substrate opposite to a substrate on which thin film devices are formed or when a frame portion that shields luminance sensors cannot be disposed, since a potential that causes the sensor portion to sense the luminance of the backlight for a short time that the observer cannot recognize and that causes it to appear to be black in the rest of the time is applied to the sensor portion, even if the substrate on which the thin film devices are formed is disposed on the backlight side, the luminance of the backlight can be detected so that the observer does not recognize the sensor portion. The liquid crystal display apparatus according to an embodiment the present invention can keep the luminance of the backlight constant even if the aged deterioration takes place in the liquid crystal display apparatus. According to the present invention in an embodiment, the luminance detection means of the backlight can be disposed on the substrate for the pixel transistors of the LCD. In addition, the luminance detection means can be formed in the process for the pixel transistors. Thus, the cost of the sensors can be decreased. In addition, since the sensors can be formed in the LCD module, it can be thinned. Additional features and advantages of the present invention are described in, and will be apparent from, the following Detailed Description of the Invention and the figures.
20050414
20100126
20060112
86341.0
G09G336
0
NGUYEN, KIMNHUNG T
LIQUID CRYSTAL DISPLAY AND BACKLIGHT ADJUSTING METHOD
UNDISCOUNTED
0
ACCEPTED
G09G
2,005
10,531,413
ACCEPTED
Method for the presentation of information concerning variations of the perfusion
The invention relates to a method for the presentation of information concerning variations of the arterial filling with blood (perfusion) of organs of living beings on the user surface (10) of a display screen, in which method the data required for the presentation (perfusion index) is derived, using an algorithm, from measuring values of a non-invasive photometric measuring process for determining the arterial oxygen saturation of the blood. The invention is characterized in that a first perfusion index is defined as a reference value and the subsequent perfusion indices are determined as relative deviations with respect to the reference value, said relative deviations being presented in the form of analog, graphic elements (42, 44) on the user surface (10) as information concerning the 10 variations of the perfusion.
1. A method for the presentation of information concerning variations of the arterial filling with blood of organs of living beings on the user surface of a display unit, in which method the data required for the presentation is determined, using an algorithm, from measuring values produced by a non-invasive photometric measuring process for determining the arterial oxygen saturation of the blood, wherein a first perfusion index is defined as a reference value and the subsequent perfusion indices are determined as relative deviations with respect to the reference value, said relative deviations being presented as information concerning the variations of the perfusion on the user surface. 2. A method as claimed in claim 1, wherein the determination of the reference value takes place automatically at the beginning of the photometric measuring process. 3. A method as claimed in claim 1, wherein the instant of determination of the reference value can be chosen at will. 4. A method as claimed in claim 1, wherein the reference value is stored on a memory chip. 5. A method as claimed in claim 1, wherein the reference value as well as the subsequent perfusion indices are scaled by a factor. 6. A method as claimed in claim 5, wherein the factor is adjustable. 7. A method as claimed in claim 1, wherein the variation of the perfusion is presented in numerical form. 8. A method as claimed in claim 1, wherein analog graphic elements are used for the presentation. 9. A method as claimed in claim 8, wherein bar elements are used as the graphic elements. 10. A method as claimed in claim 9, wherein the relative variations of the perfusion are represented by different bar lengths. 11. A method as claimed in claim 8, wherein a representation in conformity with a tachometer display is used as the graphic element. 12. A method as claimed in claim 8, wherein the display is formed as a multidimensional type in conjunction with other physiological variables, notably as a spider diagram. 13. A method as claimed in claim 1, wherein an upper alarm limit and a lower alarm limit are provided. 14. A method as claimed in claim 13, wherein the alarm limit is adjustable. 15. A method as claimed in claim 13, wherein an acoustic and/or optical alarm signal is triggered when the alarm limit is exceeded. 16. (canceled) 17. A method of determining the quality of the measuring values derived by means of a photometric measuring process, wherein the signal quality is determined by the modulation factor (AC/DC) of one or more wavelengths in combination with one or more of the following variables: saturation-independent perfusion index transmission factor extent of ambient disturbances, such as stray light, EM radiation, and the like shape of the PLETH signal strength and/or duration of artifacts. 18. A method of presenting the quality of the measuring values (signal quality) derived by means of the photometric measuring process, notably as claimed in claim 17, wherein this information is graphically presented on the user surface by way of different coloring of icons and/or background areas, the coloring depending on said quality. 19. A method as claimed in claim 18, wherein the icons are identical to the graphic elements used for the presentation of the perfusion. 20. A method as claimed in claim 18, wherein the icons are independent graphic elements. 21. A device, comprising a pulsoximeter for determining arterial O2 saturation and for calculating perfusion index in order to determine information concerning variation of the perfusion, means for detection of interference signals, and for estimating the quality of the measuring values acquired and the information concerning a variation of the perfusion, and means for presenting the information.
The invention relates to a method for the presentation of information concerning variations of the perfusion as disclosed in claim 1, to a method for the presentation of the quality of the measuring values (signal quality) acquired during a photometric measuring process as claimed in the claims 16 to 18, and to a device for carrying out the method as disclosed in claim 21. As is known, in the field of patient monitoring special patient data such as, for example, perfusion, oxygen saturation of the arterial blood (SPO2 value), ECG curves and the like are important for the evaluation of the condition of a patient. Information as regards the perfusion can be derived only indirectly in normal practice. To this end, the clinical staff can fall back on measuring values resulting from the measurement of the oxygen saturation of the arterial blood. The measurement of the arterial oxygen saturation of the blood or the arterial hemoglobin is usually performed continuously in a non-invasive manner by means of a photometric measuring process, that is, the so-called pulsoximetry. A peripheral part of the body, usually a finger, is then irradiated by means of a sensor. The sensor usually comprises two light sources for the emission of light and a corresponding photodetector for the measurement of the light absorption. Pulsoximetry is based on two principles. On the one hand, the oxygen-enriched hemoglobin (oxyhemoglobin) and the oxygen-reduced hemoglobin (desoxyhemoglobin) differ as regards their ability to absorb red and infrared light (spectrophotometry) and on the other hand the amount of arterial blood in the tissue changes, and hence also the absorption of light by this blood, during the pulse (plethysmography). A pulsoximeter determines the SPO2 value by emitting red and infrared light and by measuring the variations of the light absorption during the pulse cycle. Whereas the clinical staff is presented with the oxygen saturation of the blood, that is, the SPO2 value, in the form of a numerical value, for information concerning the perfusion the staff has to take recourse to an interpretation of the plethysmography curve which is presented in the context of the pulsoximetry; this curve also shows inter alia the variation of the volume of a part of the body which is induced by the perfusion. Because the perfusion is a clinically relevant parameter which is used, for example, to signal the changing of physiological factors, the effect of anesthesia or the like, this way of deriving information concerning the perfusion is found to be very detrimental. On the one hand, the read-out accuracy is limited as the information has to be read from a curve which is not especially conceived for this purpose, meaning that this information has to be estimated, whereas on the other hand the amplification must be invariable for the presentation of the curve, making an evaluation of the shape of the curve practically impossible in the case of a very low perfusion. Moreover, a change of the curve amplitude in the plethysmogram is also dependent on the oxygen saturation and not only on the amount of blood flowing into the part of the body, for example, a finger. U.S. Pat. No. 4,867,165 A1 discloses a method for determining the perfusion whereby the perfusion can be quantified. To this end, a so-called perfusion index is determined from measuring values of the pulsoximetry process by means of an algorithm. It has been found to be a drawback of this method, however, that it yields absolute values only so that the detection of a variation of the perfusion by the clinical staff must take place by continuous observation and comparison of numerical values. It is an object of the invention to mitigate this problem by way of a method for the presentation of information concerning variations of the perfusion, thus facilitating the reading out of this information while avoiding said drawbacks. In respect of the method this object is achieved as disclosed in the characterizing part of claim 1 whereas in respect of the device it is achieved as disclosed in claim 21. Further features of the invention are disclosed in the claims 16 to 18 and in the dependent claims. The invention is based on the recognition of the fact that information represented by autonomous graphic elements can be observed faster and simpler than information that has to be derived by interpretation of curves or comparison of several numerical values. In accordance with the invention, the numerical data (perfusion index) required for the graphic presentation of the variations of the perfusion is determined continuously from measuring values of the photometric measuring process while using an algorithm. A first perfusion index is defined as a reference value and the relative deviations of the subsequent perfusion indices are determined in relation to this reference value. These relative deviations are represented by analog graphic elements on the user surface of the display screen as information concerning the variation of the perfusion. Thus, it is simply possible to read out the relative variation of the perfusion, which is presented in the form of analog graphic elements. Such a representation is very advantageous, because the clinical staff is presented with significant and ready-for-use information concerning the variation of the perfusion. Interpretation on the basis of the plethysmography curve or by continuous observation and comparison of numerical values is no longer necessary. Moreover, the size of presentation of the plethysmography curve can now be automatically adapted to the signal, thus facilitating interpretation of the curve characteristic. Preferably, the reference value is automatically determined at the beginning of the photometric measuring process. The instant for determining the reference value, however, can also be chosen at will by the clinical staff. It is thus ensured that a negative effect on the reference value, for example, due to a temporary state of shock of the patient or the like, can be precluded by way of a suitable choice of the instant for determining the reference value. For reasons of flexibility, for example, for the comparison of two reference values of a patient which have been determined at different instants, such values can be stored on a memory chip. In order to enable adjustment of the size of the graphic element and hence of the presentation of the information concerning variations of the perfusion, the reference value as well as the subsequent perfusion indices can be normalized or scaled with a factor. Preferably, this factor is individually adjustable. The individual adjustability offers the advantage that the representation can be readjusted in dependence on a relevant situation, for example, also during an operation, so that an optimum presentation of the information concerning variations of the perfusion is always ensured. In order to ensure a clear, readily recognizable presentation of the information, the information concerning variations of the perfusion is presented in the form of bar elements. The relative variations of the perfusion are preferably represented by way of different lengths of the bars. The use of different bar lengths for the representation of the relative variation has been found to be advantageous, because it ensures in a simple manner a fast optical and intuitive recognition of a change of information by the clinical staff. In order to facilitate the recognition of critical variations of the perfusion there is provided an upper alarm limit and a lower alarm limit, each of which is individually adjustable. When a critical value is reached, that is, when the adjusted alarm limits are exceeded, such an event can then be accentuated by means of an optical and/or acoustic signal. Preferably, the quality of the measuring values (signal quality) acquired during the photometric measuring process is presented on the user surface of the display screen by way of a different color of icons or background areas, that is, the color green for everything in order, yellow for dubious and red for poor. The estimation of the signal quality can be performed, for example, by evaluation of a combination of various parameters such as, for example, transmission level, interference level, artifact level, signal waveform, perfusion index or the like. The additional presentation of the signal quality is of major importance to the clinical staff, because it enables an evaluation of the measuring values derived from pulsoximetry as well as an evaluation of the information concerning the variations of the perfusion. Moreover, the coloring ensures intuitive observation, which in turn substantially simplifies the interpretation of the indicated signal quality. Preferably, the same graphic elements are used for the presentation of the variations of the perfusion and for the presentation of the signal quality. Thus, a bar element provided for the presentation of the variation of the perfusion may at the same time be colored, that is, green for the signal quality o.k., yellow for a reduced signal quality, or red for a poor signal quality. This form of presentation, where the icons for the presentation of the signal quality are identical to the graphic elements for the presentation of the variations of the perfusion, has been found to be advantageous, because it results in a space-saving display format. A further space-saving possibility for presentation consists in that a background area, for example, the background of the bar elements, the plethysmography curve or also the background of the numerical display for the oxygen saturation, is characterized by a corresponding color. Coloring of other elements, for example, of the plethysmography curve itself, is also feasible. However, it is also possible to present the icons as independent graphic elements, notably as a segment or bar representation, as color-encoded surface elements, or in the form of three circular elements arranged like a traffic light. The device for carrying out the method includes a pulsoximeter for determining the arterial O2 saturation and for calculating the perfusion index for the determination of the information concerning the variation of the perfusion, means for detecting interference signals, notably motion artifacts, and for estimating the quality of the acquired measuring values and hence the information concerning a variation of the perfusion, and means for displaying the information. Further advantages and feasible applications of the present invention are disclosed in the following description in conjunction with the embodiment which is shown in the drawing. The invention is described more or less diagrammatically hereinafter on the basis of an embodiment as shown in the drawing. Therein: FIG. 1 is a diagrammatic representation of a user surface of a display screen as used in the field of patient monitoring, FIG. 2 shows a measuring cap which is fitted on the tip of a finger and comprises two light-emitting diodes and a photoreceiver, FIG. 3 shows a part of a further user surface with graphic elements for the presentation of the perfusion, FIG. 4 shows a part of a user surface with graphic elements for the presentation of the perfusion and independent graphic elements for the presentation of the signal quality, and FIG. 5 shows a further part of a user surface with graphic elements for the presentation of the variation of the perfusion. For a better understanding of the invention a brief description will first be given of the procedures used thus far for the determination of the perfusion of a patient. FIG. 1 shows a typical user surface 10 as used in the field of patient monitoring. The Figure shows inter alia a plurality of dynamically varying patient data, such as an ECG (electrocardiography) curve (derivative I) 12, a further ECG curve (derivative II) 14, a plethysmography curve 16 as well as a CO2 respiration curve 18. To the right of the real-time curves 12, 14, 16 and 18 the associated physiological values are displayed in numerical form. For example, to the right of the plethysmography curve 16 the current value of the oxygen saturation of the arterial blood (SPO2 value) 20 is shown with associated alarm limits 22. With regard to the perfusion to be monitored, thus far the plethysmography curve 16 was observed by the clinical staff in order to derive information as regards the current perfusion by interpretation of the varying curve amplitude. As is known, the plethysmography curve 16 is determined by means of a photometric measuring process, that is, the so-called pulsoximetry. Pulsoximetry is a spectrophotometric method for the non-invasive determination of the arterial oxygen saturation of the blood. To this end, use is made of a measuring cap 24 as shown in FIG. 2, which cap comprises two light-emitting diodes 26, 28 and a photoreceiver 30 and is fitted on the tip 32 of a finger of the patient to be monitored. The arteries 36 and veins 38 extending in the tissue 34 and the capillaries 40 present between the arteries 36 and veins 38 are denoted by dashed lines. The light-emitting diodes 26 and 28 emit light of different wavelength, for example, 660 nm and 950 nm, to the photoreceiver 30. The photoreceiver 30 measures the intensity variation of the light which is due to a variation of an arterial blood volume and converts this information into a current signal which serves inter alia to present the plethysmography curve 16 on the user surface 10. Since photometric measuring methods are well known, for the sake of simplicity the measuring method will not be shown or elaborated further. In order to enable direct representation of the variations of the perfusion of a patient, a known algorithm is used to determine the so-called perfusion index from the measuring values continuously produced by pulsoximetry. After a first perfusion index has been defined as a reference value, the relative deviations of the subsequently calculated perfusion indices are determined relative to the reference value. Such relative deviations then serve as information concerning the variation of the perfusion and are presented on the user surface 10 in the form of graphic elements. Because artifacts due to optical disturbances or motion of the patient are recognized prior to the calculation of the perfusion index and filtered by the algorithm, it is ensured that the information displayed in respect of the variation of the perfusion is highly accurate. For reasons of simplicity, the algorithms necessary for the calculation of the perfusion indices and the presentation of the graphic elements on the user surface 10 will not be elaborated further herein. FIG. 3 shows a part of a further user surface 10 as used in the field of patient monitoring. In addition to the plethysmography curve 16 and the current SPO2 value 20 with associated alarm limits 22, information concerning the variation of the perfusion is also shown. The information is represented by means of two bar elements 42, 44. The numerical value of the perfusion 46 is displayed to the right of the bar elements 42, 44. Moreover, a symbol 48 indicates that corresponding alarm limits for the perfusion have been deactivated. Whereas the bar element 42 symbolizes the reference value so that the length of the bar element 42 is constant, the bar element 44 represents, by way of its variable length, the variation of the perfusion in relation to the reference value. The fact that the length of the bar element 44 is variable is denoted by the dashed line 50. The variation of the perfusion can then be readily and intuitively read out by the clinical staff via the different bar length. In order to ensure optimum presentation, the bar elements 42, 44 can be scaled, that is, the length of the bar element 42 can be individually adjusted, causing a corresponding variation of the length of the bar element 44. The additional display of the estimate of the signal quality as derived by evaluation of various parameters such as the transmission level, interference level, artifact level, signal waveform and perfusion index, is realized by way of corresponding coloring of the bar elements 42, 44 shown. For example, a green bar element indicates a good signal quality while a yellow element indicates a dubious signal quality and a red bar element indicates a poor signal quality. FIG. 4 shows a further possibility for the representation of the signal quality. FIG. 4 again concerns a part of a user surface 10 as used in the field of patient monitoring. The user surface 10 again displays the plethysmography curve 16, the SPO2 value 20 with alarm limits 22 and the bar elements 42, 44 for presenting the variation of the perfusion with the associated numerical value 46. Three circular elements 52 are arranged horizontally adjacent one another as graphic elements for the presentation of the signal quality, that is, underneath the numerical value 46 of the perfusion. The signal quality is indicated in known manner by way of corresponding coloring of the circular elements, that is, green=good signal quality, yellow=mediocre signal quality, and red=poor signal quality. FIG. 5 shows a further version in which only the variation of the perfusion is represented via the element 44, 50 in addition to the numerical information 20, 22 and 46 so that more room is available for the display of the plethysmography curve 16. The reference value is indicated by way of a further graphic element 54, for example, the tip of an arrow or a line. LIST OF REFERENCES 10 user surface for patient monitoring 12 ECG curve, derivative I 14 ECG curve, derivative II 16 plethysmography curve 18 CO2 respiration curve 20 SPO2 value 22 alarm limits 24 measuring cap 26 first light-emitting diode 28 second light-emitting diode 30 photoreceiver 32 finger cap 34 tissue 36 arteries 38 veins 40 capillaries 42 first bar element 44 second bar element 46 numerical value of the perfusion 48 symbol for deactivated alarm limits 50 variation of the length of the second bar element 52 independent graphic elements for indicating the signal quality 54 marking of the reference value
20050415
20090811
20060727
93563.0
A61B502
0
NATNITHITHADHA, NAVIN
METHOD FOR THE PRESENTATION OF INFORMATION CONCERNING VARIATIONS OF THE PERFUSION
UNDISCOUNTED
0
ACCEPTED
A61B
2,005
10,532,127
ACCEPTED
Resource allocation management
The invention relates to resource allocation in communications systems (1). In such a system (1), the pool of resources that can be provided to connected user equipment (400, 410) for usage in conducting communications services are divided into multiple resources classes. This class division is based on a characteristic allocation time of resource allocation procedures that can be applied on resources of the different classes. For each class, a resource utilization measure is determined. It is then determined, based on this measure, whether or not a resource allocation procedure associated with the current class should be triggered. This selective triggering can be realized through a comparison between the measure and a threshold associated with the current class. Both the measure determination and selective triggering are performed for a given class before continuing with a next class, preferably starting with the class having slowest resource allocation procedures.
1. A resource allocation method in a communications system (1) having resources, said method comprising the steps of: dividing said resources into multiple different resource classes based on an associated characteristic allocation time, for each resource class: determining a resource utilization measure; and selecting whether or not to trigger resource allocation based on said resource utilization measure. 2. The method according to claim 1, wherein said determining step and said selecting step are first performed for a resource class having a given characteristic allocation time and are then performed for another resource class having a relatively shorter characteristic allocation time. 3. The method according to claim 1, wherein said selecting step comprises the steps of: comparing said resource utilization measure with a threshold (Tk) associated with said resource class; and triggering resource allocation if said resource utilization measure exceeds said threshold (Tk). 4. The method according to claim 3, wherein a first threshold (TFAST) associated with a first resource class having a first characteristic allocation time is larger than a corresponding second threshold (TSLOW) associated with a second resource class having a second characteristic allocation time, said first allocation time being relatively shorter than said second allocation time. 5. The method according to claim 4, wherein said communications system (1) provides a guaranteed minimum amount of resources of said first class to a connected user equipment (400; 410), and a resource utilization measure of said first resource class exceeds said first threshold (TFAST) and a resource utilization measure of said second resource class exceeds said second threshold (TSLOW), said method comprising the steps of: triggering resource allocation for said second resource class; and temporarily allocating a first resource amount of said first resource class to said user equipment (400; 410) during progression of said resource allocation for said second resource class, said first resource amount being relatively smaller than said guaranteed minimum resource amount, whereby a total resource utilization is temporarily reduced during said progression of said resource allocation for said second resource class. 6. The method according to claim 5, further comprising the step of reallocating a second resource amount of said first resource class to said user equipment (400; 410) after completion of said resource allocation for said second resource class, said second resource amount being equal to or larger said guaranteed minimum resource amount. 7. The method according to claim 3, wherein said dividing step comprises the step of dividing said resources into a first resource class and a second recourse class, said method comprising the step of calculating said threshold (TSLOW) associated with said second resource class based on said threshold (TFAST) associated with said first resource class. 8. The method according to claim 1, wherein said resources are radio resources and said method comprising the step of providing said radio resources to user equipment (400; 410) connected to said communications system (1) for enabling utilization of communications services (402; 412, 414) available for said user equipment (400; 410). 9. The method according to claim 1, wherein said characteristic allocation time is a total time required for allocating or reallocating a resource of said resource class. 10. The method according to claim 1, wherein said dividing step comprises the step of dividing said resources into a first resource class and a second resource class, where a resource of said first resource class is allocable with an allocation procedure of a first allocation procedure set and a resource of said second resource class is allocable with an allocation procedure of a second allocation procedure set, said first allocation procedure set comprises at least one of: restricting available transport format combinations (TFC) for user equipment (400; 410) connected to said system (1); and performing an Adaptive Multi Rate (AMR) mode switch for said user equipment (400; 410), and said second allocation procedure set comprises least one of: performing a channel switch from a dedicated high bit-rate channel to a dedicated low bit-rate channel for said user equipment (400; 410); performing a channel switch from a dedicated channel to a common channel for said user equipment (400; 410); performing a handover from a first radio access network to a second radio access network for said user equipment (400; 410); performing a handover from a first carrier frequency to a second carrier frequency for said user equipment (400; 410); and dropping an ongoing call for said user equipment (400; 410). 11. The method according to claim 1, wherein said determining step is performed periodically. 12. The method according to claim 1, wherein said determining step is performed upon a triggering event selected from at least one of: a change in the number of available channels for connected user equipment (400; 410); a change in the number of connected user equipment (400; 410); a change in the number of provided services (402; 412, 414) per user equipment (400; 410); a change in QoS requirements of an on-going communications service (402; 412, 414) for connected user equipment (400; 410); a reception of an updated mobility measurement report; a reception of an updated interference measurement report; and a change in data traffic. 13. The method according to claim 1, further comprising the step of selecting any resource to be allocated based on information of QoS requirements for connected user equipment (400; 410). 14. The method according to claim 1, further comprising the step of selecting any resource to be allocated based on resource saving estimation information. 15. The method according to claim 1, wherein said determining step comprises the step of estimating a total power of communications links used for said resource class. 16. A resource allocation system (100) provided in a communications system (1) having resources, said resources being divided into multiple different resource classes based on an associated characteristic allocation time, said resource allocation system (100) comprising means for performing, for each resource class: determination (120) of a resource utilization measure; and selectively triggering (130) of resource allocation, in dependence of said resource utilization measure. 17. The system according to claim 16, wherein said means (120, 130) is configured for first performing said measure determination and said selectively allocation triggering for a resource class having a given characteristic allocation time and then performing said measure determination and selectively allocation triggering for another resource class having a relatively shorter characteristic allocation time. 18. The system according to claim 16, wherein said selectively allocation triggering means (130) comprises: means for comparing (132) said resource utilization measure with a threshold (Tk) associated with said resource class; and means for triggering (130) said resource allocation if said resource utilization measure exceeds said threshold (Tk). 19. The system according to claim 18, wherein a first threshold (TFAST) associated with a first resource class having a first characteristic allocation time is larger than a corresponding second threshold (TSLOW) associated with a second resource class having a second characteristic allocation time, said first allocation time being relatively shorter than said second allocation time. 20. The system according to claim 19, wherein said communications system (1) provides a guaranteed minimum amount of resources of said first class to a connected user equipment (400; 410), and a resource utilization measure of said first resource class exceeds said first threshold (TFAST) and a resource utilization measure of said second resource class exceeds said second threshold (TSLOW), said means (130) is configured for: triggering of resource allocation for said second resource class; and temporarily allocation of a first resource amount of said first resource class to said user equipment (400; 410) during progression of said resource allocation for said second resource class, said first resource amount being relatively smaller than said guaranteed minimum resource amount. 21. The system according to claim 20, further comprising means (130) for reallocating a second resource amount of said first resource class to said user equipment (400; 410) after completion of said resource allocation for said second resource class, said second resource amount being equal to or larger said guaranteed minimum resource amount. 22. The system according to claim 18, further comprising: means for dividing (200) said resources into a first resource class and a second recourse class; and means for calculating (170) said threshold (TSLOW) associated with said second resource class based on said threshold (TFAST) associated with said first resource class. 23. The system according to claim 16, wherein said characteristic allocation time is a total time required for allocation means (130) to allocate or reallocate a resource of said resource class. 24. The system according to claim 16, wherein said determination means (120) is configured for determining said resource utilization measure periodically. 25. The system according to claim 16, wherein said determination means (120) is configured for determining said resource utilization measure in response to triggering input information. 26. The system according to claim 16, comprising means (140) for selection of any resource to be allocated based on information of QoS requirements for connected user equipment. 27. The system according to claim 16, comprising means (140) for selection of any resource to be allocated based on resource saving estimation information. 28. The system according to claim 16, wherein said determination means (120) is configured for estimating a total power of communications links used for said resource class. 29. The system according to claim 16, wherein said resource allocation system (100) is provided in a network node of said communications system (1). 30. Communications system (1) having resources, said system (1) comprising: means for dividing (200) said resources into multiple different resource classes based on an associated characteristic allocation time; and resource allocation means (100) for performing, for each resource class: determination of a resource utilization measure; and selectively triggering of resource allocation, in dependence of said resource utilization measure. 31. The system according to claim 30, wherein said resource allocation means (100) is configured for first performing said measure determination and said selectively allocation triggering for a resource class having a given characteristic allocation time and are then performing said measure determination and selectively allocation triggering for another resource class having a relatively shorter characteristic allocation time. 32. The system according to claim 30, wherein said selectively allocation triggering means (100) comprises: means for comparing (132) said resource utilization measure with a threshold (Tk) associated with said resource class; and means for triggering (130) said resource allocation if said resource utilization measure exceeds said threshold (Tk). 33. The system according to claim 32, wherein a threshold (TFAST) associated with a first resource class having a first characteristic allocation time is larger than a corresponding threshold (TSLOW) associated with a second resource class having a second characteristic allocation time, said first allocation time being relatively shorter than said second allocation time. 34. The system according to claim 32, wherein said resource dividing means (200) is configured for dividing said resources into a first resource class and a second recourse class, said system (1) comprising means for calculating (170) said threshold (TSLOW) associated with said second resource class based on said threshold (TFAST) associated with said first resource class. 35. The system according to claim 30, wherein said characteristic allocation time is a total time required for said resource allocation means (100) to allocate or reallocate a resource of said resource class. 36. The system according to claim 30, wherein said determination means (120) is configured for estimating a total power of communications links used for said resource class. 37. The system according to claim 30, wherein said resources are radio resources and said communication system (1) comprises means for providing said radio resources to user equipment (400; 410) connected to said system (1) for enabling utilization of communications services (402; 412, 414) available for said user equipment (400; 410). 38. A resource allocation method in a communications system (1), said method comprising the steps of: providing a guaranteed minimum amount of resources of a first resource class and resources of a second resource class, a characteristic allocation time of said first resource class being relatively shorter than a corresponding characteristic allocation time of said second resource class; triggering resource allocation for said second resource class; and temporarily allocating a first resource amount of said first resource class during progression of said resource allocation for said second resource class, said first resource amount being relatively smaller than said guaranteed minimum resource amount, whereby a total resource utilization is temporarily reduced during said progression of said resource allocation for said second resource class. 39. The method according to claim 38, further comprising the step of reallocating a second resource amount of said first resource class after completion of said resource allocation for said second resource class, said second resource amount being equal to or larger said guaranteed minimum resource amount. 40. The method according to claim 38, wherein said temporarily allocating step comprises the steps of: calculating, for said first resource class, a first resource utilization measure; comparing said first resource utilization measure with a first threshold (TFAST) associated with said first resource class; and triggering said temporary resource allocation if said first resource utilization measure exceeds said first threshold (TFAST). 41. The method according to claim 38, wherein said triggering step comprises the steps of: calculating, for said second resource class, a second resource utilization measure; comparing said second resource utilization measure with a second threshold (TSLOW) associated with said second resource class; and triggering resource allocation for said second resource class: if said resource utilization measure exceeds said second threshold (TSLOW). 42. The method according to claim 39, wherein said reallocation step comprises the steps of: calculating, for said first resource class, a first resource utilization measure in response to ending said resource allocation for said second class; comparing said first resource utilization measure with a third threshold (h*TFAST) associated with said first resource class; and triggering said reallocation of said second resource amount if said first resource utilization measure is below said third threshold (h*TFAST). 43. The method according to claim 38, further comprising the steps of: determining a total packet delay (DTOTAL) for user equipment (400; 410) connected to said communications system (1) and utilizing resources of said first resource class; comparing said total packet delay (DTOTAL) with a delay threshold (T); and reallocating a second amount of said first resource class if said total delay (DTOTAL) exceeds said delay threshold (T), said second amount being equal to or larger than said guaranteed minimum resource amount. 44. The method according to claim 38, further comprising the steps of: determining a total packet delay (DTOTAL) for user equipment (400; 410) connected to said communications system (1) and utilizing resources of said first resource class; comparing said total packet delay (DTOTAL) with a first delay threshold (T); comparing a packet delay (DTFC) introduced by said temporarily resource allocation with a second delay threshold (kT) if said total delay (DTOTAL) exceeds said first delay threshold (T); and reallocating a second resource amount of said first resource class if said delay (DTFC) introduced by said temporarily resource allocation exceeds said second delay threshold (kT), said second resource amount being equal to or larger than said guaranteed minimum resource amount. 45. The method according to claim 38, wherein said communications system (1) provides streaming services (402; 412, 414) by means of at least one resource of said guaranteed minimum amount of resources and/or said resources of said second resource class to user equipment (400; 410) connected to said system (1). 46. The method according to claim 39, wherein said temporarily resource allocating step comprises the step of temporarily reducing allowed bit-rate below a guaranteed minimum bit-rate by restricting allowed Transport Format Combinations (TFC) and said reallocating step comprises the step of increasing said allowed bit-rate to at least said guaranteed minimum bit-rate by releasing said imposed TFC restrictions. 47. A resource allocation system (100) in a communications system (1) providing a guaranteed minimum amount of resources of a first resource class and resources of a second resource class, a characteristic allocation time of said first resource class being relatively shorter than a corresponding characteristic allocation time of said second resource class, said resource allocation system (100) comprising: means for triggering (100) resource allocation for said second resource class; and means for temporarily allocating (100) a first resource amount of said first resource class during progression of said resource allocation for said second resource class, said first resource amount being relatively smaller than said guaranteed minimum resource amount, whereby a total resource utilization is temporarily reduced during said progression of said resource allocation for said second resource class. 48. The system according to claim 47, further comprising means (100) for reallocating a second resource amount of said first resource class after completion of said resource allocation for said second resource class, said second resource amount being equal to or larger said guaranteed minimum resource amount. 49. The system according to claim 47, wherein said temporarily allocating means (100) comprises: means for calculating (120), for said first resource class, a first resource utilization measure; means for comparing (132) said first resource utilization measure with a first threshold (TFAST) associated with said first resource class; and means for triggering (130) said temporary resource allocation if said first resource utilization measure exceeds said first threshold (TFAST). 50. The system according to claim 47, wherein said triggering means (100) comprises: means for calculating (120), for said second resource class, a second resource utilization measure; means comparing (132) said second resource utilization measure with a second threshold (TSLOW) associated with said second resource class; and means for triggering (130) resource allocation for said second resource class if said resource utilization measure exceeds said second threshold (TSLOW). 51. The system according to claim 48, wherein said reallocation means (100) comprises: means for calculating (120), for said first resource class, a first resource utilization measure in response to ending said resource allocation for said second class; means for comparing (132) said first resource utilization measure with a third threshold (h*TFAST) associated with said first resource class; and means for triggering (130) said reallocation of said second resource amount if said first resource utilization measure is below said third threshold (h*TFAST). 52. The system according to claim 47, further comprising: means for determining (150) a total packet delay (DTOTAL) for user equipment (400; 410) connected to said communications system (1) and utilizing resources of said first resource class; means for comparing (132) said total packet delay (DTOTAL) with a delay threshold (T); and means for reallocating (130) a second resource amount of said first resource class if said total delay (DTOTAL) exceeds said delay threshold (T), said second resource amount being equal to or larger than said guaranteed minimum resource amount. 53. The method according to claim 47, further comprising: means for determining (150) a total packet delay (DTOTAL) for user equipment (400; 410) connected to said communications system (1) and utilizing resources of said first resource class; means for comparing (132) said total packet delay (DTOTAL) with a first delay threshold (T); means for comparing (132) a packet delay (DTFC) introduced by said temporarily resource allocation with a second delay threshold (kT) if said total delay (DTOTAL) exceeds said first delay threshold (T); and means for reallocating (130) a second resource amount of said first resource class if said delay (DTFC) introduced by said temporarily resource allocation exceeds said second delay threshold (kT), said second resource amount being equal to or larger than said guaranteed minimum resource amount. 54. The system according to claim 47, wherein said communications system (1) is adapted for providing streaming services (402; 412, 414) by means of at least one resource of said guaranteed minimum amount of resources and/or said resources of said second resource class to user equipment (400; 410) connected to said system (1). 55. The system according to claim 48, wherein said temporarily resource allocating means (100) is configured for temporarily reducing allowed bit-rate below a guaranteed minimum bit-rate by restricting allowed Transport Format Combinations (TFC) and said reallocating means (100) is configured for increasing said allowed bit-rate to at least said guaranteed minimum bit-rate by releasing said imposed TFC restrictions.
TECHNICAL FIELD The present invention generally refers to resource management in communications systems, and in particular to resource allocation in such systems. BACKGROUND A communications system manages and provides resources for use by e.g. its connected users for the purpose of enabling utilization of communications services in the system. For example, a radio communications system provides radio resources that its mobile users then utilize for conducting e.g. voice, packet transmission and streaming services. The communications system typically only has access to a limited pool of resources, which are portioned out between the different users and services. Thus, the users and services can be regarded as competing for the limited amount of resources. In addition, in some communications system, or for certain resource types, the demands for resources change at specific events. Such events could be the addition of a new service, the closing of a communications session or a change in the requirements set by the end-user application. Often some explicit signaling follows these kinds of events. This signaling is then used to trigger the execution of a resource allocation procedure. For example, each time a new call is to be set up in a Global System for Mobile communications (GSM) system, a resource allocation unit or system has to look for an available channel, a time slot (radio resource) is then allocated to the user, or the call request is denied (which may result in a blocked call or a failed handover). In this example, the resource, i.e. time slot, is explicitly allocated and retrieved by a resource allocation procedure initiated by the allocation unit. In other communications system, or for other resource types, the demand for resources may dynamically change due to other reasons. For instance, in a power controlled mobile communications system, such as Universal Mobile Telecommunications System (UMTS) or Code Division Multiple Access (CDMA) 2000 systems, the power control loop adapts the transmitted power in response to changes in the radio conditions experienced over the radio connection. Such condition changes can be the result of the mobility of the user equipment or caused by changes in the interference level experienced by the receivers. However, even for fixed radio connections, the power demand may vary due to changes in interference levels (caused by other systems), due to mobility issues or due to changes in the propagation environment (e.g. due to changes in the weather conditions). In this case, a resource allocation has to be continuously (or periodically) updated, so that the allocated resources match a current resource demand. A particular aspect of some communications systems is that the resource allocation architecture is split into several layers. For example, the fast power control in Universal Terrestrial Radio Access Network (UTRAN) is a standardized procedure at link level, which treats each connection independently. As a consequence, the fast power control algorithm is sometimes not seen as a resource allocation algorithm. In this context, the resource allocation procedures are then viewed as trying to influence the resource demand. For example, the resource demand for a certain channel may be reduced, at least in average, by reducing the bit-rate available on that channel. Accordingly, even in systems where the resource cannot directly be affected by a resource allocation procedure (as is the case with the power in UTRAN, discussed above), there might be procedures that ultimately influence the resource demand. For example, a down-switch from a dedicated channel with high bit-rate to a dedicated channel with lower bit-rate or to a common channel can be regarded as a resource pre-emption procedure and therefore can be used to cope with changes, such as an unexpected increase, in the resource demands. In the present description, the expression “resource allocation procedure” includes any procedure that ultimately leads to a change in the amount of used resources, even if the procedure does not directly effect the resource usage. Thus, the expression also includes resource (re)allocation and pre-emption procedures. A general case of a communications system with a limited pool of resources is a communications system, in which a sender transmits, in the same time, signals to a number of receivers. This can be exemplified by the downlink transmission between a base station and a number of mobile units in a UMTS system. A common pool of (radio) resources (e.g. the total downlink power, or carrier power) is shared between the different links. The specific amount of resources allocated to a link depends, among others, on the characteristics of the communications service provided by the sender on that link, but also on other external factors that cannot be controlled by the sender. For example, the amount of power required by a link in a mobile radio communications system depends on the bit-rate required by the communications service and can therefore be controlled by the sender by changing the provided bit-rate. However, the amount of power required by the link also depends on factors out of control for the sender, such as the position and movement of the mobile user equipment, the interference induced by other systems, etc. Since the total amount of used resources (total resource utilization) in a communications system with shared resources is the sum of the amount of resources used on each link, i.e. allocated for each user, the increase in total resource utilization can be caused by an increase in the number of links and/or by an increase in the amount of resources used by the individual links. There is typically no problem as long as the total resource utilization is below the total amount of available resources, but as the total resource utilization increases too much and the resources become scarce, actions have to be taken to limit or reduce the resource utilization. One way to limit the total resource utilization is to hinder the increase in the number of links, a procedure called admission control in the art. An alternative solution is to remove a link belonging to a user with low priority, when a high priority user requires access to a service. This is the case with SOS calls in a GSM system. However, the increase in the total resource demand or utilization can, as was mentioned above, be due to increases in the amount of resources used for the links. Such increases in demanded resources can be caused by the mobility of the user equipment, changes in the behavior of a provided service, etc. In this case, the amount of resources presently allocated to one or several links has to be decreased, a procedure called congestion control in the art. In a general case, in which users have different priorities and the services provided to the users have different demands, the admission and congestion control can be seen as particular cases of a resource allocation procedure. A relevant example is when the increased amount of resources allocated to a link with high priority, e.g. due to an increase of demanded bit-rate, the addition of a new bearer to a multi-bearer connection, etc., is done by reducing the amount of resources allocated to a low priority link. The common solution for a communications system to prevent the resource demand or utilization from exceeding the maximum total resource limit, which is often determined by hardware limitations, is to initiate a resource allocation. However, this resource allocation can in most cases be performed by means of several different allocation procedures. A problem with the prior art solutions is then how to select which allocation procedure to employ, but also how to select which link to be affected by the resource allocation, in the case of a choice between different procedures and/or links that leads to the same end-result. For example, some resource allocation procedures, such as channel down-switch, require rather extensive signaling and handshaking between the sender and the receiver and consequently require a long time before the allocation becomes effective. Other resource allocation procedures do not require handshaking and therefore have a relatively shorter execution time. This scenario is exemplified in FIG. 1. At time t0 the communications system is in a situation where the resource demand is unacceptable high and therefore a resource allocation procedure must be applied in order to reduce the overall resource utilization. Assume that in this situation two different procedures can be employed in order to reduce the resource utilization with the same amount. One of these two procedures requires handshaking between the sender and the receiver and, thus, has a long execution time (slow procedure). The second procedure is fast, i.e. has shorter execution time. In addition, both procedures result in the same quality of service (QoS) requirements for a user, as exemplified by the provided bit-rate of 64 kps. Call t1 a time after the execution of the procedures, i.e. when the resource allocation is completed. Assume that a new resource shortage occurs and additional resources must be released (resulting in a reduction of bit-rate to 48 kps). Further assume that for the first case, i.e. employing a fast resource allocation procedure in time t0, now only slow allocation procedures are available. However, for the second case, i.e. employing a slow resource allocation procedure in time t0, now both fast and slow allocation procedures are available. At time t2, the second resource allocation is completed. The situations at time t0, t1 and t2 can be regarded as states in a state machine. From an initial state A at time t0 two different resource allocation procedures can be employed. Depending on the employed procedure, one of two states (B or C) is reached at time t1. From the point of view of the amount of utilized resources and from the QoS (bit-rate) point of view, the two states are identical. However, the states differ in the procedures available for the next transition. Thus, transition from state B (to D) can only be performed with a slow procedure, while transition from state C can be done with a fast procedure (to E) or a slow procedure (to F). A typical prior art allocation unit or system is generally adapted for always employing a fast resource allocation procedure, if available. With reference to FIG. 1, this corresponds to selecting a fast allocation procedure at time t0, i.e. the transition from state A to B. However, it might then be possible that the subsequent resource allocation, i.e. from B to D, is time critical. Since now only slow procedures are available according to FIG. 1, system instability might occur if the resource demand becomes too large before the slow allocation is completely executed. SUMMARY The present invention overcomes these and other drawbacks of the prior art arrangements. It is a general object of the present invention to provide an efficient resource management in communications system. It is another object of the invention to provide a dynamic resource allocation in communications system. Yet another object of the invention is to provide a resource allocation that maintains the possibility of employing fast resource allocation procedures. A particular object of the invention is to provide a resource allocation that does not increase a packet delay experienced by streaming users above guaranteed quality of service (QoS) levels. These and other objects are met by the invention as defined by the accompanying patent claims. Briefly, the present invention involves resource allocation in communications system. According to the invention, the pool of resources provided by the communications system, or a portion or a sub-system thereof, is divided into different resource classes based on an associated characteristic allocation time. Thus, resources from a given class can be allocated by one or several resource allocation procedures having a characteristic execution time. Correspondingly, resources of another resource class can be allocated by one or several other allocation procedures having other characteristic execution times. The characteristic allocation or execution time then corresponds to a total time from the triggering of a particular allocation procedure to the completion of the allocation. It may be possible that there is only one allocation procedure available for a given resource class. However, it may be possible to allocate resource of a certain class by means of several different allocation procedures, where these procedures have approximately the same allocation time or speed. Furthermore, the resources are divided into multiple classes, i.e. two or more classes, with different associated allocation times. For example, the resources can be divided into two classes. In such a case, a first class comprises resources allocable with fast resource allocation procedures and a second class comprises resources allocable with slow resource allocation procedures. Slow procedures generally require extensive signaling and handshaking between the communications system and the unit, to which the system provides the resources. This handshaking and signaling result in a long execution time, typically in the order of several hundreds of milliseconds. In contrast to the slow procedures, fast resource allocation procedures typically have an execution time of a few or even less than hundred milliseconds. The resource allocation method comprises that, for each resource class, a resource utilization measure is determined or estimated. This measure is preferably based on the total resource utilization for the current class. In a typical embodiment, the resource utilization measure is the amount of power of the current class that is used on communications links in the system. Based on this resource utilization measure, it is determined whether or not to trigger one or several resource allocation procedures on resources of the current class. The general object of this allocation is to reduce the resource utilization measure. Note that decreasing the utilization measure does not necessarily lead to a reduced amount of resources allocated from the affected class. In a preferred embodiment of the invention this selective allocation triggering is performed by comparing the resource utilization measure of the current class with an associated threshold. If the measure then exceeds the threshold, a resource allocation is initiated. This utilization measure determination and selective triggering are repeated for all resource classes, preferably starting with the class containing resources that are allocable with the resource allocation procedures having the longest characteristic allocation time. The measure determination and selectively triggering are then performed for the class with the next second longest allocation time and so on ending with the class with the shortest allocation time. Since the characteristic allocation times for the classes differ, several allocation procedures may run parallel for the different classes. The advantage of dividing resource into different classes according to the invention and investigating and possibly allocating each resource class individually is that the possibility for the communications system of always having a pool of fast resource available for allocation increases. This means that the communications system most often, and preferably always, has access to a fast resources allocation procedure to use when the total resource utilization in the system becomes too large. Thus, when resources become scarce, the available fast allocation procedures can be triggered for quickly releasing some resources and thereby avoid the risk of system instability. For a mobile radio communications system having radio resources of two resource classes, examples of slow resource allocation procedures include a channel switch from a dedicated channel with a first bit-rate to a dedicated channel with a second different bit-rate (dedicated channel re-configuration) and a channel switch from a dedicated channel to a common (non-power-regulated) channel. Slow procedures also comprise a handover from one radio access network to another radio access network and handover between different carrier frequencies (Inter-Frequency Handover (IFHO)). Also dropping an on-going call for connected mobile user equipment can in some applications be regarded as a slow allocation procedure. A fast allocation procedure, in particular for affecting the downlink power of a downlink channel, is to limit access to the number of transport blocks available for transmission. Such a limitation in the available transport format combinations (TFCs) results in a reduction in the provided bit-rate and consequently a reduction in the downlink power. In some applications it may not be possible to allocate resources (reduce the resource utilization) of a certain class without breaking a QoS contract. Thus, the communications system may currently provide a guaranteed amount of resources to a user. For the example with a mobile radio communications system with a fast allocable resource class and a slow allocable resource class, a situation can occur where the resource utilization measure of the slow allocable class exceeds its associated threshold and a slow resource allocation procedure is triggered. However, during the relatively long progression of this resource allocation, the radio conditions may worsen leading to an increase of this utilization measure. It may even be possible that this measure actually exceeds the threshold for the fast allocable class. In such a case, the pool of fast allocable resources become zero and no fast resource allocation procedures are available for reducing the total resource utilization in the communications system. Thus, the system has to wait for the completion of the slow allocation procedure until the resource utilization can be lowered. However, during this long execution the resource demands can increase further causing system instability. According to the invention, a fast resource allocation procedure is then temporarily employed for releasing resources from a user that presently is provided a guaranteed amount of resources, e.g. reducing available transport blocks to a level below the guaranteed one. As a consequence, the system will temporarily deliver a less-than-guaranteed amount of resources to a user. Once the slow allocation procedure is completed, the amount of resources allocated to this user may the increased, e.g. by releasing a previously imposed TFC limitation. Thus, although a user at a certain moment may be provided with less than guaranteed amount of resources, the average resource amount provided over time to that user is at least according the guaranteed level. This embodiment of temporarily reducing the bit-rate (through use of TFC limitations) may result in breaking QoS contracts, in particular for streaming users, since the reduced transport bit-rate leads to data being accumulated in the sender's buffer and therefore to increased packet delay. By monitoring the total packet delay and the delay originating from TFC limitation for different users, imposed TFC limitations may be released (if the delays become too large) before QoS contracts are broken. The invention offers the following advantages: Enables combined usage of slow resource allocation actions and fast resource allocation actions; Ensures system stability by reducing the probability for the party effect and reducing the probability for the communications system to get into congestion; Provides efficient resource utilization; Enables usage of a low margin between working point and a maximum resource consumption level; Ensures that delay for streaming users is kept within contracted QoS levels. Other advantages offered by the present invention will be appreciated upon reading of the below description of the embodiments of the invention. SHORT DESCRIPTION OF THE DRAWINGS The invention together with further objects and advantages thereof, may best be understood by making reference to the following description taken together with the accompanying drawings, in which: FIG. 1 schematically illustrates different resource states of a communications system reachable by performing slow or fast resource allocation procedures; FIG. 2 is a flow diagram of an embodiment of a resource allocation method according to the present invention; FIG. 3 is a flow diagram of an embodiment illustrating the measure determination and selectively trigger steps of FIG. 2 in more detail; FIG. 4 is a schematic overview of an example of a communications system according to the present invention; FIG. 5 is a time diagram illustrating the lapse of resource measures according to the invention over time; FIG. 6 is a time diagram illustrating lapse of a resource measure according to the invention over time; FIG. 7 is a flow diagram of additional steps of the resource allocation method of FIG. 4; FIG. 8 is a diagram illustrating the division of resource into different resource classes according to the present invention; FIG. 9 is another time diagram illustrating the lapse of resource measures according to the invention over time; FIG. 10 is a flow diagram of another embodiment illustrating the measure determination and selectively trigger steps of FIG. 4 in more detail; FIG. 11 is a flow diagram of an embodiment illustrating additional steps of the method of FIG. 10; FIG. 12 is a block diagram schematically illustrating a resource allocation system according to the present invention; and FIG. 13 is a block diagram schematically illustrating the allocation trigger of FIG. 12 in more detail. DETAILED DESCRIPTION Throughout the drawings, the same reference characters will be used for corresponding or similar elements. The present invention relates to management of resources, and in particular to allocation of resources in communications systems. In the present description the expression “resource allocation” refers to both resource allocation and reallocation and to resource pre-emption discussed in the background section, unless otherwise specified. Thus, in order to facilitate understanding of the invention, resource allocation is used throughout the description, also for traditional resource pre-emption and reallocation. Note that, according to the present invention, a resource allocation procedure can be used for allocating more, i.e. assigning, recourses to one or several services, links and connected user equipment. Furthermore, a resource allocation procedure can also be used for reducing the amount of resources for one or several services, links and connected user equipment. According to the present invention the pool of available resources provided by a communications system, or a portion or a sub-system thereof, is divided into different resource classes or types based on an associated characteristic allocation time or speed. In other words, different resources may be allocated by different allocation procedures, where each procedure has a characteristic execution time. This time corresponds to a total time from the triggering of the particular allocation procedure to the completion of the allocation. It may be possible that there is only one allocation procedure available for a specific resource class. However, it may be possible to allocate resource of a certain class by means of several different allocation procedures, where these procedures have approximately the same allocation time or speed. Furthermore, the resources are divided into multiple classes, i.e. two or more classes, with different associated allocation times. For example, the resources can be divided into two classes. In such a case, a first class comprises resources allocable with fast resource allocation procedures and a second class comprises resources allocable with slow resource allocation procedures. Slow procedures generally require extensive signaling and handshaking between the communications system and the unit, to which the system provides the resources. This handshaking and signaling result in a long execution time. For a radio communications system, such slow resource allocation procedures include a channel switch from a dedicated channel with a first bit-rate to a dedicated channel with a second different bit-rate (dedicated channel re-configuration) and a channel switch from a dedicated channel to a common (non-power-regulated) channel. Slow procedures also comprise a handover from a first radio access network to another radio access network and handover between different carrier frequencies, i.e. Inter-Frequency Handover (IFHO). Also dropping an on-going call for connected mobile user equipment can in some applications be regarded as a slow allocation procedure. Fast allocation procedures include reducing the bit-rate, e.g. by restricting available transport format combinations (TFCs), provided to mobile user equipment and performing an Adaptive Multi Rate (AMR) mode switch. In the following description, “fast resources” (“slow resources”) refer to resources allocable with a fast allocation procedure (slow allocation procedure), e.g. one of the procedures identified above. It is also possible to employ a division resulting in more than two resource classes, e.g. a slow allocable resource class, medium allocable class, fast allocable class and a very fast allocable class. The actual number of resource classes may depend on the communications system, available allocation procedures, available communications services and other factors, such as expected resource utilization, traffic situation, etc. It may, further, be possible for a communications system to use a static resource class definition or change the class definition over time. FIG. 2 illustrates a resource allocation method according to the present invention. The method starts with step S1, where the available resources are divided into different resource classes based on the allocation or execution time (speed) for the allocations procedure(s) that can be employed for respective class, which was discussed above. The method then continues by performing the steps S2 and S3 for each resource class. In step S2, a resource utilization measure is determined for the current class. This measure preferably corresponds to or is based on the total amount of resources utilized in the communications system for the current class, and possible the amount of utilized slower resources. A typical example of such a measure is the amount of power that may be allocated by procedures of the current class. In a radio communications system, by the “amount of power” is understood an estimate of the average power, where the average is considered, for example, over a radio frame. For example, in the case with one fast resource class and one slow resource class, the measure associated with the slow allocable class corresponds to the amount of power allocable with slow procedures. However, the measure associated with the fast allocable class preferably corresponds to the amount of power allocable with both slow and fast procedures. This principle may be applied also to the situation with more than two resource classes. Once the resource utilization measure is determined, i.e. either explicitly calculated or estimated, for the current class, step S3 selectively triggers resource allocation based on the measure. Thus, in this step S3, it is determined or selected whether or not to allocate resources in the current class based on the utilization measure. For example, a resource allocation procedure associated with the current class could be triggered if the measure is too large. If is determined in step S3, based on the measure, that a resource allocation is to be trigged, an allocation procedure that can allocate resources of the current class is selected, if there is a choice between several different procedures having similar allocation times. This procedure is then employed for performing an allocation of resources from the current resource class. It is also possible to employ more than one allocation procedure of the current class in step S3. The general object of the allocation is to reduce the resource utilization measure of the current class. Decreasing the utilization measure for a class, through performing allocation procedures on resources of the current class for a user, does not necessarily leads to a reduced amount of resources allocated to that user. This means that the experienced quality, e.g. bit-rate, may be kept the same, despite the fact that actions are taken for the resources provided to the user and that the utilization measure for the class is changing. For example, if a user is currently allowed to utilize only 64 kps on a 128 kps dedicated channel and a down switch to a 64 kps dedicated channel is initiated as the selected allocation procedure, the service will experience no sudden quality change (i.e. no change in bit-rate) and the amount of resources utilized will be fairly the same. Both the step S2 and step S3 are repeated for each resource class, which is schematically represented by the line 500 in the figure. Thus, for the example with two resource classes, step S2 and step S3 are first performed for the first resource class and are then performed for the second resource class. According to a preferred embodiment of the invention steps S2 and S3 are preferably first performed for the resource class having the longest allocation time. The method then continues by repeating the steps S2 and S3 for the class with the next second longest allocation time and so on, ending with the class with the shortest allocation time. Since the characteristic allocation times for the classes differ, several allocation procedures may run parallel for the different classes. For example, if the utilization measure of a slow resource class is too large, a slow resource allocation procedure is triggered on the resources of this class. If the utilization measure of a fast resource class also is too large, a fast resource allocation is initiated with at least one of its fast procedures. If the execution time of the slow procedure is large enough, the fast allocation is triggered and possible also ended before the slow allocation is completed. In other words, the fast allocation procedure may be triggered and ended during the progression of the execution of the slow procedure. The advantage of dividing resource into different classes according to the invention and investigating and possibly allocating each resource class individually is that the possibility for the communications system of always having a pool of fast resource available for allocation increases. This means that the communications system most often, and preferably always, have access to a fast resource allocation procedure to use when the total resource utilization in the system becomes too large. Thus, when resources become scarce the available fast allocation procedures can be triggered for quickly releasing some resources and thereby avoid the risk of system instability. The resource allocation method according to the invention, or more precisely step S2 and step S3 of FIG. 2, is preferably executed when the resource utilization or demand in the communications system becomes too large. This may be due to one or several triggering events including changes in the number channels or links used in the system, the number of users connected to the system or the number of services per user. Furthermore, a change in the quality of services (QoS) requirements of an on-going service may result in a too large increase in resource utilization. Reception of updated measurement reports on e.g. mobility and interference changes in the system could be another triggering event. Also changes in the channel characteristics due to completion of a previously initiated procedure, for example a channel switch, and changes in the data traffic (this could be viewed as an external trigger, for example when measurements of sender buffer size or throughput are received, but could alternatively be viewed as a periodically triggering event, for example investigating whether to trigger allocation per radio frame in a radio communications system) could be a trigger according to the invention. The resource demands may also change dynamically, as was discussed in the background section. FIG. 3 is a flow diagram of an embodiment of the invention illustrating the steps S2 and S3 of FIG. 2 in more detail. In the figure, N corresponds to the number of resource classes that are to be affected by the allocation method of the invention. This number N is equal to or larger than two. Note that it in some applications could be possible to have one or several resource classes that are not to be allocated with the allocation method of the invention. In such a case, these “additional classes” are not included in the number N. In step S10, a class counter k is provided and set to one, i.e. starting with the first resource class. As was discussed above, this first class is preferably the class having resources allocable with the slowest resource allocation procedure(s). Step S11 investigates whether we currently are looking at the last class, i.e. if the class counter k equals N. If k=N the method ends. However, if the current class is not the last class, the method continues to step S12, where the resource utilization measure is determined for the current class. In the next step S13, this determined measure is compared to a threshold Tk, associated with the current class, in order to determine whether any allocation procedure belonging to this class should be initiated. If the measure exceeds the threshold, an allocation procedure should be performed on resources of the current class. It is possible to have other more advanced triggering approaches than a comparison of the measure with a threshold as triggering criteria. In addition, information of the amount with which the measure has to be decreased, i.e. the amount by which the measure exceeds the threshold, could be determined. The triggering may be enhanced, for example, by using filters, counters or other hysteresis mechanisms, without changing the triggering principle. If the measure exceeds the threshold, the method continues to step S14. In this step S14, the entity to be affected is selected. This selection step chooses which communications service(s), link(s) (channel(s)) and/or user equipment to be effected by a resource allocation. It also selects which and the amount of resources of the current resource class that are to be allocated. The amount of resources to be allocated is preferably selected based on the information specifying the amount by which the measure exceeds the threshold. The entity selection can be made by taking into the account the impact that the resource allocation (reduction) has upon different user equipment. Thus, a selection that does not lead to dropping an on-going service (connection) or breaking a QoS contract is most often preferred. In either case, the number of users, links and services and the amount of resources to be affected by the allocation may be done with any of the selection procedures or policies used in the art, including such procedures and polices traditionally employed for congestion control algorithms. Once the relevant entities are selected in step S14, a resource allocation procedure is initiated on resources of the current class for the selected entities in step S15. If there is a choice between several resource allocation procedures for the present class, one or some, possibly all, of the available procedures could be triggered in step S15. The exact choice of procedure is preferably done according to the network operator's preferences to give priority to one or another type of service, or to obtain a specific network behavior. Thereafter, in step S16, the class counter is increased by and the method continues back to step S11. Thus, steps S11 to S16 are repeated for all relevant classes until the counter k equals N. For each loop (steps S11 to S16), the characteristic allocation time associated with the current class preferably becomes shorter and shorter. If it is concluded in step S13 that the utilization measure does not exceed the threshold, the method continues to step S16. Note that if the exact amount, with which the measure must be decreased, is not determined, an iterative procedure can be employed. Then only one service (and one procedure) is selected in step S14. After execution of the allocation procedure for the selected service, the utilization measure is updated as if the procedure had already been executed. The triggering criterion is tested again in step S13. A new service is then selected in step S14 if the updated measure still exceeds the threshold in step S13. Thus, steps S13 to S15 are repeated for one service at a time and the measure is updated each time the small loop of steps S13 to S15 is completed until the measure does not exceed the threshold any longer. Then the method continues to the next class (to step S16). In the following, the invention will be exemplified by a mobile radio communications system providing radio resources to connected mobile user equipment or mobile units. However, the invention is not limited thereto, but can be applied to other types of systems and/or resources. Thus, the resources can be used for providing communications services on links between a general sender and a general receiver. In a typical situation, the sender is a base station or another network node of a communications system providing (radio) resources to connected mobile units. However, the resources could alternatively be employed for communication between base stations or network nodes between different systems and/or within one system. Thus, in a general case the present invention can be applied to a system comprising a node with a limited amount of resources that are assigned to connections with other units. This node could be a wireless access point, e.g. base station, but also other types of nodes, including routers in wired or wireless communications system. These other units can be viewed as “end” nodes or terminals in system. In FIG. 4 a mobile radio communications system 1 according to the present invention is illustrated. The communications system 1 comprises a resource allocation system or unit 100 arranged in one or several network nodes of the system 1 and is adapted for managing resource allocation. This allocation system 100 performs the portioning of radio resources from a common pool of resources, schematically illustrated by 200, to different services 402; 412, 414 and different connected mobile units 400; 410. The system 100 also selectively triggers resource allocation when the available radio resources become scarce. The radio resources are employed by the system 1 for providing communications services, schematically represented by 402; 412, 414, to its connected mobile units 400; 410. It is possible for the system 1 to provide a single service 402 to a mobile unit 400, but also multiple services 412, 414 to a single mobile unit 410. The communications services 402; 412, 414 are provided by means of communications channels or links 2; 12, 14 established between network nodes, e.g. base stations, in the system 1 and the mobile units 400; 410. In FIG. 4 this is represented by one channel or link for each service. The allocation system 100 typically receives input data and information 300 from other units 310; 320; 330; 340 in the communications system 1. For example, the allocation system 100 receives information of QoS requirements 340 of the services, a current resource allocation 330, execution time (speed) of available resource allocation procedures 320 and additional configuration settings 310, which are discussed in more detail below. These inputs can be databases 310; 320; 330; 340 implemented, for example, as registers in the system 1. The input data 300 can be used for determining when to initiate a resource allocation method of the invention and if an allocation procedure is to be triggered, which resources, links, users and/or services to select for the allocation. Different end-user applications and units are characterized by different demands, e.g. sensibility of propagation delay, certain bit-rate demands, etc. In order to increase the resource allocation efficiency, bearer communications services may be adapted to these application-dependent characteristics so that the resource cost of providing the desired end-user quality can be reduced by selecting an appropriate service. The Universal Mobile Telecommunications System (UMTS) standard [1] provides a set of service classes and QoS attributes. For conversational Radio Access Bearer (RAB) services, these defined attributes include a guaranteed bit-rate (the communications system must provide it but the end-user application is not forced to use it), a maximum bit-rate (which can be higher than the guaranteed bit-rate and which the system only provides if enough resources are available) and a maximum propagation delay. Corresponding attributes exist also for streaming RAB services, whereas for interactive and background services only the guaranteed bit-rate is defined. The QoS requirements 340 may include these QoS attributes (guaranteed and minimum bit-rate and/or maximum propagation delay). The current resource allocation 330 can comprise the current channel type used for each service, the code power (the peak power used for that channel or link). The allocation time data 320 could include information of available resource allocation procedures and their respective execution times. The additional configuration database 310 could provide information-restricting utilization of the allocation procedures in some particular cases. For increasing the understanding of the invention, an exemplified allocation scenario will now be described for a UMTS system with reference to FIG. 5. In this example the resource of interest are the downlink carrier power (total downlink power). This should merely been seen as a typical resource example. In general, the principles of the invention can be utilized also in the power management on the uplink. This may be especially important in a scenario with multi-RABs on the uplink, because this increases the probability for services with different QoS requirements to be handled at the same time. The same principle could also be used also when it comes to other resources, such as the uplink interference measured by the system. However, most of the actions that the system can take to reduce the uplink interference require handshaking with the mobile user equipment. As a consequence, the difference in the execution times of the available allocation procedures (typically channel switch and handover to another carrier or to another system) is smaller. This means that the quantitative gain would be somewhat less. Furthermore, in the present example the resource allocation procedures (resources) are grouped into two classes, slow procedures (slow resource class) and fast procedures (fast resource class). For the slow class, the following procedures are available: dedicated to dedicated channel switch; dedicated to common channel switch; handover from Universal Terrestrial Radio Access Network (UTRAN) to Global System for Mobile communications (GSM)/General Packet Radio Service (GPRS) radio access network handover between different frequencies (IFHO); and dropping calls. Possible fast procedures include: TFC limitation; and AMR mode switch. Assume that the UMTS system includes a connected speech user (conversational RAB service) and a Web browsing user (interactive RAB service). Further assume that the lowest AMR mode that can be provided to speech users is 10.2 kps and that Web users may be provided with a 64 kps dedicated channel or a 128 kps dedicated channel. In this example, code power measurements are considered to be available for the resource allocation system or unit (for an accurate estimate of the amount of resources used by each link), typically in a Radio Network Controller (RNC) in the system. According to the invention and the discussion in connection with FIG. 2, the allocation system triggers execution of fast and slow resource allocation procedures depending on the level of the fast and slow resource utilization measure, respectively. Fast (slow) measure should be interpreted as the resource utilization measure associated with the fast (slow) resource class. In this example the slow measure is the amount of power that may be allocated only by slow allocation procedures, whereas the fast measure is the total downlink power. Consider, also for the sake of simplicity that the triggering criterion is a simple comparison with thresholds TSLOW and TFAST. Assume that the network operator of the communications system has selected a configuration, e.g. stored in database 310 of FIG. 4, according to which the TFC limitation cannot be used to reduce the bit-rate below 32 kps when the 128 kps dedicated channel is used. However, it may limit the bit-rate even to 0 when the 64 kps dedicated channel is in use. In FIG. 5, the triggering thresholds are set to TSLOW=6 W and TFAST=13 W. For the sake of simplicity it is assumed that the speech user has 100% voice activity (no Discontinuous Transmission (DTX)) and that there is always data available for the Web browsing user in the send buffer. At moment t0 the speech user is in the 10.2 kps AMR mode and uses 1 W for its radio link. The Web browsing user utilizes the 128 kps channel to 100%, i.e. no TFC limitations, and uses 10 W. As any other channels are ignored in this example, the total downlink is 1+10=11 W, which is the value of the fast measure. Since TFC limitations can be used to reduce the bit-rate of the Web browsing user from 128 to 32 kps, but not lower (due to the operator selected configurations), the amount of slow allocated resources for the Web-browsing user are the average power that this user would consume if the TFC was used to limit the bit-rate to 32 kps. This amount can be estimated to 10 × 32 128 = 2.5 ⁢ W . On the other hand, the speech user is already using the lowest AMR mode (corresponding to the guaranteed bit-rate) and therefore the amount of slow allocated resources for this user (service) is exactly 1 W. Therefore, at moment t0 the slow resource utilization measure is 1+2.5=3.5 W. Note that in the present example, the fast resource utilization measure can actually be related to a measured value, while the slow resource utilization measure is an estimate. Therefore, a different value than 3.5 W might be obtained if other prediction or estimation models are employed. In this example a linear model is used. However, other models can be employed to estimate the average link power and the average total power when the TFC limitations are used for reducing the bit-rate from 128 to 32 kps. At moment t1 the speech user has not moved and it still uses the same link power of 1 W. However, the Web browsing user has moved and now uses a link power slightly larger than 12 W. Performing the same estimation as at moment t0 results in a value for the slow resource utilization measure of slightly above 1 + 12 × 32 128 = 4 W and the fast measure (total power) slightly above 1+12=13 W. As the slow measure is below the associated threshold (TSLOW), no slow allocation procedures are triggered. However, the fast measure slightly exceeds the 13 W threshold and therefore a fast allocation procedure is initiated. Thus, in this example, a TFC limitation from 128 to 64 kps is triggered. At moment t2, the fast TFC limitation is completely executed and the updated measures now are 4 W (same as moment t1) and 1 + 12 × 64 128 = 7 ⁢ W , respectively. At moment t3 the transmission conditions for the Web browsing user has not changed, but the power consumption of the speech user has increased so that its link power now is slightly above 3 W. As a consequence, the slow measure is slightly above 3 + 12 × 32 128 = 6 ⁢ W , while the fast measure is slightly above 3 + 12 × 64 128 = 9 ⁢ W , respectively. As the slow measure slightly exceeds its corresponding threshold TSLOW, a slow allocation procedure is triggered. Note that the allocation procedure is initiated despite the fact that the total average power (fast measure) is under control. There are presently three slow allocation procedures available: dropping the speech call, switching the 128 kps dedicated channel to a common channel or switching the 128 kps dedicated channel to a 64 kps dedicated channel. The first procedure has the disadvantage of breaking a QoS contract. The other two procedures do not break any QoS contract but the last one is to be preferred because it offers a better QoS to the Web browsing user. The exact choice of procedure is done according to the network operator's preferences to give priority to one or another type of service, or to obtain a specific network behavior. This operator policy is preferably available for the resource allocation system, e.g. in the configuration database 310 of FIG. 4, so that the allocation system can perform the selection between the available procedures. It is also preferred if the configuration database provides rules for prioritizing between different allocation procedures depending on the service type and requirements. In addition, it should preferably also provide rules for prioritizing between users with the same service(s). For example, among two users with the same communications service type, the one using most resources (highest code power) or the one having the highest bit-rate can be selected for being affected by the procedure. This applies for any resource class. At moment t4, the 128 kps to 64 kps dedicated channel switch is completed and the average power used by the Web browsing user is 6 W. The user is still provided with 64 kps, so that the QoS for this user is not affected by the executed allocation procedure. Note in FIG. 5 that the execution time (t5-t4) for this slow procedure is much longer than a corresponding execution time (t2-t1) for the fast procedure. Since TFC limitations are allowed, according to the operator configurations, to reduce the bit-rate to 0 kps, the amount of slow allocated resource for the Web-browsing user is at t4 equal to 6 × 0 64 = 0 ⁢ W . (However, this assumption is a simplification used in this example for the sake of simplicity. In practice, the amount of slow allocated resources is larger than zero due to the associated control channel that consumes some resources. But, as previously mentioned, the exact way to estimate the amount of resource to be used by a channel in different circumstances does not affect the principles of the invention). Thus, the slow resource utilization measure is 3+0=3 W and the fast resource utilization measure is 3+6=9 W. As was discussed in the foregoing, the increase in resource utilization may be caused by other factors than mobility or degradation of the radio environment. A request to set-up a new RAB service may trigger fast and/or slow allocation procedures. For example, the request for a link set-up received from a new speech user may lead to resource release (reduction) from a Web browsing user. In addition, the set-up request from a user with high priority may lead to the drop of a speech call with lower priority. This does not necessarily means that no resources are allocated to the Web browsing user. At moment t5 a request for a new link is received from a speech user whose link power is estimated to be 4.5 W. If the new link would be admitted, the slow measure would be 3+0+4.5=7.5 W and the fast measure would be 3+6+4.5=13.5 W. If the link request is permitted, the two measures exceed respective thresholds and therefore the admission is typically denied. However, if the new speech user has higher priority than the user that is already present in the system, the admission of the new user leads to the drop of the currently connected speech user, which is a slow allocation procedure. Note that the admission of the new user may temporarily lead to a total power (fast measure) increase above the TFAST threshold. Therefore, three allocation procedures are initiated and will run in parallel: the admission of a new user (slow procedure), the dropping of the old speech user (slow procedure) and the reduction of the bit-rate of the Web browsing user from 64 to 32 kps by TFC limitation (fast procedure). In the short time interval between t5 and t6, which is need for the TFC limitation to be executed, it is possible for the average total downlink power to increase above 13 W. This uncertainty is due to the fact that the execution of setting up a new link and disconnecting another connection are two uncoordinated transitory procedures. However, the restricted time during which the fast measure exceeds its threshold is a very short period compared to the time interval required to complete the set-up and/or disconnection. At moment t6 the slow measure can be at most 3+0+4.5=7.5 W (if the new connection is already set-up, but the old one is not yet disconnected), while the power used by the Web browsing user is 6 × 32 64 = 3 ⁢ W . Therefore, the fast measure is at most 3+3+4.5=10.5 W. At moment t7 the disconnection of the old speech user is completed. The amount of slow allocated resources now consists of the resources used by the new speech user, i.e. 4 W. Furthermore, the fast measure is 4 + 6 × 32 64 = 7 ⁢ W . According one aspect of the invention, the resource allocation method may be augmented with a triggering mechanism that allocates resources without waiting for an explicit request for increased resource allocation. For example, with reference to FIG. 5, TFC limitations are used to limit the total power utilization during the link admission process, in order to avoid the unacceptable increase of the average total downlink power during this transitory period (t7-t5). At moment t7, the fast resource utilization monitor (total downlink power) is below its associated threshold of 13 W and it would be possible to remove the TFC limitation imposed on the Web browsing user. In such a case, the user is allowed to utilize up to 64 kps. Since this operation is the reverse of the TFC limitation, their execution times are similar, i.e. removing an imposed TFC limitation is also a fast resource allocation procedure. When this resource assigning procedure is completed at moment t8, the fast measure is 4+6=10 W. Thus, when the demands for resources decrease and the measures for the different classes decrease, resources may be allocated or assigned for users, thereby increasing the amount of resources utilized for certain services and users. This could be accomplished by, for each resource class, compare its associated utilization measure with a second threshold (h*T). Then if the measure falls below this second threshold, more resources are allocated to certain users. The value of this second threshold h*T could be equal to or lower than the value of the first threshold (T). However, in order to avoid a self-induced oscillatory behavior in the system, the second threshold h*T is preferably lower than the first threshold T, realized e.g. by setting 0<h<1. The marginal between the two threshold (which depends on the value of h) can be set based on input information from the communications system, e.g. present and expected future traffic situation, expected future resource utilization, etc. In addition, if two thresholds are used for more than one resource class, the marginal of respective class may the same for all classes or may differ between different classes. Furthermore, if several different procedures for the same resource class can be taken and/or if different users or services can be selected for this resource assigning allocation, then priority and configuration principles can be employed in a similar way to the corresponding principles used when selecting procedures, users and services for resource limiting allocation procedures, discussed above. Since the different resource classes are managed separately it is possible for an resource assigning (“unshrinking”) procedure to be taken in one class in the same time with a resource limiting (“shrinking”) procedure in another class. FIG. 6 illustrates the principles of using two different thresholds for each resource class, or some of the classes, here represented by the resource class allocable with fast procedure. During the transition from time t0 to time t1, the fast resource utilization measure increases and actually exceeds its associated first threshold TFAST. As a consequence, a fast resource allocation procedure, e.g. TFC limitation, is triggered on some of the resource for the purpose of reducing this measure below the threshold TFAST. At moment t2, the resource allocation procedure is completed. At moment t3, one of the connected users has moved so that it now uses less link power than at t2. Due to this power reduction, the fast measure now is below its second associated threshold h*TFAST. Thus, more fast resources can be allocated to a user by means of triggering a fast allocation procedure, e.g. releasing the earlier imposed TFC limitation. At moment t4, this resource allocation is completed, increasing the value of the measure. FIG. 7 illustrates the above-described additional steps of the resource allocation method of the present invention. If the measure of the current class does not exceed the first threshold Tk, as determined in step S13 in FIG. 3, the method continues to the additional step S17. Here it is investigated whether the measure is below a second threshold hk*Tk. If the measure exceeds this second threshold the method continues to step S16 in FIG. 3. However, if the measure is smaller than hk*Tk more resources of the current class can be allocated to connected user, e.g. by imposing an earlier imposed resource utilization limitation, in step S18. The method then continues to step S16 in FIG. 3. A (automatic) threshold setting procedure can be employed for setting the values of some of the threshold values employed for the different resource classes. In a preferred embodiment of the invention only one threshold is explicitly set, while the other thresholds are (automatically) determined based on this threshold. In order to understand the purpose of this threshold setting, a closer analysis of the two classes case as exemplified in FIG. 5 follows. The sudden increase in the resource demand at moment t5 is only slowly coped with by the slow allocation procedures. Under these circumstances the fast procedures are attenuating these effects in a similar way as the dampers of a car are working on rough terrain. Thus, fast procedures are employed at moment t5 to reduce the resource demand. Consequently, the pool of fast allocable (shrinkable) resources, i.e. those resources that cannot be allocated by slow procedures, is reduced from 13.5−7.5=6 W at moment t5 to 10.5−7.5=3 W at moment t6. This is similar to the squeeze of the car's dampers when the wheel passes over a stone. When the threat for a congested situation ceases, i.e. the execution of the slow procedure(s) is completed, a reverse fast allocation procedure is used to expand the resource utilization, so that the pool of fast allocable resources increases from 7-4=3 W at moment t7 to 10-4=6 W at moment t8. Thus, the pool of fast allocable resources temporarily decreases from 6 W to 3 W, in order to cope with the sudden increase in the slow allocated resources, and then returns to the initial value (6 W). The difference between the two thresholds TFAST and TSLOW can be regarded as the uncompressed (unshrinked) length of the car's dampers. As the optimal length of these dampers depends on the expected roughness of the road, the optimal difference between the two thresholds can be related to the expected variations of the slow allocated resources. This in turn depends, for example, on how large the unexpected increase can be, i.e. on the dynamics of the radio environment in the radio communications system, how fast the slow procedures can be completely executed, how frequent these resource demanding events are, etc. An automatic procedure could use e.g. TFAST as reference and then determine the other threshold (TSLOW) in an adaptive fashion, based on a feedback loop. The resource allocation unit or another unit in the communications system may evaluate the probability ε for the slow allocated resources (the measure of this slow resource class) to be equal to or larger than TFAST. If such a situation would occur, the pool of fast allocable (shrinkable) resources is reduced to zero and no fast allocation procedures can any longer be employed for reducing the total resource utilization below TFAST. The current value of TSLOW can then be updated with the purpose of keeping the probability ε at an acceptable level. A too large probability ε means that the slow allocated resources are allowed to increase too much with respect to TFAST and therefore slow procedures should be triggered at a lower level than the current value of this slow resource measure. Consequently, at a high probability ε, the value of TSLOW should be decreased. It is also possible to use different evaluation criteria and different updating procedures, e.g. jumping and scaling, than the above discussed without changing the basic concept of this embodiment. The principles may also be applied to systems with more than two different resource classes. In such a case, one or several thresholds may be fixed and the remaining thresholds could be determined based on some or all of these fixed values. As was discussed above, the resource allocation system of the invention can be configured in such a way that in certain circumstances it is not allowed to execute a specific resource allocation procedure, even if this procedure would be practically possible. The reason why such an available procedure is not allowed to be used could be the QoS requirements or that a certain system behavior is desired. For example, if the bit-rate currently provided to a, service already is as low as the guaranteed bit-rate, an allocation procedure that further reduces the bit-rate is not allowed, although it might be available. With reference to FIG. 8, in the case of two (fast and slow) resource classes, the slow allocated resources can be regarded as comprising guaranteed resources that must be provided to users in order to fulfil QoS contracts, but also slow resources that are allocated in a best-effort fashion. In the present application, the expression “shrinkability” refers to the amount of resources (e.g. power) in a cell that can be reduced without breaking any QoS contracts. In this context, “fast shrinkability” corresponds to the amount of resources (power) in a cell that can be reduced by fast resource allocation procedures, such as TFC limitations, without breaking any QoS contract. Correspondingly, “slow shrinkability” refers to the amount of resources (power) that can be reduced in a cell by slow resource allocation procedures, i.e. other procedures than the fast TFC limitations, without breaking any QoS contract. Slow allocated resources can then be viewed as comprising the sum of guaranteed resources and slow shrinkability. In addition, “(fast) negative shrinkability” is referred to the amount of resources (power) in a cell that can be reduced by fast allocation procedures (TFC limitation) resulting in a reduction of the bit-rate below the guaranteed bit-rate level. If the slow resource utilization measure exceeds the threshold associated with the fast class, the only way to reduce the total resource consumption below this threshold is to wait for the completion of one or several slow resource allocation procedures, since no fast procedures may be employed (the pool of fast allocable resources is zero) to avoid the congested situation. In this case only guaranteed resources are left for allocation, see 600 in FIG. 8. This unfavorable situation may be coped with according to another aspect of the invention. In this aspect, allocation procedures that otherwise would not be allowed are temporarily used, i.e. the guaranteed resources are (re)allocated. In the general case, if the measure associated with the i-th resource class exceeds the threshold of the j-th class (j>i), then procedures belonging to the classes i+1 to j, that otherwise are not allowed to be used due to configuration and/or QoS reasons, may temporarily be employed for reducing the actual resource utilization during progression of the triggered resource allocation procedure of class i. In the particular case with two classes, this means that fast allocation procedures that are not allowed due to these configurations or QoS reasons could temporarily be employed if the slow resource utilization measure exceeds TFAST. By “temporarily employed” is meant the fact that a reversed procedure is preferably used after a while, when the subsequently resource demand becomes reduced, such as after completion of slow resource allocation procedure(s), to restore the initial fast resource conditions. Consider the example in FIG. 9, where the triggering threshold for the slow allocated resource measure is set to 6 W and the fast measure (average total power) is set to 7.5 W. In this example, a first user is consuming 2 W for its guaranteed bit-rate and a second user utilize streaming services of 48 kps on a 64 kps dedicated channel. These 48 kps are a guaranteed bit-rate for the streaming service. Assume that the streaming user would consume 4 W if he used the channel at 100% capacity. Therefore, he presently uses 4 × 48 64 = 3 ⁢ W . Further assume that available slow allocation procedures are limited dropping a call and handover to another system (another carrier or another radio access network). Available fast procedures are TFC handling (limitation and recovery). The slow measure is 2+3=5 W at moment t0. Since both users have allocated only guaranteed resources, the average total power (fast measure) is equal to the slow measure. This means that the value of the fast measure is identical with the value of the slow measure and that the pool of resources allocable with fast procedures is zero. The first user then moves to an area with poor radio conditions so that it demands more and more resources, while the demands of the streaming user remain unchanged. Following this trend, at moment t1, the slow measure exceeds is threshold of 6 W. As a consequence, a slow procedure is triggered. Assume that a handover to another system is initiated for the first user and the execution of this procedure is not completed until moment t4. Meanwhile, the increasing trend continues until the slow measure exceeds at moment t2 the threshold of the fast resource class. According to the configuration, TFC limitation (fast allocation procedure) cannot be used to permanently release resources in this case (compare with exceeding the max limit in FIG. 8). However, according the invention, resources can temporarily be released (allocated) from the fast resource class. Thus, TFC limitation is used to reduce the bit-rate of the streaming user from 48 to 32 kps. Thereafter the streaming user only utilizes 4 × 32 64 = 2 ⁢ W . After the execution of the fast procedure (moment t3), the power consumption is reduced to below the 7.5 W threshold and the congested situation is avoided. If this exception to the rule of not breaking QoS contracts not would have been employed, the average total power would have further increased and the risk for an unstable communications system would have been unacceptable. At moment t4, the handover of the first user to another system is competed and the slow resource measure becomes 2 W. Furthermore, there is no risk that removing the TFC limitation would lead to a new increase of the slow measure above the threshold TFAST. Therefore, at moment t4, a fast procedure of removing the TFC limitation is triggered and at moment t5 the user bit-rate of 48 kps is restored to the guaranteed value for the streaming user. In this case, the slow measure becomes 4 × 48 64 = 3 ⁢ ⁢ W and the value of the fast measure is still the same as this slow measure value. In addition, the TFC limitation to 48 kps can be removed (t5) too and thus providing 64 kps at moment t6, after completion of the fast resource assigning procedure. Thus, although the communications system temporarily delivers a bit-rate below the guaranteed level for a user, the average bit-rate over time for that user is still according to the QoS contract. In other words, fulfillment of QoS requirements and guaranteed service levels could be viewed as in average delivering the guaranteed contracted service, although at some instances the lower level is provided. This lower than agreed provided level could be compensated by, at other instances, providing a higher than guaranteed level. When using this aspect of the invention of temporarily employing non-allowed resource allocations, there is a risk that the quality provided to the users becomes lower than the desired values. For example, in UMTS, the QoS requirements may become lower than the values contracted through the RAB attributes. In the following the present invention will be exemplified, but not limited to, the management of streaming services. However, the teaching could alternatively be applied to other forms of services. In this example, the idea is to monitor the packet delay for the streaming user that has been affected by a non-allowed resource allocation procedure. The reason for this is that a reduced transport bit-rate results in data being accumulated in the sender's buffer and therefore to increased delay. According to this aspect of the invention, the bit-rate limitation associated with the temporary resource allocation is ceased (i.e. the initial bit-rate is restored, or another higher than this initial bit-rate is provided) when the delay threatens to exceed the maximum delay attribute in the QoS contract. Since the communications system may comprise several streaming users that can be selected for being affected by the temporary TFC limitation, a priority mechanism that protect the users that have previously been affected by this procedure can be employed. Also a mechanism for differentiating between the delay cased by the temporary TFC limitation and the delay caused by the service by sending data at a higher bit-rate than the guaranteed through the contract could be used. For a better understanding of this aspect of the invention, an implementation for UMTS systems is described in the following. In this example, the “maximum delay” parameter in the QoS attribute list of the streaming RAB is explicitly considered. The amount of data in the downlink Radio Link Control (RLC) buffer is used to estimate the actual delay. The algorithm proposed and disclosed herein can then use this estimate in order to fulfil the QoS guarantees. However, the packet delay may also increase due to traffic variations in the source traffic, e.g. when the streaming server sends data at higher rate than the contracted RAB, or due to other throughput affecting algorithms. The delay monitoring is therefore done to distinguish between the delay introduced by TFC limitations and the delay due to other causes. Since the TFC limitation procedure will reduce the available number of transport block and hence postpone the transmission of some bits, the buffer size will increase. These extra bits, caused by the lower bit-rate, can be written as: L TFC = ∑ i = 1 users ⁢ ⁢ last ⁢ ⁢ TTI ⁢ ( BR guaranteed - BR i , now ) × TTI i , ( 1 ) where LTFC are the extra bits in the buffer, BRguaranteed is the guaranteed bit-rate, BRi, now is the current bit-rate during the current Transmission Timing Interval (TTI) and TTIi is the current TTI length. The summation is over all TTIs during the lifetime of the user connection. The total overall delay is then: Lnow=LifNoTFC+LTFC, (2) where Lnow and LifNoTFC are the current buffer length and the buffer length without any TFC limitations, respectively. Using expression (1) and (2) together and dividing both sides with BRnow, results in an expression for the delay (DTFC) originating from the TFC limitation: D TFC = L TFC BR now ⁢ = ∑ i = 1 users ⁢ ⁢ last ⁢ ⁢ TTI ⁢ BR guaranteed ⁡ ( 1 - BR i , now BR guaranteed ) × TTI i BR now , ( 3 ) but also an expression for the overall delay, according to: D TOTAL = ⁢ L now BR now = ⁢ D ifNoTFC + ⁢ ∑ i = 1 users ⁢ ⁢ last ⁢ ⁢ TTI ⁢ BR guaranteed ⁡ ( 1 - BR i , now BR guaranteed ) × TTI i BR now , ( 4 ) where DTOTAL is the current delay and DifNoTFC is the delay for the bits currently in the buffer if no extra “TFC-postponed” were added. By inspection of equation (4), it is evident that if BRi, now is equal to BRguaranteed for every TTI, i.e. no TFC limitation, during the lifetime of the user connection, no extra bits are added up. Thus, no additional delay occurs, i.e. DTOTAL=DifNoTFC. It is also worth mentioning that the “system observable” is the total buffer size, i.e. Lnow and the corresponding DTOTAL, and that the other quantities, e.g. LifNoTFC and LTFC, can be obtained by secondary calculations. When the bit-rate for a streaming user has been reduced, the quality measure in the present example is defined for that user to be acceptable if the total delay (DTOTAL) is below a pre-defined limit and if the TFC generated delay is lower than a pre-defined threshold, such as lower than a fraction of the total delay: ok=if [(DTOTAL<T) AND (DTFC<kT)] (5) Equation (5) is used by the system to fulfil the QoS contract and therefore ensure the quality perceived by the end user. The flow diagram of FIG. 10 illustrates the principles of for this example. The allocation method starts in step S1 of FIG. 2 and moves to step S20, where it is investigated if a congestion situation is present. In step S21, the resource utilization measure for the slow resource class is compared to its associated threshold. If the measure exceeds the threshold, a slow resource allocation procedure should be triggered. Step S22 investigates if there are any slow resources to allocate (slow shrinkability). If no, an on-going call is dropped in step S23. However, if slow allocable resources are available, a slow allocation procedure is initiated in step S24. The method then continues to step S25, where the utilization measure for the fast resource class is compared to its threshold. If the measure is below (or equal to) the threshold the method ends, but if the measure exceeds the threshold a fast allocation procedure should be initiated. The method then continues to step S26 where the availability of fast resources to allocate (fast shrinkability) is investigated. If fast allocable resources are available, a fast allocation procedure is triggered in step S27 and the method then ends. However, although no fast resources are available, it might possible to temporary limit the available TFC for a user, at least until the slow allocation procedure is completed. If it is concluded in step S28 that TFC limitations can be employed, such a fast allocation procedure is initiated in step S27. Thus, by rapidly (execution time of a fast procedure such as TFC limitation is typically in the order of one or several TTIs) reducing the number of used transport blocks, the total downlink power consumption can be scaled down during the progression of the slow allocation procedure (which often takes at least several hundreds of milliseconds to be completely executed). Using this temporary bit-rate-reducing algorithm, additional delay may be induced by the extra “non-sent” bits that accumulate in the buffer. To avoid this, once the congested situation is over, as determined in step S20, step S29 can investigate if there is any shrinked users present, i.e. any users that are affected by TFC limitations. If such users are present, more resources may be assigned to them by releasing the imposed TFC limitations in step S30. FIG. 11 is a flow diagram illustrating additional steps of selecting whether or not to release previously imposed TFC limitations. If step S29 determines that a user, for the time being, uses a lower transport block configuration, due to a TFC limitation, step S31 checks the current total delay. If the total delay is found to be too large, i.e. over a pre-defined threshold T, the number of available transport blocks are restored for that user in step S32. If the total delay is found to be smaller than the threshold T in step S31, another check is performed in step S33 to investigate if the portion of the total delay caused by the TFC limitation is too large. If this portion (DTFC) exceeds a second threshold kT (0<k<1), the TFC limitation has been in use too long (or too intense) and the bit-rate should be increased in step S32, since the RAB contract runs a risk of being broken. The other main-path in the figure, is when some user previously has been “shrinked” but is presently not. In this case, step S34 first checks the current total delay and if the delay is found to be smaller than the threshold T, no contract is broken and no additional action is taken, i.e. remain on current TFC. If the delay is too large, the fraction of the total delay caused by TFC limitation is investigated in step S35. If this fraction is small, it is concluded that the total delay is too large but it is not caused by the imposed TFC limitation, but by some other actions. Such other actions could be when the core network (streaming server) provides data at a rate larger than guaranteed and, thus, risking to fill the buffer faster than expected. However, if the fraction is large, the TFC limitation has caused a too low bit-rate during a too long period. The user should then preferably be assigned a higher bit-rate in step S36. If TFC limitations are still present, this increase in bit-rate can be obtained by simply restoring the number of transport blocks for the considered user. FIG. 12 is a schematic block diagram of a resource allocation system or unit 100 according to the present invention. The system 100 comprises an input and output (I/O) unit 110 adapted for conducting communication with external units in the communications system. In particular, this I/O unit 110 is adapted for receiving input information and data, which is used by the system 100 for performing an efficient resource management. In addition, the I/O unit 110 is adapted for transmitting resource portioning or allocation commands to a resource portioning unit that performs the actual portioning of resources for different services, links and connected end terminal (user equipment) for the communications system if such portioning unit is not provided in the allocation system 100. The I/O unit 110 may also send information of possibly triggered allocation procedures to an external allocation database 330, thereby allowing updating data of a current resource allocation. Determination means or unit 120 is provided in the allocation system 100 for determining, i.e. estimating or explicitly calculating, the resource utilization measures for the different resources classes. The determination means 120 typically receives input information, e.g. code power/peak power used for different channel, from other units, such as a database or register 330 comprising information of the current resource allocation, in the communications system for performing its determination functionality. A selective allocation trigger 130 is provided in the system 100 for determining, based on the resource utilization measures from determining means 120, if resource allocation procedure(s) should to be triggered for the different resource classes. This allocation 130 is preferably adapted for performing the selective allocation triggering based, for each resource, on a comparison of the utilization measure with a threshold value associated with the current class. This comparison is preferably initiated for the resource class having access to the slowest resource allocation procedures, i.e. longest execution time, and then for classes with resources allocable with increasingly faster allocation procedures. These different (slow and fast) allocation procedure functions could be implemented in the resource allocation system 100, such as in the trigger 130. Alternatively, the allocation procedures could be provided elsewhere in the communications system. In such a case, the trigger 130 generates a trigger signal, which is transmitted to the correct external allocation functionality. The trigger 130 preferably also determines which allocation procedure(s) to employ for each resource class, if there is a choice. In addition, the system 100 preferably includes selection means or unit 140 for selecting, which entity/entities to be affected by a possible resource allocation procedure as initiated by the trigger 130. This selection means 140 preferably determines which service(s), link(s) and resources to be affected of any allocation procedure. In order to facilitate this determination, the selection means 140 preferably receives input information from external units, such as databases 310, 320 and 340 comprising information of restricting utilization of the allocation procedures in some particular cases, information of available resource allocation procedures and their respective execution times and information of QoS requirements and contracts, respectively. As an alternative this entity selection functionality could be provided elsewhere in the communications system. Optional packet delay determination means 150 can be provided in the system 100 for determining or estimating the total current packet delay for connected user equipment and preferably packet delay introduced due to an imposed TFC limitation. The resource allocation system 100 may optionally also comprise a storage 160 adapted for storing thresholds used by the trigger 130 for determining when to trigger a resource allocation procedure and for which resource class(es). This threshold storage 160 could alternatively be provided in, or in connection with, the operator configuration database 310. An optional threshold manager 170 could be provided in the system 160 for managing the thresholds in the storage 160. This manager 170 is, in particular, adapted for entering the thresholds in the storage 160. Furthermore, the manager 170 can calculate or set some or all thresholds based on input information from external units 310, 320, 330 and 340. The manager 170 may also be adapted for (automatically) calculating the thresholds of some classes based on predetermined value(s) of one threshold or multiple thresholds. The units 110, 120, 130, 140, 150 and 170 of the resource allocation system 100 may be provided as software, hardware or a combination thereof. The units may be implemented together, e.g. in a single network node in the communications system, such as in a node in a base station system. Alternatively, a distributed implementation is also possible with some of the units provided in different network nodes of the communications system. For a radio communications system, the resource allocation system 100 could be provided in a Radio Network Controller (RNC), such as in a Drift RNC (D-RNC), a Controlling RNC (C-RNC) and/or a Serving RNC (S-RNC). As these units are traditionally employed for e.g. controlling radio resource allocation, data-flow control, congestion and admission control in radio communications, the resource allocation system 100 is preferably in a common RNC unit having the functionality of the traditional D-RNC, C-RNC and S-RNC units, or a common D-RNC and S-RNC unit, or in one, some or all of D-RNC, C-RNC and S-RNC. In particular for an embodiment of the resource allocation system 100 that is adapted for managing (restricting or increasing) the number of available transport blocks (TFC), a common D-RNC and S-RNC unit is preferred. In such a case, no inter-unit communications are required between the D-RNC unit, traditionally being employed for monitoring resource allocation and having (a layer three) functionality that considers all links, and the S-RNC unit, traditionally monitoring the data traffic on all links and having RLC—Medium Access Control (MAC) (layer two) functionality. Thus, TFC manipulating (increasing or reducing the number of available transport blocks) on a downlink channel can be employed as a fast resource allocation procedure for controlling the utilization of another resource type, i.e. average code power or carrier power. FIG. 13 is a schematic block diagram illustrating an embodiment of the selective allocation trigger 130 of FIG. 12 in more detail. In this embodiment, the trigger preferably comprises comparison means or unit 132 adapted for comparing the resource utilization measure of a current class, as provided from determining means 120 in FIG. 12, with the threshold(s) of the current class (from storage 160) for selectively triggering a resource (reducing or assigning) allocation procedure. Furthermore, the comparison means can be adapted for comparing packet delay values from delay determining means 150 of FIG. 12, with different delay thresholds. The trigger 130 also preferably comprises means or unit 134 for selecting an allocation procedure (or possibly several procedures) to employ for the current class if the comparison means 132 determines that a resource allocation procedure is to be initiated. Thus, for a current resource class there may be several allocation procedures available for the selecting means 134 to select among. The actual choice of procedure(s) may be based, at least partly, on input information from external units, but also on how much the measure of the current class exceeds the associated threshold. The units 132 and 134 of the selective allocation trigger 130 may be provided as software, hardware or a combination thereof. The units may be implemented together. Alternatively, a distributed implementation is also possible. It will be understood a person skilled in the art that various modifications and changes may be made to the present invention without departure from the scope thereof, which is defined by the appended claims. REFERENCES [1] 3GPP TS 23.107 v5.10.0; 3rd Generation Partnership Project; Technical Specification Group Services and System Aspects; Quality of Service (QoS) concept and architecture, September 2003.
<SOH> BACKGROUND <EOH>A communications system manages and provides resources for use by e.g. its connected users for the purpose of enabling utilization of communications services in the system. For example, a radio communications system provides radio resources that its mobile users then utilize for conducting e.g. voice, packet transmission and streaming services. The communications system typically only has access to a limited pool of resources, which are portioned out between the different users and services. Thus, the users and services can be regarded as competing for the limited amount of resources. In addition, in some communications system, or for certain resource types, the demands for resources change at specific events. Such events could be the addition of a new service, the closing of a communications session or a change in the requirements set by the end-user application. Often some explicit signaling follows these kinds of events. This signaling is then used to trigger the execution of a resource allocation procedure. For example, each time a new call is to be set up in a Global System for Mobile communications (GSM) system, a resource allocation unit or system has to look for an available channel, a time slot (radio resource) is then allocated to the user, or the call request is denied (which may result in a blocked call or a failed handover). In this example, the resource, i.e. time slot, is explicitly allocated and retrieved by a resource allocation procedure initiated by the allocation unit. In other communications system, or for other resource types, the demand for resources may dynamically change due to other reasons. For instance, in a power controlled mobile communications system, such as Universal Mobile Telecommunications System (UMTS) or Code Division Multiple Access (CDMA) 2000 systems, the power control loop adapts the transmitted power in response to changes in the radio conditions experienced over the radio connection. Such condition changes can be the result of the mobility of the user equipment or caused by changes in the interference level experienced by the receivers. However, even for fixed radio connections, the power demand may vary due to changes in interference levels (caused by other systems), due to mobility issues or due to changes in the propagation environment (e.g. due to changes in the weather conditions). In this case, a resource allocation has to be continuously (or periodically) updated, so that the allocated resources match a current resource demand. A particular aspect of some communications systems is that the resource allocation architecture is split into several layers. For example, the fast power control in Universal Terrestrial Radio Access Network (UTRAN) is a standardized procedure at link level, which treats each connection independently. As a consequence, the fast power control algorithm is sometimes not seen as a resource allocation algorithm. In this context, the resource allocation procedures are then viewed as trying to influence the resource demand. For example, the resource demand for a certain channel may be reduced, at least in average, by reducing the bit-rate available on that channel. Accordingly, even in systems where the resource cannot directly be affected by a resource allocation procedure (as is the case with the power in UTRAN, discussed above), there might be procedures that ultimately influence the resource demand. For example, a down-switch from a dedicated channel with high bit-rate to a dedicated channel with lower bit-rate or to a common channel can be regarded as a resource pre-emption procedure and therefore can be used to cope with changes, such as an unexpected increase, in the resource demands. In the present description, the expression “resource allocation procedure” includes any procedure that ultimately leads to a change in the amount of used resources, even if the procedure does not directly effect the resource usage. Thus, the expression also includes resource (re)allocation and pre-emption procedures. A general case of a communications system with a limited pool of resources is a communications system, in which a sender transmits, in the same time, signals to a number of receivers. This can be exemplified by the downlink transmission between a base station and a number of mobile units in a UMTS system. A common pool of (radio) resources (e.g. the total downlink power, or carrier power) is shared between the different links. The specific amount of resources allocated to a link depends, among others, on the characteristics of the communications service provided by the sender on that link, but also on other external factors that cannot be controlled by the sender. For example, the amount of power required by a link in a mobile radio communications system depends on the bit-rate required by the communications service and can therefore be controlled by the sender by changing the provided bit-rate. However, the amount of power required by the link also depends on factors out of control for the sender, such as the position and movement of the mobile user equipment, the interference induced by other systems, etc. Since the total amount of used resources (total resource utilization) in a communications system with shared resources is the sum of the amount of resources used on each link, i.e. allocated for each user, the increase in total resource utilization can be caused by an increase in the number of links and/or by an increase in the amount of resources used by the individual links. There is typically no problem as long as the total resource utilization is below the total amount of available resources, but as the total resource utilization increases too much and the resources become scarce, actions have to be taken to limit or reduce the resource utilization. One way to limit the total resource utilization is to hinder the increase in the number of links, a procedure called admission control in the art. An alternative solution is to remove a link belonging to a user with low priority, when a high priority user requires access to a service. This is the case with SOS calls in a GSM system. However, the increase in the total resource demand or utilization can, as was mentioned above, be due to increases in the amount of resources used for the links. Such increases in demanded resources can be caused by the mobility of the user equipment, changes in the behavior of a provided service, etc. In this case, the amount of resources presently allocated to one or several links has to be decreased, a procedure called congestion control in the art. In a general case, in which users have different priorities and the services provided to the users have different demands, the admission and congestion control can be seen as particular cases of a resource allocation procedure. A relevant example is when the increased amount of resources allocated to a link with high priority, e.g. due to an increase of demanded bit-rate, the addition of a new bearer to a multi-bearer connection, etc., is done by reducing the amount of resources allocated to a low priority link. The common solution for a communications system to prevent the resource demand or utilization from exceeding the maximum total resource limit, which is often determined by hardware limitations, is to initiate a resource allocation. However, this resource allocation can in most cases be performed by means of several different allocation procedures. A problem with the prior art solutions is then how to select which allocation procedure to employ, but also how to select which link to be affected by the resource allocation, in the case of a choice between different procedures and/or links that leads to the same end-result. For example, some resource allocation procedures, such as channel down-switch, require rather extensive signaling and handshaking between the sender and the receiver and consequently require a long time before the allocation becomes effective. Other resource allocation procedures do not require handshaking and therefore have a relatively shorter execution time. This scenario is exemplified in FIG. 1 . At time t 0 the communications system is in a situation where the resource demand is unacceptable high and therefore a resource allocation procedure must be applied in order to reduce the overall resource utilization. Assume that in this situation two different procedures can be employed in order to reduce the resource utilization with the same amount. One of these two procedures requires handshaking between the sender and the receiver and, thus, has a long execution time (slow procedure). The second procedure is fast, i.e. has shorter execution time. In addition, both procedures result in the same quality of service (QoS) requirements for a user, as exemplified by the provided bit-rate of 64 kps. Call t 1 a time after the execution of the procedures, i.e. when the resource allocation is completed. Assume that a new resource shortage occurs and additional resources must be released (resulting in a reduction of bit-rate to 48 kps). Further assume that for the first case, i.e. employing a fast resource allocation procedure in time t 0 , now only slow allocation procedures are available. However, for the second case, i.e. employing a slow resource allocation procedure in time t 0 , now both fast and slow allocation procedures are available. At time t 2 , the second resource allocation is completed. The situations at time t 0 , t 1 and t 2 can be regarded as states in a state machine. From an initial state A at time t 0 two different resource allocation procedures can be employed. Depending on the employed procedure, one of two states (B or C) is reached at time t 1 . From the point of view of the amount of utilized resources and from the QoS (bit-rate) point of view, the two states are identical. However, the states differ in the procedures available for the next transition. Thus, transition from state B (to D) can only be performed with a slow procedure, while transition from state C can be done with a fast procedure (to E) or a slow procedure (to F). A typical prior art allocation unit or system is generally adapted for always employing a fast resource allocation procedure, if available. With reference to FIG. 1 , this corresponds to selecting a fast allocation procedure at time t 0 , i.e. the transition from state A to B. However, it might then be possible that the subsequent resource allocation, i.e. from B to D, is time critical. Since now only slow procedures are available according to FIG. 1 , system instability might occur if the resource demand becomes too large before the slow allocation is completely executed.
<SOH> SUMMARY <EOH>The present invention overcomes these and other drawbacks of the prior art arrangements. It is a general object of the present invention to provide an efficient resource management in communications system. It is another object of the invention to provide a dynamic resource allocation in communications system. Yet another object of the invention is to provide a resource allocation that maintains the possibility of employing fast resource allocation procedures. A particular object of the invention is to provide a resource allocation that does not increase a packet delay experienced by streaming users above guaranteed quality of service (QoS) levels. These and other objects are met by the invention as defined by the accompanying patent claims. Briefly, the present invention involves resource allocation in communications system. According to the invention, the pool of resources provided by the communications system, or a portion or a sub-system thereof, is divided into different resource classes based on an associated characteristic allocation time. Thus, resources from a given class can be allocated by one or several resource allocation procedures having a characteristic execution time. Correspondingly, resources of another resource class can be allocated by one or several other allocation procedures having other characteristic execution times. The characteristic allocation or execution time then corresponds to a total time from the triggering of a particular allocation procedure to the completion of the allocation. It may be possible that there is only one allocation procedure available for a given resource class. However, it may be possible to allocate resource of a certain class by means of several different allocation procedures, where these procedures have approximately the same allocation time or speed. Furthermore, the resources are divided into multiple classes, i.e. two or more classes, with different associated allocation times. For example, the resources can be divided into two classes. In such a case, a first class comprises resources allocable with fast resource allocation procedures and a second class comprises resources allocable with slow resource allocation procedures. Slow procedures generally require extensive signaling and handshaking between the communications system and the unit, to which the system provides the resources. This handshaking and signaling result in a long execution time, typically in the order of several hundreds of milliseconds. In contrast to the slow procedures, fast resource allocation procedures typically have an execution time of a few or even less than hundred milliseconds. The resource allocation method comprises that, for each resource class, a resource utilization measure is determined or estimated. This measure is preferably based on the total resource utilization for the current class. In a typical embodiment, the resource utilization measure is the amount of power of the current class that is used on communications links in the system. Based on this resource utilization measure, it is determined whether or not to trigger one or several resource allocation procedures on resources of the current class. The general object of this allocation is to reduce the resource utilization measure. Note that decreasing the utilization measure does not necessarily lead to a reduced amount of resources allocated from the affected class. In a preferred embodiment of the invention this selective allocation triggering is performed by comparing the resource utilization measure of the current class with an associated threshold. If the measure then exceeds the threshold, a resource allocation is initiated. This utilization measure determination and selective triggering are repeated for all resource classes, preferably starting with the class containing resources that are allocable with the resource allocation procedures having the longest characteristic allocation time. The measure determination and selectively triggering are then performed for the class with the next second longest allocation time and so on ending with the class with the shortest allocation time. Since the characteristic allocation times for the classes differ, several allocation procedures may run parallel for the different classes. The advantage of dividing resource into different classes according to the invention and investigating and possibly allocating each resource class individually is that the possibility for the communications system of always having a pool of fast resource available for allocation increases. This means that the communications system most often, and preferably always, has access to a fast resources allocation procedure to use when the total resource utilization in the system becomes too large. Thus, when resources become scarce, the available fast allocation procedures can be triggered for quickly releasing some resources and thereby avoid the risk of system instability. For a mobile radio communications system having radio resources of two resource classes, examples of slow resource allocation procedures include a channel switch from a dedicated channel with a first bit-rate to a dedicated channel with a second different bit-rate (dedicated channel re-configuration) and a channel switch from a dedicated channel to a common (non-power-regulated) channel. Slow procedures also comprise a handover from one radio access network to another radio access network and handover between different carrier frequencies (Inter-Frequency Handover (IFHO)). Also dropping an on-going call for connected mobile user equipment can in some applications be regarded as a slow allocation procedure. A fast allocation procedure, in particular for affecting the downlink power of a downlink channel, is to limit access to the number of transport blocks available for transmission. Such a limitation in the available transport format combinations (TFCs) results in a reduction in the provided bit-rate and consequently a reduction in the downlink power. In some applications it may not be possible to allocate resources (reduce the resource utilization) of a certain class without breaking a QoS contract. Thus, the communications system may currently provide a guaranteed amount of resources to a user. For the example with a mobile radio communications system with a fast allocable resource class and a slow allocable resource class, a situation can occur where the resource utilization measure of the slow allocable class exceeds its associated threshold and a slow resource allocation procedure is triggered. However, during the relatively long progression of this resource allocation, the radio conditions may worsen leading to an increase of this utilization measure. It may even be possible that this measure actually exceeds the threshold for the fast allocable class. In such a case, the pool of fast allocable resources become zero and no fast resource allocation procedures are available for reducing the total resource utilization in the communications system. Thus, the system has to wait for the completion of the slow allocation procedure until the resource utilization can be lowered. However, during this long execution the resource demands can increase further causing system instability. According to the invention, a fast resource allocation procedure is then temporarily employed for releasing resources from a user that presently is provided a guaranteed amount of resources, e.g. reducing available transport blocks to a level below the guaranteed one. As a consequence, the system will temporarily deliver a less-than-guaranteed amount of resources to a user. Once the slow allocation procedure is completed, the amount of resources allocated to this user may the increased, e.g. by releasing a previously imposed TFC limitation. Thus, although a user at a certain moment may be provided with less than guaranteed amount of resources, the average resource amount provided over time to that user is at least according the guaranteed level. This embodiment of temporarily reducing the bit-rate (through use of TFC limitations) may result in breaking QoS contracts, in particular for streaming users, since the reduced transport bit-rate leads to data being accumulated in the sender's buffer and therefore to increased packet delay. By monitoring the total packet delay and the delay originating from TFC limitation for different users, imposed TFC limitations may be released (if the delays become too large) before QoS contracts are broken. The invention offers the following advantages: Enables combined usage of slow resource allocation actions and fast resource allocation actions; Ensures system stability by reducing the probability for the party effect and reducing the probability for the communications system to get into congestion; Provides efficient resource utilization; Enables usage of a low margin between working point and a maximum resource consumption level; Ensures that delay for streaming users is kept within contracted QoS levels. Other advantages offered by the present invention will be appreciated upon reading of the below description of the embodiments of the invention.
20051024
20100831
20060629
58922.0
H04L1226
0
CEHIC, KENAN
RESOURCE ALLOCATION MANAGEMENT
UNDISCOUNTED
0
ACCEPTED
H04L
2,005
10,532,151
ACCEPTED
Method for determining the current position of the heads of vehicle occupants
The invention relates to a method for determining the current position (A, B, C, D) of a head (9) of an occupant (8) in the passenger compartment (2) of a motor vehicle (1), said head moving toward an automatic dynamic disabling zone (6) in front of an airbag module (5). To this end, the invention makes use of the idea that the best position for a measurement with regard thereto is the point in space where the ideal direction of movement (14) of the head (9) is perpendicular to an ideal line of sight (17) of the camera (160. The measurement is then preferably carried out when the geometric center (10) of the head (9) crosses this point. In a preferred embodiment, the calculation of the actual movement vector of the head (9) is taken as a basis, said head being preferably perpendicular in a current line of sight (18) of the camera (16). The invention advantageously increases the potential for protecting an occupant (8) in a motor vehicle (1). It is thus suited, in particular, for use in occupant protection systems of modern motor vehicles (1).
1-14. (canceled) 15. A method for determining a current position of a head of an occupant in a passenger compartment of a motor vehicle, the head moving toward an automatic dynamic disabling zone in front of an airbag module, which comprises the steps of: providing an image acquisition unit having an ideal line of sight being substantially perpendicular to an ideal direction of movement of the occupant; recording an image scenario in the passenger compartment of the motor vehicle containing the occupant at least cyclically with the image acquisition unit and image information relating to the occupant being detected; determining both a position of a geometric center of the head and an apparent size of the head in the ideal direction of movement in a respective current scenario image; defining current lines of sight of the image acquisition unit as a vector, from a defined position of the image acquisition unit to a respective current position of the geometric center of the head; calculating respective current angles values between the ideal line of sight and the current lines of sight of the image acquisition unit; storing the respective current angles values and the apparent size of the head in a storage unit; and using the apparent size of the head stored in the storage unit at which an absolute sum of a difference between the respective current angle values and 0° was minimal to be an actual size of the head. 16. The method according to claim 15, which further comprises using a 3D camera as the image acquisition unit, the 3D camera operating according to a method selected from the group consisting of a stereoscopic method, a pencil of light method, and a time of flight method. 17. The method according to claim 15, which further comprises basing the defined position of the image acquisition unit on a center of a lens aperture of the image acquisition unit. 18. The method according to claim 17, which further comprises using a stereo camera as the image acquisition unit and basing the defined position on a center of a left lens aperture of the stereo camera. 19. The method according to claim 15, which further comprises recording continuously, via the image acquisition unit, images of a relevant scenario, at least 25 images per second. 20. The method according to claim 15, which further comprises dimensioning a size of the storage unit such that at least all measured values of a slow head movement from a first head position to a second head position can be stored. 21. The method according to claim 15, which further comprises using a ring buffer store as the storage unit, the ring buffer store being first filled and from then on an oldest value is always replaced by a current value. 22. The method according to claim 15, which further comprises filtering recordings of a head movement by filters and/or movement models. 23. The method according to claim 15, which further comprises combining different views of the occupant for forming a 3D overall view of the occupant. 24. The method according to claim 23, which further comprises: simulating a front of the occupant for the 3D overall view; and calculating a distance between the automatic dynamic disabling zone or the airbag module and the front of the occupant. 25. The method according to claim 15, which further comprises recording continuously, via the image acquisition unit, images of a relevant scenario, at least 30 images per second. 26. The method according to claim 15, which further comprises recording continuously, via the image acquisition unit, images of a relevant scenario, at least 35 images per second. 27. The method according to claim 24, which further comprises simulating a facial profile of the occupant. 28. A method for determining a current position of a body part of an occupant in a passenger compartment of a motor vehicle, the body part moving toward an automatic dynamic disabling zone in front of an airbag module, which comprises the steps of: providing an image acquisition unit having an ideal line of sight being substantially perpendicular to an ideal direction of movement of the occupant; recording an image scenario in the passenger compartment of the motor vehicle containing the occupant at least cyclically with the image acquisition unit and image information relating to the occupant being detected; determining both a position of a geometric center of the body part and an apparent size of the body part in the ideal direction of movement in a respective current scenario image; defining current lines of sight of the image acquisition unit as a vector, from a defined position of the image acquisition unit to a respective current position of the geometric center of the body part; calculating respective current angles values between the ideal line of sight and the current lines of sight of the image acquisition unit; storing the respective current angles values and the apparent size of the body part in a storage unit; using the apparent size of the body part stored in the storage unit at which an absolute sum of a difference between the respective current angle values and 0° was minimal to be an actual size of the body part. 29. The method according to claim 28, which further comprises determining a size of a torso as the body part. 30. A method for determining a current position of a head of an occupant in a passenger compartment of a motor vehicle, the head moving toward an automatic dynamic disabling zone in front of an airbag module, which comprises the steps of: providing an image acquisition unit having an ideal line of sight being substantially perpendicular to an ideal direction of movement of the occupant; recording an image scenario in the passenger compartment of the motor vehicle containing the occupant at least cyclically with the image acquisition unit and image information relating to the occupant being detected; determining both a position of a geometric center of the head and an apparent size of the head in a ideal direction of movement in a respective current scenario image; defining current lines of sight of the image acquisition unit as a vector, from a defined position of the image acquisition unit to a respective current position of the geometric center of the head; calculating respective current angles between the ideal direction of movement of the head and the current lines of sight of the image acquisition unit; storing the respective current values for angles and the apparent size of the head in a storage unit; and using the apparent size of the head stored in the storage unit at which an absolute sum of a difference between the respective current angle values and 90° was minimal to be an actual size of the head. 31. The method according to claim 30, which further comprises using a 3D camera as the image acquisition unit, the 3D camera operating according to a method selected from the group consisting of a stereoscopic method, a pencil of light method, and a time of flight method. 32. The method according to claim 30, which further comprises basing the defined position of the image acquisition unit on a center of a lens aperture of the image acquisition unit. 33. The method according to claim 32, which further comprises using a stereo camera as the image acquisition unit and basing the defined position on a center of a left lens aperture of the stereo camera. 34. The method according to claim 30, which further comprises recording continuously, via the image acquisition unit, images of a relevant scenario, at least 25 images per second. 35. The method according to claim 30, which further comprises dimensioning a size of the storage unit such that at least all measured values of a slow head movement from a first head position to a second head position can be stored. 36. The method according to claim 30, which further comprises using a ring buffer store as the storage unit, the ring buffer store being first filled and from then on an oldest value is always replaced by a current value. 37. The method according to claim 30, which further comprises filtering recordings of a head movement by filters and/or movement models. 38. The method according to claim 30, which further comprises combining different views of the occupant for forming a 3D overall view of the occupant. 39. The method according to claim 38, which further comprises: simulating a front of the occupant for the 3D overall view; and calculating a distance between the automatic dynamic disabling zone or the airbag module and the front of the occupant. 40. The method according to claim 30, which further comprises recording continuously, via the image acquisition unit, images of a relevant scenario, at least 30 images per second. 41. The method according to claim 30, which further comprises recording continuously, via the image acquisition unit, images of a relevant scenario, at least 35 images per second. 42. The method according to claim 39, which further comprises simulating a facial profile of the occupant. 43. A method for determining a current position of a head of an occupant in a passenger compartment of a motor vehicle, the head moving toward an automatic dynamic disabling zone in front of an airbag module, which comprises the steps of: providing an image acquisition unit having an ideal line of sight being substantially perpendicular to an ideal direction of movement of the occupant; recording an image scenario in the passenger compartment of the motor vehicle containing the occupant at least cyclically with the image acquisition unit and image information relating to the occupant being detected; determining both a position of a geometric center of the head and an apparent size of the head in a ideal direction of movement in a respective current scenario image; defining current lines of sight of the image acquisition unit as a vector, from a defined position of the image acquisition unit to a respective current position of the geometric center of the head; calculating respective current angles between current actual movement vectors of the head and the current lines of sight of the image acquisition unit; storing the respective current values for angles and the apparent size of the head in a storage unit; and using the apparent size of the head stored in the storage unit at which an absolute sum of a difference between the respective current angle values and 90° was minimal to be an actual size of the head. 44. The method according to claim 43, which further comprises: storing a respective last value for the position of the geometric center of the head; and calculating a respective current movement vector from the stored last and current 3-dimensional positions of the head. 45. A device for determining a current position of a head of an occupant in a passenger compartment of a motor vehicle, the head moving toward an automatic dynamic disabling zone in front of an airbag module, the device comprising: an image acquisition unit having an ideal line of sight being substantially perpendicular to an ideal direction of movement of the occupant, said image acquisition unit programmed to: record an image scenario in the passenger compartment of the motor vehicle containing the occupant at least cyclically with the image acquisition unit and image information relating to the occupant being detected; determine both a position of a geometric center of the head and an apparent size of the head in the ideal direction of movement in a respective current scenario image; define current lines of sight of the image acquisition unit as a vector, from a defined position of the image acquisition unit to a respective current position of the geometric center of the head; calculate respective current angles values between the ideal line of sight and the current lines of sight of the image acquisition unit; store the respective current angles values and the apparent size of the head in a storage unit; and use the apparent size of the head stored in the storage unit at which an absolute sum of a difference between the respective current angle values and 0° was minimal to be an actual size of the head. 46. A device for determining a current position of a head of an occupant in a passenger compartment of a motor vehicle, the head moving toward an automatic dynamic disabling zone in front of an airbag module, the device comprising: an image acquisition unit having an ideal line of sight being substantially perpendicular to an ideal direction of movement of the occupant, said image acquisition unit programmed to: record an image scenario in the passenger compartment of the motor vehicle containing the occupant at least cyclically with the image acquisition unit and image information relating to the occupant being detected; determine both a position of a geometric center of the head and an apparent size of the head in a ideal direction of movement in a respective current scenario image; define current lines of sight of the image acquisition unit as a vector, from a defined position of the image acquisition unit to a respective current position of the geometric center of the head; calculate respective current angles between the ideal direction of movement of the head and the current lines of sight of the image acquisition unit; store the respective current values for angles and the apparent size of the head in a storage unit; and use the apparent size of the head stored in the storage unit at which an absolute sum of a difference between the respective current angle values and 90° was minimal to be an actual size of the head.
The present invention relates to a method for determining the current position (A, B, C, D . . . ) of a head of an occupant in the passenger compartment of a motor vehicle, said head moving toward a dynamic disabling zone in front of an air bag module. Future restraint systems in motor vehicles will have to take into account the current position of the heads of vehicle occupants, in order to achieve the optimum protective effect during airbag activation. These developments are also driven by legislative initiatives, for example in the US by legislative initiative FMVSS 208. A important element of such legislation is the automatic dynamic disabling zone in front of the airbag module (hereafter referred to as the critical out of position zone or COOP. The limit of this zone is typically located at a distance of around 10 cm from the airbag module toward the occupant. If during an accident (e.g. as a result of total brake application) the head of the vehicle occupant is thrown toward the airbag module, the legislation requires the airbag to be disabled before the head or torso enters the COOP zone. A critical factor here is the distance from the part of the head (generally the face) or torso (generally the chest) facing the airbag to the airbag module. An important criterion for optimizing this function is the size of the so-called switch zone. On the one hand the airbag must be deactivated before the head enters the COOP zone but on the other hand the occupant must not be denied any protection potential at an adequate distance from the airbag. The switch zone should therefore be as small as possible. The size of the switch zone is typically around a few centimeters. Contactless systems and primarily optical systems have been developed to measure the distance of the head of the occupant from the airbag module. These optical systems are preferably 3D cameras, which operate according to the stereoscopic method, the pencil of light method or TOF (time of flight). Such image acquisition units are typically integrated up in the roof module between the vehicle seats (see FIGS. 1 and 2 below). The advantage of this integration position is that under normal circumstances the camera cannot easily be covered, e.g. by occupants reading newspapers. One disadvantage is however that when the head enters the COOP zone, the camera cannot see the part of the head facing the airbag module, i.e. generally the face. In this instance the image acquisition unit is looking at the back of the occupant's head. It is known that this problem can be resolved by assuming a mean head size. However this assumption is subject to not insignificant error in the case of bouffant hairstyles, head coverings, etc. The assumption no longer applies in such cases. The switch zone must therefore be big enough to cover most scenarios given this uncertainty. FIG. 3 illustrates this situation. In head position A (seated normally) the camera sees the face of the occupant but not the hair. In head position B (face at limit of COOP zone) the camera looks at the back of the occupant's head and sees the hair but no longer the face of the occupant. FIG. 4 shows that if a mean head size is assumed, even a slightly bouffant hairstyle can result in the camera determining a position outside the COOP even though the head has already entered the COOP. The object of the invention is to specify an improved method, which avoids the above disadvantages, and a device for the exact determination of the position of the heads of vehicle occupants. In particular the invention should allow the smallest possible switch zone to be achieved, so as not to deny the occupant any protection potential at an adequate distance from the airbag module. This object is achieved by the independent claims. Advantageous embodiments and developments, which can be deployed individually or in combination with each other, are set out in the dependent claims. A first method according to the invention for determining the exact position (A, B, C, D . . . ) of a head of an occupant in the passenger compartment of a motor vehicle, said head moving toward an automatic dynamic disabling zone in front of an airbag module, using an image acquisition unit with an ideal line of sight, which is essentially perpendicular to the ideal direction of movement of the occupant, is characterized in that the image acquisition unit is used at least cyclically to record an image scenario including the occupant, i.e. an image area including the occupant, in the passenger compartment of the motor vehicle and to detect image information relating to the occupant; in the respective current scenario image both the position of the geometric center of the head and the apparent size of the head are determined, in particular measured in the direction of movement; the respective current lines of sight of the image acquisition unit are defined as a vector from a defined position of the image acquisition unit to the respective current position of the geometric center of the head; the respective current angle α between the ideal line of sight and the current lines of sight of the image acquisition unit are calculated; the respective current values for angle α and apparent size of the head are stored in a storage unit; and the value from the storage unit for which the absolute sum of the difference between angle α and 0° was minimal is always assumed to be the size of the head. Contrary to the prior art therefore instead of a mean head size, an apparent and therefore ultimately real head size is determined. Then during the for example parallel position calculations the head sizes, which are closest to the actual head size and in the best instance may even correspond to it, are selected from the set of head sizes thus determined and used as the basis for calculation. Using a head size based on reality for determination of the current position in front of the airbag module advantageously gives a much more exact position determination than is possible with the prior art and therefore allows a significantly smaller switch zone to be achieved, thereby increasing the protection potential for the occupant of the vehicle. The present invention also relates to a method for determining the exact position (A, B, C, D . . . ) of a head of an occupant in the passenger compartment of a motor vehicle, said head moving toward an automatic dynamic disabling zone in front of an airbag module, using an image acquisition unit with an ideal line of sight, which is essentially perpendicular to the ideal direction of movement of the occupant, the image acquisition unit being used at least cyclically to record an image scenario including the occupant, i.e. an image area including the occupant, in the passenger compartment of the motor vehicle and to detect image information relating to the occupant; both the position of the geometric center of the head and the apparent size of the head being measured in the direction of movement in the respective current scenario image; the respective current lines of sight of the image acquisition unit being defined as a vector, from a defined position of the image acquisition unit to the respective current position of the geometric center of the head; the respective current angles β between the direction of movement of the head and the current lines of sight of the image acquisition unit being calculated; the respective current values for angle β and the apparent size of the head being stored in a storage unit; and the value from the storage unit for which the absolute sum of the difference between angle β and 90° was minimal being assumed to be the size of the head. This method also has the advantages mentioned above. In a preferred embodiment of the invention the image acquisition unit is a 3D camera, which operates according to the stereoscopic method, the pencil of light method, the time of flight method or another equally appropriate method. Use of a 3D camera, in particular in respect of the last mentioned method according to the invention, advantageously allows determination of the current position independently of ideal movement directions and/or lines of sight based on actual movement vectors in three-dimensional space. Instead of carrying out a position determination based on an ideal direction of movement, it is therefore preferably proposed according to the invention that the respective current angle β is calculated between a current actual movement vector of the head and the current line of sight vector of the image acquisition unit. This advantageously enhances the reliability of the method according to the invention even when an occupant is sitting with a lateral orientation, as for example occurs normally when looking out of a side window, etc. Because the respective last or previous value for the position of the geometric center of the head is preferably stored, the respective current movement vector can advantageously be calculated in a simple manner from the stored last and the current 3-dimensional positions of the head. According to the invention the defined position of the image acquisition unit is preferably based on the center of a lens aperture of the image acquisition unit, in the case of the stereo camera for example the left lens. In a further preferred embodiment of the invention, the image acquisition unit records images of the relevant scene continuously, at least 25 images per second, in particular at least 30 images per second, preferably at least 35 images per second, so that film speeds, i.e. online viewing, can actually advantageously be achieved. The size of the storage unit is such that at least all the measured values of a slow head movement from a first head position (A), i.e. an initial position, to the relevant second head position (B), namely the position with the face at the limit of the COOP area, can be stored. In one expedient embodiment of the invention the storage unit is a ring buffer store, which is first filled and from then on the oldest value is replaced by the current value. It has also proven advantageous for the recordings of the head movement to be filtered using filters such as Kalman filters and/or movement models. It should be noted specifically that instead of determining the head position, with the image acquisition unit any other appropriate part of the body of an occupant can be used as the basis for calculating the position of said occupant, such as in particular the size of the torso of the occupant in the motor vehicle. In a further preferred embodiment of the invention it is proposed that different views of the occupant be combined to provide a 3D overall view of the person. This advantageously allows simulation for example of the front or facial profile of the occupant in front of the plane of the COOP limit from the overall view and therefore more accurate calculation of its distance from the disabling zone or the airbag module than with the prior art. For the sake of completeness, it should be pointed out that the invention also of course relates to a device corresponding to the method for determining the current position (A, B, C, D . . . ) of a head of an occupant in the passenger compartment of a motor vehicle, said head moving toward an automatic dynamic disabling zone in front of an air bag module, said device being characterized by appropriate means for carrying out the method as described above. Particular problems relating to the legislative initiative FMVSS 208 mentioned above are known to be posed by the validatability and reproducibility of the head position measurements in the context of the licensing procedure for a camera system. By improving the head position determination even by a matter of centimeters, the present invention can offer crucial advantages both here and in the field. By advantageously enhancing the protection potential of an occupant in a motor vehicle thus, the present invention is in particular suitable for occupant protection systems in modern motor vehicles. The invention is described below with reference to different exemplary embodiments and in conjunction with the drawing, in which: FIG. 1 shows a schematic diagram of a top view of a typical integration location for an image acquisition unit in the passenger compartment of a motor vehicle; FIG. 2 shows a schematic diagram of a side view of the integration location according to FIG. 1; FIG. 3 shows a schematic diagram of the measurement of the head positions of an occupant assuming mean head sizes; FIG. 4 shows a schematic diagram of the incorrect measurement based on the assumption according to FIG. 3 of the head positions of an occupant with a bouffant hairstyle for example; FIG. 5 shows a schematic diagram of a first exemplary embodiment of the measurement of head positions according to the invention; and FIG. 6 shows a schematic diagram of a second exemplary embodiment of the measurement of head positions according to the invention. FIG. 1 shows a top view of the typical integration location of an image acquisition unit 16 in the passenger compartment 2 of a motor vehicle 1. FIG. 2 shows a side view of the diagram in FIG. 1. An image acquisition unit 16, for example a 3D camera, is generally integrated in a module up in the roof liner 20 between the vehicle seats 3. An airbag module 5 is housed in front of the seats 3, typically in the dashboard 4. An automatic dynamic COOP disabling zone 6 in front of the airbag 5 serves for the statutorily required protection of an occupant 8 from injury by the airbag 5, if a minimum distance therefrom is not observed. The advantage of the integration location 20 described above for the camera 16 is that under normal circumstances it cannot easily be covered, for example by occupants 8 reading newspapers. It is however a disadvantage that when the head 9 enters the COOP zone 6, the camera 16 cannot see the part of the head 9 facing the airbag module 5, generally the face 12. In this instance the camera 16 is looking at the back of the head of the occupant 9. It is known that this problem can be resolved by assuming a mean head size. This assumption is however subject to not insignificant error in the case of bouffant hairstyles, head coverings, etc. The assumption no longer applies in such cases. A switch zone 7 in front of the COOP zone must therefore be big enough to cover most scenarios given this uncertainty. FIG. 3 illustrates this situation, i.e. the measurement of head positions of an occupant 8 assuming mean head sizes. In head position A (seated normally) the camera 16 sees the face 12 of the occupant but not the hair. In head position B (face at limit of COOP zone) the camera 16 looks at the back of the head of the occupant 8 and sees the hair but no longer the face 12 of the occupant 8. FIG. 4 shows the incorrect measurement based on the assumption according to FIG. 3. If a mean head size is assumed, even a slightly bouffant hairstyle can result in the head 9 entering the COOP zone 6 but the camera still determining a position outside the COOP zone 6. FIG. 5 shows a first exemplary embodiment of the measurement of head positions according to the invention in principle. To this end the size 11 of the head 9 of the occupant 8 is determined or measured as accurately as possible, particularly at head position C. The invention hereby utilizes the idea that the best position for a measurement with regard thereto is the point in space, at which the ideal direction of movement 14 of the head 9 is perpendicular to an ideal line of sight 17 of the camera 16. The measurement is then preferably carried out when the geometric center 10 of the head 9 crosses this point. A method for determining the current size 11 of the head 9 for example implemented in an algorithm can for example be as follows: Known methods of image processing are used in the respective current 3D image to measure the position of the geometric center 10 of the head 9, as well as the apparent size 11 of the head 9 in the direction of movement 14. The current line of sight 18 of the camera 16 is defined as a vector, from a defined camera position 19, for example the center of the lens aperture, in the case of a stereo camera 16 for example the left lens, to the position of the geometric center 10 of the head 9. A current angle α between the ideal line of sight 17 and the current lines of sight 18 of the 3D camera 16 is then calculated according to known methods of linear algebra. Alternatively or even cumulatively as a plausibility check for example, a current angle β can be calculated between the ideal direction of movement 14 of the head 9 and the current lines of sight 18 of the image acquisition unit 16. The respective current values for angles α and β and apparent head size 11 are then stored, preferably in a ring buffer store (not shown), in which the oldest value is always replaced by the current value. The size of the ring buffer store is preferably dimensioned such that at least all the measured values of a slow head movement 14 from head position A to head position B can be stored. The value from the current ring buffer store for which the absolute sum of the difference between angle α and 0° or angle β and 90° was minimal is always assumed to be the size of the head. FIG. 6 shows a second exemplary embodiment of a preferred measurement of head positions according to the invention. First known image processing methods are used in the respective current 3D image to measure the position of the geometric center 10 of the head 9, as well as the apparent size 11 of the head 9 in the direction of movement 14. The current line of sight 18 of the camera 16 is also defined as a vector, from a defined camera position 19, for example the center of the lens aperture, in the case of a stereo camera 16 for example the left lens, to the position of the geometric center 10 of the head 9. Unlike in FIG. 5, the respective last, i.e. previous, values are now stored for the position 10, so that an actual movement vector 15 of the head 9 can be calculated from the stored last and current 3-dimensional head position 10. The current angle β between the actual movement vector 15 of the head 9 and the current lines of sight 18 of the 3D camera 16 are then calculated according to known methods of linear algebra. The respective current values for angle β and apparent head size 11 are then stored, again preferably in a ring buffer store (not shown), in which the oldest value is always replaced by the current value. The value from the current ring buffer store for which the absolute sum of the difference between angle β and 90° was minimal, i.e. the geometry was closest to the “perpendicular” condition, is always assumed to be the size of the head. It should be noted that the methods described above can be stabilized further by further measures. For example the head movement 14 or 15 can be filtered using known filters and movement models (Kalman filters). The above methods can also advantageously be applied correspondingly to the determination of the distance of the torso 13 of the occupant from the airbag module 5. The size of the torso 13 of the occupant 8 is then detected using the 3D camera instead of the size 11 of the head 9. The above methods can be developed still further by combining the different views of the person 8, which result from the different positions A, B, C, . . . of the person 8 in relation to the camera 16, to form a three-dimensional overall view of the person 8, e.g. front view A with person sitting normally plus side view C with person 8 next to camera 16 plus rear view B with person 8 bending. All partial views A, B, C, D, . . . , recorded during the forward movement of the person 8 by the 3D camera 16 and buffered in the ring buffer store, can also be used for the combination of partial views A, B, C, . . . of the person 8. When the person 8 is close to the COOP zone 6, practically only the rear of the person is visible to the 3D camera 16. The non-visible front 12 of the person 8 can now be simulated from the overall view determined above and the distance from the airbag module 5 can be calculated more accurately. The present invention advantageously enhances the protection potential of an occupant 8 in a motor vehicle 1. It is therefore suitable in particular for occupant protection systems in modern motor vehicles 1.
20050420
20070605
20060202
71196.0
G01C1136
0
RATCLIFFE, LUKE D
METHOD FOR DETERMINING THE CURRENT POSITION OF THE HEADS OF VEHICLE OCCUPANTS
UNDISCOUNTED
0
ACCEPTED
G01C
2,005
10,532,242
ACCEPTED
Method for checking the quality of the data transmission between a read/write device (slg) and at least one mobile data store (mds) and read/write device (slg) and mobile data store for application in the method
A method and associated apparatus for checking the data transmission between at least one read/write device (SLG) and at least one mobile data memory (MDS), in particular in an identification system having at least one mobile data memory (MDS) which is fitted to objects, for recording object-related status and/or process data, for example in a system for dispatching, transporting and/or manufacturing the individual objects. The read/write device (SLG) and/or the mobile data store (MDS) have at least one register region for input of data information concerning the quality of the data transmission between the read/write device (SLG) and the mobile data store (MDS). This register region is read by at least one external computer application station (4), for checking the quality of the data transmission between the read/write device (SLG) and the mobile data store (MDS).
1. A method for checking data transmission between at least one read/write device (SLG) and at least one mobile data memory (MDS), wherein at least one of the read/write device (SLG) and the mobile data memory (MDS) has at least one register area for entering data information relating to the quality of data transmission between the read/write device (SLG) and the mobile data memory (MDS), and wherein this register area is read by at least one external computer user station (4) for checking the quality of data transmission between the read/write device (SLG) and the mobile data memory (MDS). 2. The method as claimed in claim 1, wherein the external computer user station (4) is connected to the read/write device (SLG) for transmitting data. 3. The method as claimed in claim 2, wherein the external computer user station (4) is connected to the read/write device (SLG) via a connection module (2). 4. The method as claimed in claim 3, wherein the external computer user station (4) is connected to the read/write device (SLG) via a controller (3). 5. A read/write device (SLG) configured for using a method for checking the quality of data transmission between the read/write device (SLG) and at least one mobile data memory (MDS), as claimed in claim 1, comprising at least one register area for entering data information relating to the quality of data transmission. 6. The read/write device (SLG) as claimed in claim 5, wherein the register area is associated with at least one corresponding register area in at least one mobile data memory (MDS) for interchanging data. 7. A mobile data memory (MDS) configured for using a method for checking the quality of data transmission between at least one read/write device (SLG) and the mobile data memory (MDS), as claimed in claim 1, comprising at least one register area for entering data information relating to the quality of data transmission. 8. The mobile data memory (MDS) as claimed in claim 7, wherein the register area is associated with at least one corresponding register area in at least one read/write device (SLG) for interchanging data. 9. An identification system comprising: at least one mobile data memory that is fitted to an object; and at least one read/write device that detects at least one of object-related state data and object-related process data; wherein at least one of the read/write device and the mobile data memory has at least one register area for entering data information relating to the quality of data transmission between the read/write device and the mobile data memory; and wherein the register area is configured to be read by at least one external computer user station checking the quality of data transmission between the read/write device and the mobile data memory. 10. The identification system as claimed in claim 9, provided in at least one of a system for dispatching, transporting and manufacturing individual objects.
Method for checking the quality of data transmission between a read/write device (SLG) and at least one mobile data memory (MDS), and read/write device (SLG) and mobile data memory (MDS) for using the method The invention relates to a method for checking data transmission between at least one read/write device (SLG) and at least one mobile data memory (MDS), in particular in an identification system having at least one mobile data memory (MDS) which is fitted to objects and is intended to detect object-related state and/or process data, for example in a system for dispatching, transporting and/or manufacturing the individual objects. The invention also relates to a read/write device (SLG) and to a mobile data memory (MDS) for using the method. High-speed data transmissions between read/write devices (SLG) and mobile data memories (MDS) are known as the prior art in industrial non-contacting identification technology. The respective PTT radio regulations must be complied with as regards the frequency, field strength, modulation bandwidth, interference emissions, interference influences etc. of the air interfaces which occur in this case. When there are additional electromagnetic sources, data transmission between the read/write devices (SLG) and the mobile data memories (MDS) may be subject to interference in the air interface. The data transmission reliability is also influenced and possibly impaired by location-related conditions and environment data, for example the distance between the read/write device (SLG) and the mobile data memory (MDS), the travel speed of the mobile data memory (MDS), the ambient temperature etc. The invention is based on the object of providing a method for checking the quality of data transmission between at least one read/write device (SLG) and at least one mobile data memory (MDS). A further aim is to provide a read/write device (SLG) and a mobile data memory (MDS) for using the method. In the inventive method for checking data transmission between at least one read/write device (SLG) and at least one mobile data memory (MDS), at least one register area for entering data information relating to the quality of data transmission between the read/write device (SLG) and the mobile data memory (MDS) is provided in the read/write device (SLG) and/or in the mobile data memory (MDS). This register area is read and/or evaluated by at least one external computer user station for the purpose of checking the quality of data transmission between the read/write device (SLG) and the mobile data memory (MDS). This computer user station can be used to remotely diagnose data transmission between the read/write device (SLG) and mobile data memories (MDS) in a specific manner, and it is possible to identify and eliminate data transmission problems which occur, in particular, during commissioning of a data transmission system such as this but also when using the system in the field. The inventive method can be used to detect the quality of the air interfaces when transmitting data between the read/write device (SLG) and the mobile data memory (MDS) and to assess and evaluate said quality in the external computer user station. All communication faults or impairments such as to communication can also be detected and eliminated. According to one advantageous method variant, the external computer user station can be connected to at least one read/write device (SLG) for the purpose of transmitting data. This makes it possible to read the respective register areas in the read/write device (SLG) which relate to the quality of data transmission. The read/write device (SLG) in turn communicates with the mobile data memory (MDS) and can read the appropriate register areas which relate to the quality of data transmission and can store them in its own register areas in order to be read by the external computer user station. In accordance with another advantageous method variant, the external computer user station is connected to the read/write device (SLG) via a connection module. In a connection module such as this, data can be transmitted between the read/write device (SLG) and the external computer user station in accordance with a protocol. A connection module such as this makes it possible to transmit data, which has been transmitted, for example, from the read/write device (SLG) to the external computer user station, only after blocks have been formed, packets have been formed and protocol conformity has been checked. A connection module such as this makes it possible to transmit data between the read/write device (SLG) and the external computer user station in a more reliable and more rapid manner. In accordance with another advantageous method variant, the external computer user station can be connected to the read/write device (SLG) via a controller, for example for controlling a dispatch, transport and/or manufacturing system. In this case, the controller is used to control the processes in the respective industrial system being operated and instigates and monitors planned operation of systems such as these. When the external computer user station is connected to the read/write device (SLG) via a controller such as this, it is also possible, in addition to the items of data which are to be read from the read/write device (SLG), to read items of control data and to associate them with one another and jointly evaluate them in the external computer user station. This makes it possible to also take into account, in the external computer user station, the respective process states of the controlled industrial system when evaluating the data (relating to the quality of data transmission between the read/write device (SLG) and mobile data memories (MDS)) received from the read/write device (SLG). The inventive read/write device (SLG) has at least one register area for entering data information relating to the quality of data transmission to the mobile data memories (MDS). In addition to storing the object-related state and/or process data detected between the read/write device (SLG) and the mobile data memory (MDS), this at least one further register area also makes it possible to store data relating to the quality of data transmission, and to store the latter in order to be read by the external computer user station. The inventive read/write device (SLG) is thus also suited to remote diagnosis using an external computer user station. In one advantageous embodiment of the read/write device (SLG), the register area for entering the data information relating to the quality of data transmission is associated with a further register area in at least one mobile data memory (MDS), this further register area likewise being provided for entering data information relating to the quality of data transmission. Associating register areas such as these between the read/write device (SLG) and the mobile data memory (MDS) makes it possible for data and protocol formats to be appropriately matched to one another and for items of information which refer to one another to also be stored in corresponding register areas. This makes it easier to read the data information relating to the quality of data transmission from the respective register areas. The inventive mobile data memory (MDS) advantageously likewise has at least one register area for entering data information relating to the quality of data transmission. This likewise facilitates communication with the read/write device (SLG), as described above. The invention is explained in more detail using exemplary embodiments in the figures of the drawing, in which: FIG. 1 shows a schematic illustration of one possible connection of the mobile data memory (MDS) and the read/write device (SLG) to an external computer user station, FIG. 2 shows a specific illustration of register areas in a read/write device (SLG), and FIG. 3 shows a specific illustration of register areas in a mobile data memory (MDS). FIG. 1 shows a read/write device (SLG) and a mobile data memory (MDS) in a dispatch, transport and/or manufacturing system (which is known per se but is not shown in any more detail) for detecting object-related state and/or process data of the respective system. In this case, the read/write device (SLG) is stationary, and data is transmitted between the read/write device (SLG) and the respective mobile data memories (MDS) via an air interface 1. A read/write device (SLG) usually communicates with a plurality of mobile data memories (MDS) (not shown in any more detail). The read/write device (SLG) is connected to an external computer user station (for example a personal computer) via a connection module 2 and a controller 3, to be precise via a network (for example TCP/IP, WLAN etc.) that is known per se. The data transmitted in the network may be transmitted in accordance with various network protocols (for example ProfiBus, CAN, EtherNet etc.) which are known per se. According to the invention, the read/write device (SLG) has additional register areas F, G, H, I and J for entering data information relating to the quality of data transmission with the mobile data memory (MDS). The read/write device (SLG) also has register areas (known per se) for recording and storing the object-related state and/or process data (not shown in any more detail) which has been transmitted. Additional register areas A, B, C, D and E which are likewise used to enter data information relating to the quality of data transmission with the read/write device (SLG) are likewise provided in the mobile data memory (MDS). The computer user station 4 can now use the controller 3 and the connection module 2 to read the register areas F-J in the read/write device (SLG) and to detect the data information which relates to the quality of data transmission and is stored in said read/write device and also to eliminate data transmission errors in the event of disturbances occurring. FIGS. 2 and 3 show, by way of example, data information relating to the quality of data transmission. The data information relating to the period of time for which there was no mobile data memory (MDS) in the existing data transmission field can be stored in the register area F in the read/write device (SLG). The duration of communication with the mobile data memory (MDS) can be stored in the register area G. The register area H can record the number of collisions during multiple day operation with a plurality of mobile data memories (MDS). The number of message repetitions to the mobile data memory (MDS) can be recorded in the register I, and the number of disturbances while the mobile data memory (MDS) is receiving data can be recorded in the register area J. The register areas F-J in the read/write device (SLG) thus comprise data information relating to the quality of data transmission between the read/write device (SLG) and the mobile data memory (MDS), which data information can be read and evaluated by the external computer user station 4. This means that, when reading the register area A, for example, it is possible to establish, from the determination of a large number of collisions during operation with a plurality of mobile data memories (MDS), that the read/write device (SLG) may communicate only with a relatively small number of mobile data memories (MDS) in order to eliminate the communication disturbance. As shown in FIG. 3, in addition to register areas (which are known per se but are not shown in any more detail) for recording and storing the object-related state and/or process data that has been transmitted, the mobile data memory (MDS) has, according to the invention, register areas A-E, with the period for which the mobile data memory (MDS) is present in the data field, for example, being recorded in the register area A. The magnitude of the supply voltage of the mobile data memory (MDS) may be ascertained directly, and the field strength of the field of the mobile data memory (MDS) and the range of the field of the mobile data memory (MDS) may thus be ascertained indirectly, in the register area B. The register area C may relate to the temperature of the mobile data memory chip (MDS), the register area D may relate to the number of message repetitions to the read/write device (SLG), and the register area E may relate to the number of disturbances when the read/write device (SLG) is receiving the data. The register areas A-E may be read by the external computer user station 4 using the read/write device (SLG). In this case, the register areas G and J in the read/write device (SLG) and in the mobile data memory (MDS) are associated with one another, by way of example, and respectively relate to the number of disturbances when the read/write device (SLG) and the mobile data memory (MDS), respectively, are receiving the data. It is possible to facilitate the analysis and elimination of disturbances in the external computer user station 4 by reading and evaluating associated register areas such as these.
20051116
20090414
20060608
82386.0
G06F300
0
AFSHAR, KAMRAN
METHOD FOR CHECKING THE QUALITY OF DATA TRANSMISSION BETWEEN A READ/WRITE DEVICE AND AT LEAST ONE MOBILE DATA MEMORY, AND READ/WRITE DEVICE AND MOBILE DATA MEMORY FOR USING THE METHOD
UNDISCOUNTED
0
ACCEPTED
G06F
2,005
10,532,341
ACCEPTED
Pharmaceutical compositions comprising flavonoids and menthol
The present invention relates to use of certain antiviral fragrances for reduction of viruses, in particular vira causing common cold. In one embodiment, the invention relates to pharmaceutical compositions comprising an antiviral fragrance, preferably menthol. Said compositions preferably also comprise one or more flavonoids. The invention also relates to treatment of common cold using said compositions.
1. A pharmaceutical composition comprising i) one or more purified flavonoids; and ii) purified menthol; and iii) pharmaceutically acceptable exipients. 2. The pharmaceutical composition according to claim 1, wherein said composition essentially consists of i) one or more purified flavonoids; and ii) purified menthol; and iii) pharmaceutically acceptable exipients, wherein said exipients are not therapeutically active. 3. The pharmaceutical composition according to claim 1, wherein said composition also comprises a pharmaceutically acceptable metal complex and/or metal salt. 4. The pharmaceutical composition according to claim 3, wherein said composition essentially consists of i) one or more purified flavonoids; and ii) purified menthol; and iii) one or more metal complexes and/or metal salts; and iv) pharmaceutically acceptable expients, wherein said expients are not therapeutically active. 5. The pharmaceutical composition according to claims 3, wherein said metal is zinc. 6. The pharmaceutical composition according to claims 3, wherein the metal is zinc selected from the group consisting of Zn2+ aminochelates , Zn2+ amino acid chelates, Zn(acetate)2, Zn2+ DL-methionine, Zn2+ L-methionine, ZnGluconate and PolaPreZinc®. 7. The pharmaceutical composition according to claim 1, wherein said composition is useful for oral and/or nasal administration. 8. The pharmaceutical composition according to claim 1, wherein said composition is selected from the group consisting of lozenges, troches, capsules, syrups, tablets, lollipops, solutions, dispersions, suspensions, powders, micropheres, chewing tablets, chewing gums, sprays, droppers, pipettes and pills. 9. The pharmaceutical composition according to claim 1, wherein said composition is a slow-release composition. 10. The pharmaceutical composition according to claim 1, wherein said composition is lozenges. 11. The pharmaceutical composition according to claim 1, wherein said composition is essentially free of crude plant extracts. 12. The pharmaceutical composition according to claim 1, wherein said composition is essentially free of other terpenes than menthol. 13. The pharmaceutical composition according to claim 1, wherein said composition is essentially free of one or more selected from the group consisting of menthone, menthyl acetate, limonene and neomenthol. 14. The pharmaceutical composition according to claim 1, wherein one or more flavonoids are chelating a metal. 15. The pharmaceutical composition according to claim 1, wherein the metal is Zn2+. 16. The pharmaceutical composition according to claim 1, wherein the flavonoid is selected from the group consisting of flavonoids of the general formula: and the general formula: Wherein R2′ can be selected from: —H —OH R3′ can be selected from: —H —OH —OCH3 —OCH2CH2OH R4′ can be selected from: —H —OH —OCH3 —OCH2CH2OH R5′ can be selected from: —H —OH —OCH3 —OCH2CH2OH R6′ is —H; R3 including R31 and R32 can individually be selected from: —H —OH —O-rutinose —O-glucoside —O-glucose-p-coumaric acid —SOH —O-rhamnose R4 can be selected from: —(O) —OH R5 can be selected from: —H —OH —O—CH2CH2OH R6 can be selected from: —H —OH —OCH3 R7 can be selected from: —H —OH —O-glucose —OCH3 —OCH2CH2OH —O-glucuronic acid —O-rutinose —O-rhamnoglucoside R8 can be selected from: —H —OH 17. The pharmaceutical composition according to claim 1, wherein the flavonoid is selected from the group consisting of troxerutin, venoruton, hesperitin, naringenin, nobiletin, tangeritin, baicalein, galangin, genistein, quercetin, apigenin, kaempferol, fisetin, rutin, luteolin, chrysin, taxifolin, eriodyctol, catecithin, epicatechin gallate, epigallocatechin gallate, flavone, sideritoflavone, hypolaetin-8-O-Gl, oroxindin, 3-hydroxyflavone, morin, quercetagetin-7-O-Gl, tambuletin, gossypin, hipifolin, naringin, leucocyanidol, amentoflavone and derivatives thereof and mixtures thereof. 18. The pharmaceutical composition according to claim 1, wherein said flavonoid is not a naturally occurring flavonoid. 19. The pharmaceutical composition according to claim 1, wherein said flavonoid is a rutoside. 20. The pharmaceutical composition according to claim 1, wherein at least one flavonoid is a rutoside aglycone. 21. The pharmaceutical composition according to claim 1, wherein said flavonoid is a hydroxyethylrutoside. 22. The pharmaceutical composition according to claim 1, wherein at least one flavonoid is a hydroxyethythyrutoside aglycone. 23. The pharmaceutical composition according to claim 1, wherein said composition comprises a mixture of hydroxyethylrutosides. 24. The pharmaceutical composition according to claim 1, wherein said composition comprises a mixture of mono-, di-, tri- and tetrahydroxyethylrutosides. 25. The pharmaceutical composition according to claim 1, wherein at least one flavonoid is troxerutin. 26. The pharmaceutical composition according to claim 1, where at least one flavonoid is troxerutin aglycone. 27. The pharmaceutical composition according to claim 1, wherein the flavonoid is veneruton. 28-57. (canceled) 58. A method of treatment of a clinical condition or symptoms of a clinical condition in an individual in need thereof, comprising administering to said individual the pharmaceutical composition according to claims 1. 59. The method according to claim 58, wherein said clinical condition is a condition relating to common cold. 60. The method according to claim 58, wherein the clinical condition is common cold of the upper and/or lower respiratory tract and/or eyes. 61. The method according to claim 59, wherein the conditions relating to common cold are viral infections of the upper and/or lower respiratory tract and/or eyes. 62. The method according to claim 59, wherein the conditions relating to common cold are bacterial infections of the upper and/or lower respiratory tract and/or eyes. 63. The method according to claim 59, wherein the conditions relating to common cold are allergic conditions of the upper and/or lower respiratory tract and/or eyes. 64. The method according to claim 59, wherein the conditions relating to common cold are characterized by one or more symptoms of the group comprising coughing, sneezing, muscle pain, sore throat, irritated throat, hoarseness, headache, malaise, chilliness, fever, nasal discharge, nasal obstruction, pain relating to the sinuses, rhinitis, swelling of mucosal membranes, pharyngitis, asthma, and bronchitis. 65. The method according to claim 59, wherein the condition relating to common cold is a viral infection caused by or associated with one or more viruses selected from the group consisting of adenoviruses, parvoviruses, picornaviruses, reoviruses, orthomyxoviruses, paramyxoviruses, arenaviruses, caliciviruses, coronaviruses, orthomyxoviruses, rhinovirus, influenza virus, including influenza virus type A and B, echovirus and coxsackie virus. 66. The method according to claim 59, wherein the condition relating to common cold is a viral infection caused by or associated with one or more viruses selected from the group consisting of coronaviruses and rhinoviruses. 67. The method according to claim 59, wherein the condition relating to common cold is a bacterial infection caused by or associated with one or more bacteria selected from the group consisting of Streptococcus pheumoniae, Streptococcus Haemolyticae, Haemophilus influenxae, and Moraxella catarrhalis. 68. The method according to claim 59, wherein the condition relating to common cold is an allergic condition selected from the group consisting of rhinitis, acute and chronic bronchitis and hay fewer. 69. The method according to claim 59, wherein the condition related to common cold is an allergic condition characterised by one or more symptoms selected from the group consisting of nasal discharge, nasal congestion, sneezing, cough, swelling of mucosal membranes and rhinitis. 70. The method according to claim 58, wherein the administration is to the mucosal membrane of the upper and/or lower respiratory tract and/or of the eyes. 71. The method according to claim 58, wherein the administration is topical to the mucosal membrane of the oral cavity. 72-73. (canceled) 74. A method of reducing the amount of virus in a composition, comprising incubating said composition comprising virus with menthol. 75. The method according to claim 74, wherein said virus is rhinovirus. 76. A method of reducing the amount of virus in an individual infection with said virus, comprising administering to said individual a pharmaceutical composition comprising menthol, thereby reducing the amount of said virus in said individual. 77. The method according to claim 76, wherein said virus is rhinovirus. 78. The method according to claim 76, wherein the method further comprises administering at least one flavonoid to said individual. 79-80. (canceled) 81. The method according to claim 58, wherein said flavonoid is a hydroxyethylrutoside. 82. The method according to claim 58, wherein at least one flavonoid is troxerutin. 83. The method according to claim 58, wherein said composition also comprises a pharmaceutically acceptable metal complex and/or metal salt.
FIELD OF THE INVENTION The present invention relates to the field of pharmaceutical compositions comprising flavonoids. In particular, the invention relates to pharmceutical compositions comprising flavonoids and menthol. The invention furthermore relates to methods of treatment using said compositions, for example to methods of treating common cold or similar conditions. BACKGROUND OF THE INVENTION Common cold is in general initiated by viral infections by the so-called cold viruses, such as rhino virus, corona virus, adenovirus, coxsackie virus, RS-virus, echovirus or other cold viruses. In average all human beings suffer 2 to 3 times a year from infections in the upper respiratory passages, such as cold and flu. In general, in Denmark the majority of common colds occurring in September, October and November are caused by rhinovirus infection, whereas the majority of common cord occurring in January, February and March are caused by Coronavirus infections. In addition, allergic syndromes, for example asthma, may be initiated by common cold viruses, especially the rhinovirus. Recent observations from a polymerase chain reaction (PCR)-study (Johnston, 1993) with naturally rhinovirus infected persons indicates that the actual range for rhinovirus infections involved in common cold syndrome probably is at least twofold higher, compared to findings obtained via the traditional cell culture techniques (40%). This indicates that up to 70-75% of all patients suffering from common colds have a rhinovirus infections ongoing either as a single infection or co-infection (Spector, 1995). It has been estimated that the average pre-school child experiences 610 upper respiratory infections or common colds per year whereas the average adult experiences 24 (Sperber, 1989). The effects of the common cold can be uncommonly disruptive, forcing otherwise normal persons to stay away from work, school, etc. Individuals who are at increased risks, such as individuals suffering from bronchitis or asthma, may also experience a life-threatening exacerbation of their underlying conditions. The average annual expenditure for various cold treatments exceeds USD 2 billion in the United States, alone (Spector, 1995); in the EU a similar figure is expected. Unfortunately, research in development of novel strategies to treat common cold is complicated by the fact human rhinoviruses only have been reported to infect primates successfully and hence no practical animal model has been developed for rhinovirus infections (Rotbart, 2000). The development of natural and experimentally induced rhinovirus infections in normal persons are initiated by selected events, which can be considered to occur sequentially. The steps in the rhinovirus pathogenesis are believed to include viral entry into the outer nose, mucociliary transport of virus to the posterior pharynx, and initiation of infection in ciliated and non-ciliated epithelial cells of the upper airway. Viral replication peaks on average within 48 h of initiation of infection and persists for up to 3 weeks; Infection is followed by activation of several inflammatory mechanisms, which may include release or induction of interleukins, bradykinins, prostaglandins and possibly histamine, including stimulation of parasympathetic reflexes (the cytokines may counteract each other at certain levels resulting in a very complex pathway). The resultant clinical illness is a rhinosinusitis, pharyngitis, and bronchitis, which on average lasts one week (Gwaltney, 1995). Occasionally, a secondary bacterial or microbial infection may follow subsequently to the viral infection and a sustained and more serious inflammation may result. Previously, it was believed that the major part of the virus was produced in the upper nose region and excreted (Winther, 1993a). However, subsequent studies, comparing recovery of virus in nasopharyngeal wash specimens, nasal swabs and pharyngeal swabs showed that the nasopharyngeal wash specimens was consistently superior to the other two specimens in yielding virus (Cate, 1964). From a series of in-depth investigations (Winther, 1984a; Winther, 1984b; Winther, 1984c; Turner, 1984; Farr, 1984; Hayden, 1987; Winther, 1987a; Winther, 1987b; Winther, 1993b; Arruda, 1995; Winther, 1998) it was concluded that: (i) the virus was first recovered, at the highest concentrations, from the nasopharynx before it could be recovered in the upper nose region (turbinates). (ii) no evidence for rhinovirus induced damage of the surface ciliary lining of the inferior turbinate was noted which is in agreement with other investigators suggesting that the virus may be transported to the nasopharynx in the overlaying mucus by mucociliary clearence. (iii) there was a significant increase of the influx of neutrophils in the same area as in (ii) (iv) infection of the lining of the nasal cavity was not uniform after intranasal inoculation and seemed not to result in any cell damage at all, cf. (ii) above. (v) the rate of viral shedding in the nasopharynx was high by day 1 (post infection), whereas cold symptoms did not peak until day 3. The symptoms waned during the first week, but rhinovirus was present during the following 3 weeks. (vi) The increase of neutrophils correlates with the onset of symptoms, including sore throat. The symptoms include oedema-like symptoms, which in turn may trigger sneezing and coughing. It should be stressed that the highest concentration of virus can be recovered from the nasopharynx, and virus usually appears on the turbinate(s) one or two days later, despite the fact that virus is innoculated via the nose (in volunteers). No visible damage of the cell lining in the upper airways was ever demonstrated. Furthermore, as “sore throat” usually develops simultaneously with the appearance of virus in the nasopharynx it can be reasoned that “signal molecules” or the like (Van Damme, 1988) will be made by the relatively few rhinovirus cells infected and that these “cytokinelike molecules” subsequently may activate the “lymphatic ring”—which is located just beneath the nasopharynx—leading to the well-known sore throat, which in turn triggers a complex pattern of inflammatory reactions, involving an array of different interferons and cytokines the interaction of which is currently under in-depth investigation. Some of these factors, such as for example II-1, induce fever in patents. Bradykinines per se may be responsible for the sore throat, which is frequently associated with common cold. The fact that interferon is known to be part of the non-specific innate immune response against viral infections in man has lead to several publications as a number of groups have investigated how much interferon is produced locally during viral infections of the upper-airways. One of the earliest and probably most thorough, in vivo, investigations in man was performed by Cate et al. (Cate, 1969) on volunteers (healthy adult males from federal correctional institutions in USA). The authors were able to demonstrate, that most of the persons involved produced interferon (as demonstrated in nasal washings) during common colds at a level, which at least theoretically should have been enough to block the viral infection, per se. It has been demonstrated in a recent publication, that the immune system also takes “active part” in the spread of the inflammatory actions since experimental evidence supports the notion that rhinovirus may use some of the effector cells from the immune system as a mean for spreading the inflammatory reactions to the lower airways,(Gern, 1996) via initiation of local TNF-alpha production. It is tempting to speculate that the allergic rhinitis is initiated via this mechanism as it has been found that the pathogenesis for asthma is linked to local TNF-alpha production (Broide et al.1992). Several quarters have thus argued that the asthma syndromes are rhinovirus manifestations of post-infectious events triggered by an array of different cytokines in connection with a “switch” between the Th1 vs. Th2 response (Gern, 1999; Winther, 1998; Grünberg, 1999). Generally speaking, air-way infections or allergic rhinitis and/or asthma may pose a serious health problems as it can be potentially life-threatening for susceptible groups such as elderly people with chronic airway problems or persons suffering from a deficient immunity, such as AIDS-patients, cancer patients etc. Thus, simple and effective methods of treating these symptoms/syndromes and possibly also the underlying infections would be of immense importance. Viral and/or other microbial infections are known to initiate a complex inflammatory response (Ginsburg, 1988) from the patient which probably is mediated by several groups of responder cells including the neutrophile granulocytes, which are specifically increased during a cold. The latter represents approximately more than 95% of all the effector cells. Each min. about 6-9 millions neutrophiles enter the upper-airways and slowly pass down the interior surfaces encompassing the upper airways. It may be assumed that the neutrophiles, which are able to release very aggressive enzymes and toxic substances upon proper stimulation will keep the bacterial load of the upper-airways to an acceptable level. The small numbers of S. pyogenes or S. aureus found in nasopharynx, which otherwise is almost sterile, may stimulate the neutrophiles via the so-called super-antigens to a certain degree thereby limiting the numbers of bacteria in said areas (dynamic equilibrium/symbiosis). According to Ihrcke and co-workers (Ihrcke, 1993) the very early steps in a virus infection (or any other abnormality in the cell lining) can be related to the content and metabolism of heparan sulfate proteoglycan (the major proteoglycan associated with intact endothelial cells). The first element of the model derives from the observation that heparan sulfate is released from the intact endothelial lining of blood vessels during the very first step in an inflammatory response initiated by a viral infection. Accordingly, this loss may seriously compromise the vascular integrity and result in a local edema attracting further neutrophiles via the up-regulation of ICAM-1 markers on the endothelial cells increasing the inflammatory response further. Thus, in a separate experiment, activated neutrophiles were able to release 70% of all cell-associated heparan sulfate proteoglycan within one hour via the subsequent release of heparanase. One important function of heparan sulfate is the maintenance of the endothelial cell integrity. Loss of heparan sulfate partially abrogates the barrier properties of the endothelium and contributes to the edema and exudation of plasma proteins that characterise inflammation. It has previously been attempted to treat common cold using flavonoids. WO 02/09699 describes treatment of common cold and similar conditions, such as hayfewer using flavonoids, such as troxerutin or veneruton, either alone or in combination with metals. Flagrant used include peppermint oil. U.S. Pat. No. 6,596,313 describes compositions for oral administration that may be useful for treatment of common cold. The compositions comprise extracts from various plants. The document mentions that menthol may be used as a flagrant. The effect of a composition comprising menthol is however not disclosed. U.S. Pat. No. 6,592,896 describes oral pharmaceutical compositions comprising plant extracts. The document mentions that menthol may be used as a flagrant. The compositions may be useful for treatment of common cold. The effect of a composition comprising menthol is not disclosed. WO 01/03681 describes treatment of viral infection, including infections related to common cold with a variety of flavonoids. WO 01/49285 decsribes a medicament comprising flavonoid(s). The medicament may be useful for treatment of common cold, however this is not demonstrated. SUMMARY OF THE INVENTION It is an objective of the present invention to provide new and efficient pharmaceutical compositions for treatment of common cold and similar conditions. Interestingly, the present invention surprisingly discloses that the choice of flagrance is very important. In particular, the present invention demonstrates a surprising effect amongst different commonly used flagrance additives. Interestingly, pharmaceutical compositions comprising flavonoid and purified menthol are more efficient than similar compositions comprising other flagrances in the treatment of common cold and related conditions. Hence, it is a first objective of the present invention to provide pharmaceutical compositions comprising i) one or more purified flavonoids; and ii) purified menthol; and iii) pharmaceutically acceptable expients. It is a second obejctive of the present invention to provide use of one or more purified flavonoids and purified menthol for the preparation of a pharmaceutical composition for the treatment of a clinical condition or symptoms of a clinical condition in an individual in need thereof. It is a third objective of the present invention to provide methods of treatment of a clinical condition in an individual in need thereof, comprising administering to said individual the pharmaceutical composition according to the invention. It is a further objective of the present invention to provide a medicament for treating a clinical condition comprising purified flavonoid and purified menthol as active ingredients. DESCRIPTION OF FIGURES FIG. 1A illustrates the antiviral activity of natural HuIFN-α (designated HuIFN-alpha) versus rhinovirus-T39 at a dilution of 10−2 (designated HRV T39) in the presence and absence of menthol (1:800) (designated M). FIG. 1B illustrates the antiviral activity of natural HuIFN-α (designated HuIFN-alpha) versus rhinovirus-T39 at a dilution of 10−2,5 (designated HRV T39) in the presence and absence of menthol (1:800) (designated M). FIG. 2A illustrates the antiviral activity of Menthol at a dilution of 1:800 (designated menth) versus rhinovirus T39 (designated HRV T39). FIG. 2B illustrates the antiviral action of menthol (designated Menth) at dilutions 1:800 and 1:1600 versus rhinovirus T39 (designated HRV T39). FIG. 3A illustrates that peppermint oil (designated PPO) potentiates the production of rhinovirus T39 (designated HRV T39). FIG. 3B illustrates that peppermint oil (designated PPO) downregulate the interferon-α system using rhinovirus 10 as challenge virus at a dilution of 10−2 (designated RHV10(-2) ). Interferon-α is designated IFN. FIG. 3C illustrates that peppermint oil (designated PPO) downregulate the interferon-α (desingated IFN) system using rhinovirus 10 (designated RHV 10) as challenge virus at dilutions of 10−2 and 10−2.5. FIG. 4A illustrates the total mean symptom score per common cold patient treated with menthol-lozenges. The curves show the average and standard deviation from 3 patients (patients no. 161202, 020403 and 270403), wherein treatment was initiated 24 h p.i. FIG. 4B illustrates the total mean symptom score per common cold patient treated with Menthol-lozenges. The curves shows the average and standard deviation from groups of patients grouped according to when treatment was initiated (24 h, 48 h and 7 days p.i.). FIG. 4C illustrates differential symptom score from 5 common cold patients treated with Menthol-lozenges. The curves show symptom score for rhinitis/rhinorrhea, sore throat, sneezing, clogged nose, coughing and headache. FIG. 4D illustrate differential symptom score from 10 patient treated with PPO-lozenges (treatment initiated 24-36 h p.i.). The curves show symptom score for running nose, sneezing and clogged nose. FIG. 4E illustrates total mean symptom score for naturally infected common cold patients treated with PPO-lozenges with (ImmuMaxZn) or withour Zn2+ (ImmuMax). Treatment was initiated within 24-36 h subsequent to clinical diagnosis. FIG. 4F illustrates total mean symptom score for naturally infected common cold patients treated with PPO-lozenges with (ImmuMaxZn) or withour Zn2+ (ImmuMax). Treatment was initiated within 24 h subsequent to clinical diagnosis. DETAILED DESCRIPTION Pharmaceutical Compositions Comprising Flavonoid and Menthol Surprisingly, the present invention demonstrates that some flagrances, for example menthol has an antiviral effect, for example an antiviral effect against rhinovirus. Accordingly, in one embodiment the present invention relates to pharmaceutical compositions comprising flavonoid(s) and menthol as well as uses thereof. In particular the pharmaceutical compositions preferably comprises i) one or more purified flavonoids; and ii) purified flagrance with antiviral effect; and iii) pharmaceutically acceptable exipients. Preferably, said flagrance with antiviral effect is menthol. However any other flagrances with antiviral effect, for example citric acid or similar compounds with low pH may be used. In another embodiment the present invention relates to pharmaceutical compositions comprising one or more flavonoids, wherein said compositions are essentially free of any component of peppermint oil, which is not menthol. Preferably, said compositions are free of any components of Japanese peppermint oil. Said compositions may in addition to flavonoids comprise one or more other active ingredients, for example a metal salt and/or metal complex and/or menthol. The compositions may also comprise flavouring agents other than peppermint oil. Components of peppermint oil may for example be selected from the group consisting of menthone, menthyl acetate, limonene, neomenthol, piperitone, menthenone, isomenthone, pulegone, β-caryophyllene, β-caryophyllene-epoxide, α-pinene, β-pinene, germacrene D, 1,8-cineol, linalool, menthofurane, camphene and β-hexenyl phenylacetate. The flavonoid may be any of the flavonoids described herein below. Menthol is a terpene compound of the formula CH3C6H9(C3H7)OH. Purified menthol may have been purified from a plant or it may have been synthesised chemically. Menthol purified from a plant is preferably essentially free of any other compounds of said plant. Menthol according to the invention is preferably levo-(−)-Menthol (also designated (−)-menthol. Useful pharmceutical acceptable expients are described herein below. By the term “purified flavonoids” is meant one or more flavonoids essentially free of any other compounds. Hence, a composition of “purified flavonoids” comprises at least 90% flavonoid, preferably at least 95% flavonoid, more preferably at least 98% flavonoid, even more preferably aprroximately 100% flavonoid. A composition of “purified flavonoids” thus most preferably does not contain any other detectable compound. In particular, it is preferred that purified flavonoids are free of other compounds present in the composition from which they are purified. By way of example, if the flavonoid is purified from a plant extract, it is preferred that the purified flavonoids are essentially free of any other compounds present in the crude plant extract. Preferably, the pharmaceutical compositions of the invention are essentially free of crude plant extracts or fractions thereof. The compositions may off course comprise fractions mainly consisting of flavonoids or menthol. In one embodiment of the invention, purified flavonoids and purified menthol together constitutes at least 50%, preferably at least 60%, more preferably at least 70%, even more preferably at least 80%, yet more preferably at least 90%, even more preferably at least 95%, such as at least 98%, for example around 100% of the active ingredients of the pharmaceutical compositions of the invention. Hence, in one preferred embodiment of the invention the pharmaceutical compositions essentially consists of iv) one or more purified flavonoids; and v) purified menthol; and vi) pharmaceutically acceptable expients, wherein said expients are not therapeutically active. By the term “essentially consists of” is meant that no other ingredients are detectable by commonly used detection techniques. In another embodiment of the invention, the pharmaceutical compositions also comprise a pharmaceutically acceptable metal complex and/or metal salt. Examples of suitable metalcomplexes and salt are given herein below. In this embodiment of the invention it is preferred, albeit not mandatory for the invention that purified flavonoids and purified menthol and metal complexes/metal salts together constitutes at least 50%, preferably at least 60%, more preferably at least 70%, even more preferably at least 80%, yet more preferably at least 90%, even more preferably at least 95%0, such as at least 98%, for example around 100% of the active ingredients of the pharmaceutical compositions of the invention. Hence, in a very preferred embodiment of the invention the pharmaceutical composition essentially consists of i) one or more purified flavonoids; and ii) purified menthol; and iii) one or more metal complexes and/or metal salts; and iv) pharmaceutically acceptable expients, wherein said expients are not therapeutically active. In one embodiment of the present invention it is thus preferred that the pharmaceutical compositions do not contain other active ingredients that the above mentioned, in particular it is preferred that the composition does not comprise any vitamins, such as vitamin E. It is also preferred that the composition does not comprise antibodies. It is also preferred that the compositions do not comprise hydroxypropylcellulose. In one embodiment it is preferred that the pharmaceutical composition is essentially free of other terpenes than menthol. Hence, the pharmaceutical composition is in this embodiment of the invention preferably essentially free of one or more selected from the group consisting of menthone, menthyl acetate, limonene and neomenthol. More preferably, the composition is essentially free of one or more selected from the group consisting of menthone, menthyl acetate, limonene, neomenthol, piperitone, pulegone, β-caryophyllene, β-caryophyllene-epoxide, α-pinene, β-pinene, germacrene D, 1,8-cineol, linalool, menthofurane, camphene and β-hexenyl phenylacetate. Even more preferably, the pharmaceutical composition is essentially free of menthone, menthyl acetate, limonene and neomenthol. Yet more preferably, the pharmaceutical composition is essentially free of menthone, menthyl acetate, limonene, neomenthol, piperitone, pulegone, β-caryophyllene, β-caryophyllene-epoxide, α-pinene, β-pinene, germacrene D, 1,8-cineol, linalool, menthofurane, camphene and β-hexenyl phenylacetate. It is also preferred that the pharmaceutical composition is essentially free of one or more preferably all compounds selected from the group consisting of menthone, menthyl acetate, limonene, neomenthol, piperitone, menthenone, isomenthone, pulegone, β-caryophyllene, β-caryophyllene-epoxide, α-pinene, β-pinene, germacrene D, 1,8cineol, linalool, menthofurane, camphene and β-hexenyl phenylacetate. The term “pharmaceutical composition” should be understood in its ordinary meaning, i.e. the term does preferably not cover food, cosmetics, toothpaste and the like. Menthol as Antiviral Compound Surprisingly, the present invention demonstrates that menthol has an antiviral effect. Hence it is also an obejctive of the present invention to provide methods of reducing the amount of virus in a composition, comprising incubating said composition comprising virus with menthol. It is also an objective of the invention to provide methods of reducing the amount of virus in an individual infection with said virus, comprising administering to said individual a pharmaceutical composition comprising menthol, thereby reducing the amount of said virus in said individual. The invention also relates to uses of menthol for the preparation of a pharmaceutical composition for reduction of virus in an individual in need thereof. The individual in need thereof may be any individual. Preferably, the individual is an individual infected with one or more of the vira mentioned herein below. The virus is preferably any of the vira mentioned herein below in the section “Clinical conditions”. More preferably, said virus is rhinovirus. The methods mentioned above may also be combined with administration of one or more other active compounds. In parallel, the pharmaceutical compositions may also comprise one or more other active compounds. Said active compounds may for example be selected from the group consisting of flavonoids, metal complexes and metal salt. The reduction of virus is preferably a reduction to at the most 80%, more preferably at the most 70%, even more preferably at the most 60%, such as at the most 50%, for example at the most 40%, such as at the most 30%, for example.at the most 20%, such as at the most 10% of the initial amount of virus. More preferably, the reduction of virus results in at least 10%, preferably at least 20%, more preferably at least 30%, for example at least 40%, such as at least 50%, such as at least 60, for example at least 70%, such as at least 80%, for example at least 90% increase in cell survival in an in vitro test system. Cell survival may preferably be determined as for example described in example 2. Flavonoids “Flavonoids” useful with the present invention may be any flavonoid known to the person skilled in the art. Flavonoids are polyphenolic compounds isolated from a wide variety of plants with over 4000 individual compounds known. The term “flavonoid” according to the present invention covers both naturally, occurring flavonoids as well as synthetic derivatives thereof. Flavonoids comprise a range of C15 aromatic compounds and are found in virtually all land-based green plants. Preferred flavonoids according to the present invention includes flavonoids of the general formula: or the general formula: Wherein R2′ can be selected from: —H —OH R3′ can be selected from: —H —OH —OCH3 —OCH2CH2OH R4′ can be selected from: —H —OH —OCH3 —OCH2CH2OH R5′ can be selected from: —H —OH —OCH3 —OCH2CH2OH R6′ is —H; R3 including R31 and R32 can individually be selected from: —H —OH —O-rutinose —O-glucoside —O-glucose-p-coumaric acid —SOH —O-rhamnose R4 can be selected from: —H —(O) —OH R5 can be selected from: —H —OH —O—CH2CH2OH R6 can be selected from: —H —OH —OCH3 R7 can be selected from: —H —OH —O-glucose —OCH3 —OCH2CH2OH —O-glucuronic acid —O-rutinose —O-rhamnoglucoside R8 can be selected from: —H —OH Furthermore, flavonoid and/or flavonoid derivatives could be stereoisomers of the above mentioned. Additionally flavonoid and/or flavonoid derivatives could be dimers comprising two flavonoid subunits. Additionally, flavonoids and/or flavonoid derivatives of the present invention to be used in combination with metal could be any flavonoid and/or flavonoid derivative known to the person skilled in the art. For example such flavonoid and/or flavonoid derivative could be any of the flavonoid and/or flavonoid derivative mentioned in WO 01/03681, which is hereby incorporated in its entirety by reference. Preferably, the flavonoid and/or flavonoid derivatives are selected from molecules with the above general formulas with the proviso, that when R3′ is selected from —OH —OCH3 —OCH2CH2OH then R5′ is selected from —H and when R5′ is selected from —OH —OCH3 —OCH2CH2OH then R3′ is selected from —H Semi-synthetic flavonoids are also within the scope of the present invention. In one embodiment of the invention the flavonoid is a synthetic flavonoid, i.e. a not naturally occurring flavonoid, such as a semi-synthetic flavonoid or a synthetic derivative of a naturally occurring flavonoid. Preferably, the flavonoid according to the present invention could be selected from the group consisting of: troxerutin, venoruton, hydroxyethylrutosides, hesperitin, naringenin, nobiletin, tangeritin, baicalein, galangin, genistein, quercetin, apigenin, kaempferol, fisetin, rutin, luteolin, chrysin, taxifolin, eriodyctol, catecithin, epicatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, flavone, sideritoflavone, hypolaetin-8-O-Gl, oroxindin, 3-hydroxyflavone, morin, quercetagetin-7-O-Gl, tambuletin, gossypin, hipifolin, naringin, leucocyanidol, amentoflavone and derivatives thereof and mixtures thereof. More preferably, one or more of the R chains are —OCH2CH2OH, yet more preferably, at least two R chains are —OCH2CH2OH, most preferably three R chains are —OCH2CH2OH. In one embodiment of the invention the flavonoid does not comprise antiviral activity when tested in vitro. Furthermore, it is preferred that said flavonoid is soluble in water. In a preferred embodiment, at least one flavonoid is a rutoside, more preferably at least one flavnoid is a hydroxyethylrutoside. Even more preferably, all the flavonoids of the composition are rutosides, yet more preferably all the flavonoids of the composition are hydroxyethylrutosides. For example the pharmaceutical compositions of the invention may comprise a mixture of hydroxyethylrutosides, such as a mixture of mono-, di-, tri- and tetrahydroxyethylrutosides. In one preferred embodiment the flavonoid derivatives according to the invention comprises a mixture of mono-, di-, tri- and tetrahydroxyethylrutosides. More preferably, the mixture comprise 1% to 15% monohydroxyethylrutoside, such as from 5% tol0% monohydroxyethylrutoside, and from 25% to 50% dihydroxyethylrutoside, such as from 30% to 38% dihydroxyethylrutoside, and from 30% to 70% trihydroxyethylrutoside, such as from 45% to 55% trihydroxyethylrutoside and from 1% to 20% tetrahydroxyethylrutoside, such as from 3% to 12% tetrahydroxyethylrutoside. Most preferably, said mixture of hydroxyethylrutosides is Venoruton. The flavonoid is most preferably selected from the group consisting of troxerutin, Veneruton, pharmaceutical acceptable salts thereof and functional derivatives thereof. In one especially preferred embodiment of the present invention at least one flavonoid is troxerutin of the formula: Troxerutin of the above-mentioned formula is also known as 7,3′,4′-tris[O-(2-hydroxyethyl)]rutin (CAS no. 7085-554). The term “Troxerutin” is in the prior art also used to designate a mixture of hydroxyethylrutosides. Hence, the pharmaceutical compositions according to the present invention may also comprise such mixtures of hydroxyethylrutosides (herein designated hydroxyethylrutoside mixture). In preferred embodiments the pharmaceutical compositions comprise no other flavonoids than a hydroxyethylrutoside mixture. Preferably, the hydroxyethylrutoside mixture comprises at least 40%, for example around 46%, such as at least 50%, for example at least 60%, such as at least 70%, for example at least 80% troxerutin of the above-mentioned formula. The hydroxyehtylrutoside mixture may also comprise in the range of 2 to 10%, more preferably in the range of 3 to 7%, even more preferably around 5% monohydroxyehtylrutosides. The hydroxyehtylrutoside mixture may also comprise in the range of 20 to 50%, more preferably in the range of 30 to 40%, even more preferably around 34% dihydroxyehtylrutosides. The hydroxyehtylrutoside mixture may also.comprise in the range of 2 to 10%, more preferably in the range of 3 to 7%, even more preferably around 5% tetrahydroxyehtylrutosides. Other hydroxyethylated components, such as hydroxyehtylated quercetin, for example tetrahydroxylated quercetin may be present in small quantities. In one embodiment of the invention some or all.of the flavonoids are aglycones. For example, at least one flavonoid may be a rutoside aglycone, preferably at least one flavonoid is a hydroxyethythyrutoside aglycone, more preferably, at least one flavonoid is troxerutin aglycone. Aglycones are flavonoids from which at least one sugar group has been removed. Aglycones may be prepared using any suitable mechanism, for example by the aid of β-glucoronidase (see also Shimoi et al., 2001). The chemical formula of troxerutin aglycone is shown below: In one embodiment of the invention at least some of the flavonoids, such as essentially all flavonoids are present as metal chelates, such as chelates of iron(III), iron (II), copper(II) or zinc(II). Preferably flavonoids may be present as chelates of Zn2+. Metal chelation of polyphenols is for example described in (Hider et al., 2001) and the flavonoid metalchelate may for example be formed by any of the mechanisms described therein. Preferably, the flavonoid metal chelate is Zn2+/troxerutin or Zn2+/Veneruton. The pharmaceutical compositions according to the present invention may also comprise mixtures of more than one flavonoid. For example-such a mixture may comprise 2, such as 3, for example 4, such as 5, for example 6, such as 7, for example 8, such as 9, for example 10, such as more than 10 different flavonoids. Preferably, such a mixture comprise 8 to 10 different flavonoids. In one embodiment of the invention the flavonoid is not astragalin. Clinical Conditions The present invention relates to uses of flavonoids and menthol for the preparation of a medicament for the treatment of a clinical condition. The invention also relates to methods of treatment of a clinical condition. The-clinical condition may be any clinical condition, which may be treated using flavonoids and menthol. However, in preferred embodiments of the present invention the clinical conditions is a condition relating to common cold, such as common cold of the upper and/or lower respiratory tract and/or eyes. Conditions relating to common cold comprises common cold, a viral infection and/or a bacterial infection of the upper and/or lower respiratory tract and/or eyes, rhinitis, an allergic condition having one or more symptoms similar with the symptoms of a common cold for example allergic rhinitis initiated by rhinovirus infection, asthma like exacerbations and/or other abnormal airway functions derived from various dysfunctions of the immune system, such as for example hay fever or the like. Furthermore, conditions relating to a common cold may comprise secondary bacterial infection(s) that follow soon after a primary viral infection. Secondary bacterial infections may for example be initiated by the normal bacterial flora present in the upper and/or lower respiratory tract and/or eyes. Symptoms of conditions relating to common cold can be selected from the group comprising, but is not limited to: coughing, sneezing, muscle pain, sore throat, hoarseness, irritated throat, headache, malaise, chilliness, nasal discharge, nasal obstruction, pain relating to the sinuses, fever, rhinitis, swelling of mucosal membranes, pharyngitis, astma, and acute as well as chronic bronchitis. In the present invention the upper respiratory tract includes the mouth, nose, sinuses, throat, and the respiratory tract to epiglottis. The lower respiratory tract includes the rest of the bronchial tree including the bronchioles and lung vacuoles. The invention also relates to the treatment of eye symptoms related to the condition of the respiratory tract in that the condition may involve the mucosal lining of the respiratory tract as well of the eyes. By the term treatment as used herein is also meant prevention of symptoms whether the prevention is in fact a decrease in the development of symptoms or a prevention of the symptoms to arise in first place, e.g. upon exposure to infection. According to the present invention a pharmaceutically effective amount or a therapeutically effective amount is to be understood as an amount sufficient to induce a desired biological result. The result can be alleviation of the signs, symptoms, or causes of a disease, for example of common cold, preferably, the result is a significant alleviation of signs, symptoms or causes of common cold. For example, an effective amount is generally that which provides either subjective relief of symptoms or an objectively identifiable improvement as noted by the clinician or other qualified observer, preferably such a relief of symptoms is a significant relief. The relief may for example be evaluated based on a symptom score as disclosed herein in the examples. Accordingly, effective amounts can vary widely depending on the individual, on the disease or symptom to be treated. Most common cold patients produce interferon following infection of the respiratory tract (Cate et al., 1969), which per se in principle should be sufficient to alleviate the infection. Hence, in one preferred aspect of the present invention the treatment of a viral infection is not to be regarded as a direct antiviral effect but as a modification or inhibition of cytokines or other factors relevant for the establishment or continuation of a viral infection located in the mucosal membrane of the respiratory tract or eyes. Furthermore, the treatment preferably inhibits inflammation processes in the mucosal membrane of the respiratory tract or eyes and thereby alleviates symptoms of common cold. Accordingly, the invention relates-to use of a flavonoid and menthol for the treatment of symptoms of viral infection of the upper and/or lower respiratory tract and/or eyes, wherein the flavonoid and/or flavonoid derivative has no-antiviral effect in vitro. Thus, in one embodiment of the present invention the flavonoid does not comprise an antiviral or anti bacterial effect in vitro. In vitro antiviral and/or antibacterial effect can be determined in various laboratory tests. Preferably, such laboratory tests comprise a cultured cell line capable of being infected with the bacteria or virus to be tested as well as said bacteria or virus. More preferably, said cultured cell line is WISH cells and said virus is a rhinovirus selected from the group consisting of: rhinovirus 1A, rhinovirus 15 and rhinovirus 39. Most preferably antiviral effect is determined using the MTS method as described in example 1. When antiviral effect is measured according to the MTS method as described in example 1, a protection of less than 10%, preferably less than 7.5%, more preferably less than 5%, even more preferably less than 3%, most preferably less than 2% is to be regarded as no antiviral effect in vitro. Preferably, the effect of the flavonoid and/or flavonoid derivative is closely related to the living organism such as the effect is a modulatory effect on specific factors and biological reactions related to the affected mucosal membrane. The precise mechanisms are currently not known. Very often common cold is initiated by, associated with or followed by a viral infection, which is involved in the common cold or symptoms of the common cold. In one embodiment of the present invention the condition relating to common cold is associated with a viral infection of the upper and/or lower respiratory tract and/or eyes. The virus infection which a common cold is most often associated with or initiated by, is infection by one or more virus selected from the group consisting of: adenoviruses, parvoviruses, picornaviruses, reoviruses, orthomyxoviruses, paramyxoviruses, arenaviruses, caliciviruses, coronaviruses, orthomyxoviruses, rhinovirus, influenza virus, including influenza virus type A and B, echovirus, respiratory syncytial virus (RSV), and coxsackie virus. Rhinovirus is the most common virus identified in relation to common cold. The term rhinovirus is meant to comprise any rhinovirus for example any of the rhinoviruses 1-113. However, very often the above virus may be present in individuals with no symptoms of common cold. Preferably, the virus infection associated with common cold according to the present invention is infection by rhinovirus or coronavirus. Very often the common cold is associated with or followed by a bacterial infection, which is involved in the common cold or symptoms of the common cold. Such a bacterial infection may in one embodiment of the present invention be a secondary infection following a primary infection with for example a virus. In one embodiment of the present invention the condition relating to common cold is associated with a bacterial infection of the upper and/or lower respiratory tract and/or eyes. The bacterial infection, which may be associated with a common cold or with the symptoms thereof is most often infection by one or more bacteria selected from Streptococcus pheumoniae, Streptococcus Haemolyticae, Haemophilus influenxae, and Moraxella catarrhalis. Furthermore, common cold may be initiated by a microbial infection. Such a microbial infection may lead to similar inflammatory responses as viral infections involving the same effector cells for example neutrophiles. Accordingly, such microbial infections may be treated in a fashion similar to viral infections associated with common cold. Many allergic reactions are associated with symptoms similar to the symptoms of a common cold and it has surprisingly been shown that such symptoms of an allergic disorder may also be effectively treated by the method and use as disclosed herein. Hence, in one embodiment of the present invention the condition relating to common cold is an allergic disorder. The allergic conditions according to the present invention is preferably selected from rhinitis, asthma, acute and chronic bronchitis, and hay fewer. The most common symptoms in relation to allergies are one or more symptoms selected from nasal discharge, nasal congestion, sneezing, cough, swelling of mucosal membranes, rhinitis. More preferably, the allergic condition according to the present invention is selected from the group consisting of rhinitis and hay fewer. In a further aspect of the present invention the individual may have relief from the symptoms based on a decreasing effect of said flavonoid on the mucosal swelling associated with the infection or condition mentioned herein. In a still further aspect the present invention encompass acute allergic reactions related to insect bites and sticks and in a still further aspect to the allergic reactions from food or other allergens leading to swelling of the mucosa of the mouth and/or throat in such acute reactions. It is furthermore contained within the present invention to treat allergic conditions that is initiated by one or more agents selected from the group consisting of: pollution, house dust, common dust mite such as Dermatophagoides Farinae or Dermatophagoides Pteronyssinus, pollen such as grass pollen, tree pollen or weed pollen, mold, animal danders or feathers, fungal spores and chronic inhalation of for example, wheat flour. Accordingly, the conditions related to common cold of the present invention could be an infection or common cold or allergic condition characterised by one or more symptoms selected from the group comprising: coughing, sneezing, muscle pain, sore throat, hoarseness, irritated throat, headache, malaise, chilliness, nasal discharge, nasal obstruction, pain relating to the sinuses, rhinitis, swelling of mucosal membranes, pharyngitis, astma, and acute as well as chronic bronchitis. When the condition relating to common cold is an allergic condition, preferably such a condition is treated by administration of flavonoid and menthol without simultaneous administration of metal to the individual in need thereof. More preferably said flavonoid is selected from the group consisting of troxerutin and Veneruton®. The classical common cold results in symptoms, which lasts for approximately one week. However, in certain cases conditions relating to common cold results in symptoms, which lasts for much longer. Such long lasting common colds for example last for more than 10 days, such as more than 2 weeks, such as more than 3 weeks, for example more than one month, such as more than 6 weeks. Individual suffering from long lasting common cold are preferably treated by administration of flavonoid and menthol without simultaneous administration of metal. More preferably said flavonoid is selected from the group consisting of troxerutin and Veneruton®. In contrast, individuals suffering from a classical common cold wherein treatment is initiated 1 to 5 days following the onset of common cold symptoms, preferably 1 to 3 days following the onset of common cold symptoms may be treated by administration of both a flavonoid, menthol and metal according to the present invention. Metal Complexes and Metal Salts In one embodiment of the invention the pharmaceutical compositions comprises flavonoid, menthol and a metal complex and/or metal salt. The metal according to the present invention is preferably selected from the group consisting of zinc, manganese, cadmium, cobalt, iron and selenium. The metal may for example be in the form of Zn2+, Mn2+, Cd2+, Co2+, Fe2+ and Se2+. Most preferably the metal is zinc. Preferably zinc is Zn2+, given in the form of a salt and/or complex or derivatives thereof. Within the scope of the present invention, zinc could be in any suitable form for example as ZnGluconate, as Zn(acetate)2, as Zn2+ aminochelates , as Zn2+ amino acid chelates, as Zn2+ DL-methionine, as Zn2+ L-methionine, as histidine derivatives or as a complex with amino acids in combination with histidine, or the like such as for example PolaPreZinc®. Furthermore zinc could be in the form of zinc sulfate, zinc chloride, Nitric-acid zinc, phosphoric-acid zinc, ulmin acid zinc, zinc fluoride, zinc iodide, a zinc hydroxide, zinc carbonate, a zinc chromate, benzoic-acid zinc, zinc acetate, p-aminobenzoic-acid zinc, p-dimethylamino benzoic-acid zinc, p-zinc phenolsulfonate, p-methoxy cinnamic-acid zinc, lactic-acid zinc, gluconic-acid zinc, citric-acid zinc, salicylic-acid zinc, a zinc stearate, lauric-acid zinc, myristic-acid zinc, Oleic-acid zinc, 2,5-pyridine dicarboxylic-acid zinc, 2,6-pyridine dicarboxylic-acid zinc, 4-pyridine dicarboxylic-acid zinc, 2,4-dicarboxy pyridine zinc, 3-hydroxy-2-carboxy pyridine zinc, 3-n-propoxy-2-carboxy pyridine zinc, 3-n-hexyloxy-2-carboxy pyridine zinc, 5-n-propoxy-2-carboxy pyridine zinc, 5-n-butoxy-2-carboxy pyridine zinc, 5-(2-ethyl-hexyloxy)-2-carboxy pyridine zinc, 6-n-butoxy-2-carboxy pyridine zinc, 3-methoxy-2-carboxy pyridine zinc, 5-methoxy-2-carboxy pyridine zinc, 6-methoxy-2-carboxy pyridine zinc, 6-n-hexyloxy-2-carboxy pyridine zinc, 3methyl-2-carboxy pyridine zinc, 4-methyl-2-arboxy pyridine zinc, 4-tert-butyl-2-carboxy pyridine zinc, 5-methyl-2-carboxy pyridine zinc, 5-n-hexyl-2-carboxy pyridine zinc, 3-n-undecyl-2-carboxy pyridine zinc, 4-n-undecyl-2-carboxy pyridine zinc, 5n-butyl-2-carboxy pyridine zinc, 6-n-undecyl-2-carboxy pyridine zinc, 4nitroglycerine-2-carboxy pyridine zinc, 5-hydroxy-2-carboxy pyridine zinc, 4fluoro-2-arboxy pyridine zinc, 2-carboxy pyridine N-oxide zinc, picolinic-acid zinc, Nicotnic-acid zinc, nicotinamide zinc, 3,4-dihydroxy benzoic-acid zinc, Screw histidine zinc, hinokitiol zinc, protoporphyrin zinc, porphyrin zinc or picolinic-acid amide zinc. It is contained within the present invention that zinc could be a combination of the above mentioned zinc salts and/or a zinc complexes. Such combination could comprise two or more sorts. Preferably zinc is selected from the group consisting of Zn2+ aminochelates, Zn2+ amino acid chelates, Zn(acetate)2, Zn2+ DL-methionine, Zn2+ L-methionine, ZnGluconate and PolaPreZinc®. Preferably, zinc is in the form of ZnGluconate or PolaPreZinc®. Administration, Formulation and Effect In one aspect the present invention relates to methods of treatment involving administration of any of the pharmaceutical compositions described herein above. The invention also relates to use of flavonoid(s) for the preparation of a medicament for the treatment of a clinical condition, such as common cold. Said medicament is preferably free of all compounds of peppermint oil except menthol. In one embodiment the invention relates to use of flavonoid and menthol for the preparation of a medicament for treatment of a clinical condition, such as common cold (see herein above). The pharmaceutical compositions according to the present invention should preferably comprise an effective dosage of flavonoids and menthol and optionally of metal. It is contained within the present invention that the effective dosage is distributed over several dosage units. By way of example, if the pharmaceutical composition is formulated as lozenges, then the daily effective dosage may be distributed in 2 to 20 lozenges. It is also contained within the present invention that flavonoids and menthol are formulated individually, and that the pharmaceutical composition thus comprises two individual formulations, which may be administered simultaneously or sequentially in any order. However, preferably they are administered simultaneously. The effective dosage of flavonoids may vary according to the individual in need thereof and to the particular clinical condition. In general, the effective will be in the range of from 5 to 5000 mg daily. More preferably, the effective dosage is in the range of from 10 mg to 4000 mg, such as in the range of from 30 mg to 3000 mg, even more preferably in the range of from 40 mg to 2000 mg daily, yet more preferably, in the range of from 50 mg to 1000 mg daily. Furthermore, the effective dosage of said flavonoids could be a dosage equivalent of a dosage of troxerutin of from 5 mg to 5000 mg daily. The effective dosage of Venoruton or troxerutin or a hydroxyethylrutoside mixture or a pharmaceutically acceptable salt or a functional derivative or a metal chelat thereof is normally in the range of from 5 to 5000 mg. In general the effective dosage is in the range of from 10 mg to 4000 mg, such as in the range of from 30 mg to 3000 mg, preferably in the range of from 40 mg to 2000 mg daily, more preferably, from in the range of 50 mg to 1000 mg daily, yet more preferably in the range of from 50 to 500 mg daily, most preferably in the range of from 100 to 300 mg daily for for example an adult human being. The effective dosage of menthol is depending on the individual to be treated in general in the range of 1 mg to 200 mg daily. Preferably, the effective dosage of menthol is in the range of 5 mg to 100 mg daily, more preferably the effective dosage is in the range of 10 mg to 50 mg daily, even more preferably the effective dosage is in the range of 15 mg to 40 mg daily, yet more preferably the effective dosage is in the range of 20 mg to 35 mg daily for for example an adult human being. The administration of flavonoids and menthol according to the present invention is preferably a very frequent administration during the day. If menthol and flavonoid are formulated individually, the administration frequency may differ for flavonoid and menthol, respectively. Accordingly, the daily dosage may individually be administered in divided dosages of 1 to 36 individual dosages daily, preferably 2 to 24 times daily, more preferably 3 to 12 times daily, such as 5 to 8 times daily, for example around 6 times daily. Preferably, the first 2 doses are administrated simultaneously. The specific number of daily applications may be correlated to the individual way of administration and the severity of the symptom in question. The preferred treatment is a treatment where the medicament is present in the mucosal membrane as constant as possible due to the theory that the individual factors involved in the maintenance of the symptoms are constantly produced in the affected mucosal membrane during the illness. In one embodiment the pharmaceutical compositions comprising flavonoids and menthol according to the present invention are administrated in combination with a second treatment such as in combination with an antiviral treatment including treatment against influenza such as TaMiFlu®, treatment against rhinitis such as Picovir®; or treatment with antibodies against streptococcus; or treatment with interferons (alpha, beta or gamma) and mixtures thereof. The antiviral agents include TamiFlu or other neuraminidase inhibitors or rimantadine or antibodies against RSV. The second treatment may also be a metal complex or metal salt (see herein above). In another embodiment of the present invention the second treatment is administration of an anti-microbial agent. Preferably, the anti-microbial agent is distinct and specific, however the anti-microbial agent may also be a general antibiotic. In particular, an anti-microbial agent may be administrated to treat conditions associated with bacterial infections. The effective dosage of metal complex or metal salt depends on the particular metal complex or metal salt and the clinical condition to be treated. In general, however in the range of 0.1 mg to 1000 g metal is adminstrated daily. Preferably the metal is zinc. The effective dosage of Zinc depends upon the form of zinc component which is adminstrated. Preferably between 0.1 mg and 500 mg Zn2+ is administrated, such as between 0.5 mg and 250 mg, for example between 1 mg and 150 mg, such as between 5 mg and 100 mg, for example between 10 mg and 50 mg per dose. If the zinc compound is ZnGluconate, preferably between 5 mg and 1000 mg, more preferably between 10 mg and 500 mg, even more preferably between 10 mg and 100 mg, yet more preferably between 20 mg and 80 mg, even more preferably between 30 mg and 70 mg, most preferably around 50 mg ZnGluconate is administrated per dose. If-the zinc compound is PolaPreZinc, preferably between 1 mg and 500 mg, more preferably between 5 mg and 250 mg, even more preferably between 10 mg and 100 mg, most preferably around 25 mg. The administration of a flavonoid, menthol and metal salt and/or metal complex may be either simultaneously as separate or combined formulations or it may be sequential in any order. It is preferred to present flavonoids and/or menthol and/or metals according to the present invention in the form of a pharmaceutical formulation. Accordingly, the present invention further provides pharmaceutical formulations, either as a single composition or as a kit of parts, for medicinal application, which comprises a flavonoid and menthol as well and optionally a metal salt and/or metal complex according to the present invention or a pharmaceutically acceptable salts thereof, as herein defined, and a pharmaceutically acceptable exipient therefore. The pharmaceutical formulations according to the present invention may be prepared by conventional techniques, e.g. as described in Remington: The Science and Practice of Pharmacy 1995, edited by E. W. Martin, Mack Publishing Company, 19th edition, Easton, Pa. The phamaceutical formulation may have any form known to the person skilled in the art. For example the pharmaceutical formulation may be in the form of a solution, dispersion, emulsion, suspension, bioadhesive and non-bioadhesive gel, powder, micropheres, tablets, lozenges, chewing tablets, chewing gum, pills, capsules, cachets, suppositories, dispersible granules, drops, sprays, aerosols, insufflators, inhalators, patches, a lollipop, ointment, lotion, cream, foam, implant, syrup or balm. The skilled person may select the appropriate administration form based on the common knowledge within the field of delivery systems for pharmaceuticals. It is believed that the optimal effect is obtained by a direct topical application of the flavonoids and menthol according to the present invention on the mucosal membrane in question. Accordingly, it is preferred that the administration is topical administration directly to the mucosal membrane, more preferably, to the-mucosal membrane of the upper and/or lower respiratory tract and/or of the eyes, even more preferably the mucosal membrane of the oral cavity. The formulation should generally be distributed to a major part of the mucosal involved in the specific condition or symptom to be treated. In a preferred embodiment of the invention the pharmaceutical composition is useful for oral administration. Hence, it is preferred that the pharmaceutical composition is selected from the group consisting of lozenges, troches, capsules, syrups, tablets, lollipops, solutions, dispersions, suspensions, powders, micropheres, chewing tablets, chewing gums, sprays and pills. It is also preferred within the present invention that the pharmaceutical composition is a slow-release composition, i.e. that the release of active ingredients of the composition lasts for for example 1 min to 24 hours, such as for 1 min to 12 hours, for example from 1 min. to 6 hours, such as from 1 min to 1 hour. In a preferred embodiment of the invention the pharmaceutical composition is lozenges. The pharmaceutical composition according to the present invention usually comprise pharmaceutically acceptable exipients, which can be either solid or liquid. Preferably, such pharmaceutically acceptable exipients are not therapeutically active ingredient, but rather said exipients may be one or more substances which may act as diluents, flavouring agents, solubilisers, lubricants, suspending agents, binders, preservatives, wetting agents, tablet disintegrating agents, or an encapsulating material. Such exipients include pharmaceutical grades of mannitol, lactose, starch, magnesium stearate, sodium saccharine, talcum, cellulose, glucose, lactose, pectin, dextrin, starch, gelatin, sucrose, magnesium carbonate, tragacanth, methylcellulose, sodium carboxymethylcellulose, a low melting wax, cocoa buffer, and the like. Menthol is not regarded an exipient wihtin the meaning of the present invention. Preferably, at least one pharmaceutically acceptable exipient is Magnesium stearate. In addition, the pharmaceutical acceptable exipients may be colorants, flavours, stabilisers, buffers, artificial and natural sweeteners, dispersants, thickeners, solubilising agents, and the like. In powders, the exipient is preferably a finely divided solid, which is a mixture with the finely divided active components. In tablets, the active components are mixed with the exipient having the necessary binding capacity in suitable proportions and compacted in the shape and size desired. The powders and tablets preferably contains from one to about seventy percent of the active-compound. Formulations suitable for topical administration in the mouth include lozenges comprising active agents in a flavoured base, usually sucrose and acacia or tragacanth; pastilles comprising the active ingredient in an inert base such as gelatin and/or glycerin and/or sucrose and/or acacia; and mouthwashes comprising the active ingredient in a suitable liquid carrier. In one preferred embodiment the lozenges comprise sorbitol. The compounds of the present invention may be formulated for nasal administration. The solutions or suspensions are applied directly to the nasal cavity by conventional means, for example with a dropper, pipette or spray. The formulations may be provided in a single or multidose form. In the latter case of a dropper or pipette this may be achieved by the patient administering an appropriate, predetermined volume of the solution or suspension. In the case of a spray this may be achieved for example by means of a metering atomizing spray pump. The compounds of the present invention may be formulated for aerosol administration, particularly to the respiratory tract and including intranasal administration. The compound will generally have a small particle size for example of the order of 5 microns or less. Such a particle size may be obtained by means known in the art, for example by micronization. The active ingredient is provided in a pressurized pack with a suitable propellant such as a chlorofluorocarbon (CFC) for example dichlorodifluoromethane, trichlorofluoromethane, or dichlorotetrafluoroethane, carbon dioxide or other suitable gas. The aerosol may conveniently also contain a surfactant such as lecithin. The dose of drug may be controlled by a metered valve. Alternatively the active ingredients may be provided in a form of a dry powder, for example a powder mix of the compound in a suitable powder base such as lactose, starch, starch derivatives such as polyvinylpyrrolidine (PVP). The powder carrier will form a gel in the nasal cavity. The powder composition may be presented in unit dose form for example in capsules or cartridges of e.g., gelatin or blister packs from which the powder may be administered by means of an inhaler. Surprisingly, the present invention discloses that even though common cold is usually caused by an infection of the upper and/or lower respiratory tract, it can be treated effectively by topical administration directly to the mucosal membrane of the oral cavity. Since administration directly to the mucosal membrane of the oral cavity is very convenient for the individual to be treated, it is a considerable advantage of the present invention that administration can be performed directly to said mucosal membrane. In addition, the present invention discloses that allergic rhinitis also can be treated by applying the compounds according to the present invention directly to the musocal membrane of the oral cavity. Accordingly, the compounds according to the present invention are preferably formulated as lozenges, chewing tablets, chewing gum, drops, sprays and aerosols, which can be applied directly to the mucosal membrane of the oral cavity. Most preferably, the compounds according to the present invention are formulated as lozenges, which can be directly applied to the mucosal membrane of the oral cavity. The individual in need of a treatment according to the invention could be any individual, however preferably, such individual is a human being. The individual will generally have a score relating to symptoms based on the score system as disclosed in Patients diary, (see examples) of at least 4 to 5, such as at least 6, preferably, at least 10, more preferably the patient would have a score of at least 15, whereas an individual with a score of 3 or less is not to be regarded as sick. Generally speaking a score around 5 to 6 or lower will allow the person to continue his/her work. In a further aspect of the invention, the treatment results in a decrease in the severity of symptoms corresponding to a decrease of score as measured according to patients diary herein of at least 15% within 24 hours, such as least 25%,.more preferably of at least 30% in 24 hours from the start of the treatment. After 48 hours of treatment the scores is preferably decreased with at least 20% in 48 hours, such as with at least 30%, for example with around 40% to 60%, more preferably with at least 40%, yet more preferably with at least 50%, even more preferably with at least 60%, yet more preferably at least 70%, even more preferably at least 75% in 48 hours from the start of the treatment. 72 hours of treatment preferably results in a decrease of score as measured according to Patients Diary herein of at least 30%, preferably at least 40%, more preferably at least 50%, even more preferably at least 55%, yet more preferably at least 59%, even more preferably at least 65%, yet more preferably at least 70%, even more preferably at least 80%, yet more preferably at least 85%, even more preferably at least 90% in 72 hours from the start of the treatment. However, the preferred decrease in symptom score is dependent on the condition relating to common cold to be. treated, the scheme of treatment and the individual patient. It is in particularly preferred that at least one symptom, preferably at least 2 symptoms, more preferably at least 3 symptoms selected from the group consisting of clogged nose, rhinorrhea, coughing, headache, sneezing and sore throat are essentially eliminated after 72 hours of treatment. Flavonoids are known to possess anti-oxidative properties, and according to one further aspect, the flavonoid is a flavonoid having a singlet Oxygen Quenching measured as the rate constant of O2 quenching K of from 104 to 109 M−1 s−1. Preferably, the rate is 104 to 106 M−1 s−1. The singlet oxygen quenching can be measured using a variety of solvents known to the person skilled in the art. Preferably, the solvent is selected from the group consisting of CD3OD, a mixture of CCl4 and CH3OH of 1:3 and CH3CN. EXAMPLES Example 1 Methods Virus Titrations Rhinovirus 1A, rhinovirus 15 and rhinovirus 39 were titrated according to the tetrazolium salt (MTS)-method (Berg et al., 1990) (Hansen et al., 1989)). WISH cells were seeded in a micro tray at 3000 cells per well and incubated at 37° C., 5% CO2 overnight; the following morning the medium was replaced with 10-fold dilutions of either rhinovirus 1A, rhinovirus 15 or rhinovirus 39, respectively, in fresh medium and the trays were incubated 4-5 days at 33° C.; a microscopical examination confirmed that the CytoPathogenic Effect (CPE) was fully developed (CPE equal to 100%). The minimal amount of virus (i.e.: the highest dilution.of the virus in question) which produced 100% destruction was used as “challenge virus” in the subsequent experiments. To quantitate the CPE in terms of % destruction, MTS (Berg and Owen, 2003) was added to all cultures and after 3 h incubation at 37° C. (without CO2) the trays were read in a scanner as previuosly described (Berg et al., 1990). Control cell cultures, that were not infected with virus, were included in the experiment; the latter gave the highest OD as these cells were not damaged; depending on the concentration of virus added to the different wells, the OD492 varied, accordingly: 100% CPE yielded a low OD(<0.200); 0% CPE corresponding to no infection at all (controls cell) gave a high OD (>1.200). Interferon Titration Interferon titration was performed as follows (cf. Berg et al., 1990): 3.000 WISH cells were seeded in a microtray and on the following morning, the medium was replaced with 2-fold dilutions (from a 0-30 units/ml stock solution) of HuIFN-α-2b (Intron A) in fresh medium comprising 2% serum. After incubation overnight, the medium was replaced with fresh medium comprising challenge virus and incubated at 33° C., 5% CO2 for 3-5 days and processed further as described in Example 2. Example 2 FIGS. 1A, 1B, 2A, and 2B Experiment: 1 g pure Menthol(−) from Sigma was dissolved into 3 ml 100% Ethanol and kept at 4° C. (Menthol stock solution). Japanese peppermint oil (PPO) was produced each time from the bottle(stored at 4° C. from the supplier (local hospital pharmacy(RH)). The two stock solutions were used at dilutions (final) as indicated in the text/figures. 1:800 dilutions of Menthol(−) were added to interferon dilutions on confluent monolayer cultures yielding the interferon units/ml as indicated in FIG. 1A and 1B and rhinovirus, RHV-T-39 was added at 10−2 dilution (FIG. 1A) or 10−2,5 (FIG. 1B) diluted from a virus stock preparation of RHV-39 and the cells were incubated at 33° C. for 3-4 days until control cultures infected with the virus alone yielded 100% destruction as seen in a microscope; at that time MTS (3-[4,5-dimethylthiazol-2-yl]-5-[3-carboxymethyloxyphenyl]-2[4-sulphonyl]-2H-tetrazolium)/PMS (phenazine methosulfate) was added and the dehydrogenase in the intact cells produced a color which subsequently was measured in an ELISA scanner as previously described(Hansen et al., 1989; Berg et al., 1990). The results were graphed with the concentration of interferon on the horizontal scale and the OD492 readings on the vertical scale. Results: The lower curve (RHVT39 in FIG. 1a) illustrates the variation of the virus infection in the individual wells. As can be seen the OD-level is around 0.15 corresponding to a 50-fold reduction in the signal compared to non-infected control cell (black triangle: Cell control(-IFN)); upper curve). Conclusion: The presence of Menthol yields a significant protection amounting to 10-15% compared to uninfected control cells(cf. protection levels at IFN=0 units/ml); At the interferon range between 0 and 8 units/ml the interferon curve+menthol is significantly above the interferon curve, demonstrating a specific potentiation. Similar results are also seen at a lower virus concentration (10−2,5—FIG. 1b). To further elucidate the action of menthol on the growth of human rhinoviruses the following experiments was performed: monolayers of WISH cells in microtrays were titrated with rhinoviruses in the presence or absence of menthol at various dilutions, respectively, cf. FIG. 2A: At a dilution of 1:800 (made from the menthol stock solution described above) there was a significant increase in the protection as the menthol curve is located at a significant higher level at the dilution range of the virus (102-103), corresponding roughly to a 50% increase in protection compared to virus controls receiving no menthol, at all. This finding was reproducibly found, cf. for example FIG. 2B displaying similar result from a subsequent experiment. The protection was seen with all three rhinoviruses employed (RHV 1A, 17, and 39A), cf. (Berg et al., 2003) Conclusion of FIGS. 1A -2B: The above described experiments demonstrate that menthol has a direct effect on the growth of rhinoviruses, per se, and thus can be considered to exert antiviral activity in man infected with rhinoviruses or other related upper respiratory viruses known to induce the common cold syndromes. Furthermore, it also indicates that the natural interferon system, known to be activated in man during common cold infections (Cate et al., 1969), can be potentiated further, much in the same way as described recently by Berg et al. (Berg et al., 2001). Example 3 FIG. 3A, 3B, and 3C To compare Japanese peppermint oil (PPO) with menthol a series of analog experiments as described in the preceding paragraphs were executed: monolayers of WISH cells in microtrays were titrated with rhinoviruses in the presence or absence of PPO at various dilutions in PBS (phosphate bufferede saline) of standard stock solutions of Japanese Peppermint Oil in 95% alcohol (supplied from the Rigshospitalets Pharmacy, Denmark) without any success as it turned out that PPO (diluted 1:100 in PBS) is rather toxic to WISH cells. Furthermore, dose-response curves between virus dilutions and dilutions of PPO in PBS proved without any meaning as no systematic decrease or dependency could be observed. The problem was solved when no pre-diluted PPO was added directly into the cell cultures infected with rhinoviruses. In stead, reproducible and meaningful results were obtained when the cultures were incubated with an extra microtray containing specific dilution of PPO in water (both trays were wrapped together in plastic foil and incubated in a small box with 5% CO2/water at 33° C.). Apparently, the specific partial pressure of the PPO from the PPO-solution produced a certain amount of “PPO-gas”, which in turn was absorbed by the relevant cell cultures infected with rhinovirus cultures, without causing toxic problems, per se in control cell cultures. Thus, microtrays filled with 200 μl of with standard PPO diluted 1:1000 in water incubated together with the microtray with cells and viruses proved to be very efficient when a non-toxic PPO-enviroment was to be established in the cell cultures infected with virus. The PPO treated wells had reproducibly a low, but distint odour of PPO after this treatment. The results from such an experiment are shown in FIG. 3A: Two identical microtrays containing exactly the same virus dilutions in the appropriate wells are processed identically; one tray is incubated in an closed box containing no PPO but 5% CO2 at 33° C.; the other microtray is incubated together with a microtray filled with 200 μl PPO diluted 1:1000 in each well; both microtrays were wrapped together with plastic film and incubated in a closed box at the same conditions as the former box until a distinct CPE has developed in the control cell cultures (after 3-4 days) and processed using the MTT/MTS-PMS technigue as described previously (Berg et al., 1990; Berg et al., 2001; Berg et al., 2003) and below. As expected the standard rhinovirus curve (HRV control) rises as a steep curve together with the increase in the dilution of the virus indicating that the virus infection depends on the innocculum, per se. At 103.5 dilution it looks as no infection occurs, However, the parallel virus titration curve, in the presence of PPO 1:1000 (in the “empty” microtrays) proves to have a very dramatic influence on the production of virus, per se, as full production of virus now occurs irrespective of the dilution of the added virus; thus, the minute amount of PPO—received in a gaseous form by the wells containing the infected cells—is, indeed able to potentiate the production, remarkably. This phenomenons has not previously been described in the literature as far as PPO and Rhinovirus is concerned. To elucidate if PPO should any influence on the interferon system, per se, a standard interferon titration was performed with rhinovirus and WISH cells (Berg et al., 2001) in the presence or absence of PPO-cf. above described experiment, as seen in FIG. 3B and 3 C; the results demonstrate directly that PPO also depresses the IFN-system, per se, especially at lower concentration range (i.e.: <10 units/ml) depending on the challenge virus concentration employed (cf. 10−2 vs. 10−2.5). Similar results were observed using different vira (HRV 1A or HRV 14). It is therefore likely that other RNA viruses, in particular RNA viruses belonging to the respiratory viruses wil react similarly to exposure to PPO. Conclusions: Japanese Peppermint oil (PPO) increases the growth of rhinovirus 39 and other rhinoviruses and down-regulates the protective action of the natural, human leukocyte interferon system. Example 4 FIGS. 4A, B,C,D, Treatment of Common Cold Patients In order to evaluate the new and surprising, in vitro, findings several studies were performed in common cold patients infected naturally. These studies had the objective to examine if the marked difference from the in vitro studies between PPO and Menthol also would be reflected in, in vivo, studies. The studies were undertaken essentially as described in patent application WO 02/09699, which is hereby incorporated by reference in its entirety. The patients were treated with either menthol lozenges or PPO lozenges. Menthol Lozenges 50 mg Troxerutin 25 mg Zn Gluconate 4-5 mg (−) menthol 882 mg sorbitol 10 mg magnesium stearat PPO Lozenges 50 mg Veneruton© 25 mg Zn Gluconate 4-5 mg (−) menthol882 mg sorbitol 10 mg magnesium stearat In order to evaluate the effect of treatment the following Patients Diary was filled in by the patients and symptom score was calculated. Patients Diary This scheme should preferably be filled out in the evening. How are your current condition with regard to the symptoms below. In the scheme below, please state the strength of your symptoms today by inserting an X at the appropriate place: every symptom should have points: 0 means that you have not had any symptoms at all; 4 means that you have had the worst symptoms available; etc. 0=no symptoms, 1=a minimum of symptoms; 2=unpleasant symptoms; 3=considerably unpleasant symptoms; 4 =very unpleasant symptoms Symptom points 0 1 2 3 4 Cough Headache Hoarseness Nasal discharge Sneezing Nasal obstruction Sore throat Irritated throat Malaise Sore muscles Fever Have you had any side effects of the treatment? Yes No Specify Do you also take any other medical treatment or other kinds of treatment apart from this test treatment? Yes No Specify The scheme above may preferable be used for identifying persons in need of a treatment according to the invention and to compare the effect with other treatments or placebo. A total score of 3 to 5 or less is-regarded to be a normal condition. Most of the patients included in this section have been treated at Doctor's Office within 24-30 h after the onset of the classical common cold symptoms; preferentially, patients with fewer ar allergic rhinitis or the like were excluded from these studies. Each patient was instructed to fill out the patients diary every day (day 0=1st visit to the Doctor's Office) and to follow the mode of administration: one lozenge should be applied on or under the patient's tongue and it should melt in a minimum period of 4-5 min. (no fluid or food should be taken the next 15-20 min.) If necessary, the patient could take the next lozenge after 30 min.; a total number of 57 lozenges per day was equal to the maximal dose per day. Last lozenge should be taken just before bedtime. Treatment was in general continued for 3 to 4 days. A few patients—who are not included in the enclosed figures as they reported back by telephone—expressed a surprisingly fast recovery after treatment with menthol-lozenges, as already less than 5-6 of the menthol-lozenges stopped the rhinoea and sore throat—this effect was not observed with similar patients treated with the PPO-lozenges. To further examine quantitatively the efficacy of the treatment with Menthol-lozenges common cold patients who all had reported to the Doctor's Office within 24-30 h subsequent to the appearance of the typical symptoms (no fewer, beginning rhinoea, sneezing, etc.) were treated for 3-4 days with Menthol lozenges as described above. The patients returned their diaries and the specific symptoms scores (SS) were evaluated as shown in FIG. 4A. The following results were noted: FIG. 4A shows the symptoms score of 3 patients treated wiht menthol lozenges, where treatment was initiated 24 h post infection (p.i.) Table 1. Reduction in symptom score (SS) using menthol-lozenges (cf. FIG. 4A) reduction in SS after 1 day treatment=32% reduction in SS after 2 days treatment=77% reduction in SS after 3 days treatment=90% These results are more favorable compared to an earlier study with a group of similar patients treated with the PPO-lozengers using a similar adminstation regime (see table 2 and FIG. 4E). This study is described in detail in previous patent appl. No. WO 02/09699, example 7. 8 patients were treated with PPO-lozenges without Zn2+. 12 patients were treated with PPO-lozenges. Treatment was initiated 24-36 h p.i. The symptom score of the above-mentioned group of 3 patients (treatment initiated 24h p.i. ) is also displayed in FIG. 4B, together with a group of 2 patients, (treatment initiated 48h p.i). As can be seen both groups have a similar 90% reduction in SS at day 3. Allergy and treatment initiated 7 days p.i. change dramatically the outcome, and are therefore routinely excluded in the usual protocol. The two groups of patients in FIG. 4B were further examined in a group of 5 (shown in FIG. 4C) with regards to differential symptom scores: it appears that 3 symptoms are 100% eliminated at day 3 after treatment with menthol-lozenges. This was not observed with a parallel treatment using PPO-lozenges, cf. FIG. 4D, where some symptoms remains after 3 days treatment. Tabel 2. Reduction in symptom score (SS) using PepperMint Oil (PPO)-lozenges (cf. FIG. 4E) reduction in SS after 1 day treatment=34% reduction in SS after 2 days treatment=71% reduction in SS after 3 days treatment=80% Furthermore, the variation in SS between the two groups treated with menthol- or PPO-lozenges, respectively (compare results of FIGS. 4D and 4E) were significantly smaller in the menthol-treated group as a more constant and fast response was noted; An additional advantage of the menthol-lozenges is that the metal taste from the ZnGluconate was practically eliminated in the menthol lozenges. Conclusion: The In vitro findings indicate that Menthol has specific antiviral effects vs. rhinoviruses (-1A, -14, and -T39). These findings may explain the reason for ImmuTroxZn-Menthol lozenges appear to be more efficient compared to ImmuTroxZn-PPO lozenges in the treatment of common cold. Example 5 One patient who experienced the usual common cold symptoms (incl. a minor fever) was treated with a special lozenge containing no Zinc, a 3× higher content of Troxerutin than the Menthol-lozenge of example 4 (150 mg per lozenge) and 5 mg Menthol (ImmuTrox(150 mg)Menthol(5 mg)). The administration was performed as described in example 4. After the first two lozenges the sore throat disappeared within 30 min.; coughing and rhinitis decreased substantially within 2-3 h; a total of 4 lozenges were applied the first day with and the treatment continued the following two days (4 lozenges per day): more than 80-90% of the usual symptoms were absent at day 3. Conclusion: Lozenges comprising only Troxerutin and Menthol are also efficient in the treatment of common cold. Example 6 Male patient (MT) allergic to certain grass species (Alopecurus pratensis, etc.) presented also a common cold at the Doctor's Office 3-4 days after the allergy and the cold had started; the patient was unhappy about all the rhinoea and was coughing. The patient was treated with ImmuTroxZnMent lozenges (50 mg Troxerutin, 25 mg Zn Gluconate, and 5 mg Menthol) as described in example 4 and returned the protocol 3-4 days later; on the day of initiation of treatment the SS was 25; 24h later the SS was reduced to 7, 48 h later SS was reduced to 1; 72 h later: SS=0. The patient noted that his allergy was significantly reduced. Several weeks later the patient reported that his grass allergy had changed and that it was no longer so bothersome. Conclusion: it appears that the ImmuTroxZnMen lozenges also has a direct anti-allergic effects. This observation later has been reported by other patients suffering from allergic rhinitis and the like. 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<SOH> BACKGROUND OF THE INVENTION <EOH>Common cold is in general initiated by viral infections by the so-called cold viruses, such as rhino virus, corona virus, adenovirus, coxsackie virus, RS-virus, echovirus or other cold viruses. In average all human beings suffer 2 to 3 times a year from infections in the upper respiratory passages, such as cold and flu. In general, in Denmark the majority of common colds occurring in September, October and November are caused by rhinovirus infection, whereas the majority of common cord occurring in January, February and March are caused by Coronavirus infections. In addition, allergic syndromes, for example asthma, may be initiated by common cold viruses, especially the rhinovirus. Recent observations from a polymerase chain reaction (PCR)-study (Johnston, 1993) with naturally rhinovirus infected persons indicates that the actual range for rhinovirus infections involved in common cold syndrome probably is at least twofold higher, compared to findings obtained via the traditional cell culture techniques (40%). This indicates that up to 70-75% of all patients suffering from common colds have a rhinovirus infections ongoing either as a single infection or co-infection (Spector, 1995). It has been estimated that the average pre-school child experiences 610 upper respiratory infections or common colds per year whereas the average adult experiences 24 (Sperber, 1989). The effects of the common cold can be uncommonly disruptive, forcing otherwise normal persons to stay away from work, school, etc. Individuals who are at increased risks, such as individuals suffering from bronchitis or asthma, may also experience a life-threatening exacerbation of their underlying conditions. The average annual expenditure for various cold treatments exceeds USD 2 billion in the United States, alone (Spector, 1995); in the EU a similar figure is expected. Unfortunately, research in development of novel strategies to treat common cold is complicated by the fact human rhinoviruses only have been reported to infect primates successfully and hence no practical animal model has been developed for rhinovirus infections (Rotbart, 2000). The development of natural and experimentally induced rhinovirus infections in normal persons are initiated by selected events, which can be considered to occur sequentially. The steps in the rhinovirus pathogenesis are believed to include viral entry into the outer nose, mucociliary transport of virus to the posterior pharynx, and initiation of infection in ciliated and non-ciliated epithelial cells of the upper airway. Viral replication peaks on average within 48 h of initiation of infection and persists for up to 3 weeks; Infection is followed by activation of several inflammatory mechanisms, which may include release or induction of interleukins, bradykinins, prostaglandins and possibly histamine, including stimulation of parasympathetic reflexes (the cytokines may counteract each other at certain levels resulting in a very complex pathway). The resultant clinical illness is a rhinosinusitis, pharyngitis, and bronchitis, which on average lasts one week (Gwaltney, 1995). Occasionally, a secondary bacterial or microbial infection may follow subsequently to the viral infection and a sustained and more serious inflammation may result. Previously, it was believed that the major part of the virus was produced in the upper nose region and excreted (Winther, 1993a). However, subsequent studies, comparing recovery of virus in nasopharyngeal wash specimens, nasal swabs and pharyngeal swabs showed that the nasopharyngeal wash specimens was consistently superior to the other two specimens in yielding virus (Cate, 1964). From a series of in-depth investigations (Winther, 1984a; Winther, 1984b; Winther, 1984c; Turner, 1984; Farr, 1984; Hayden, 1987; Winther, 1987a; Winther, 1987b; Winther, 1993b; Arruda, 1995; Winther, 1998) it was concluded that: (i) the virus was first recovered, at the highest concentrations, from the nasopharynx before it could be recovered in the upper nose region (turbinates). (ii) no evidence for rhinovirus induced damage of the surface ciliary lining of the inferior turbinate was noted which is in agreement with other investigators suggesting that the virus may be transported to the nasopharynx in the overlaying mucus by mucociliary clearence. (iii) there was a significant increase of the influx of neutrophils in the same area as in (ii) (iv) infection of the lining of the nasal cavity was not uniform after intranasal inoculation and seemed not to result in any cell damage at all, cf. (ii) above. (v) the rate of viral shedding in the nasopharynx was high by day 1 (post infection), whereas cold symptoms did not peak until day 3. The symptoms waned during the first week, but rhinovirus was present during the following 3 weeks. (vi) The increase of neutrophils correlates with the onset of symptoms, including sore throat. The symptoms include oedema-like symptoms, which in turn may trigger sneezing and coughing. It should be stressed that the highest concentration of virus can be recovered from the nasopharynx, and virus usually appears on the turbinate(s) one or two days later, despite the fact that virus is innoculated via the nose (in volunteers). No visible damage of the cell lining in the upper airways was ever demonstrated. Furthermore, as “sore throat” usually develops simultaneously with the appearance of virus in the nasopharynx it can be reasoned that “signal molecules” or the like (Van Damme, 1988) will be made by the relatively few rhinovirus cells infected and that these “cytokinelike molecules” subsequently may activate the “lymphatic ring”—which is located just beneath the nasopharynx—leading to the well-known sore throat, which in turn triggers a complex pattern of inflammatory reactions, involving an array of different interferons and cytokines the interaction of which is currently under in-depth investigation. Some of these factors, such as for example II-1, induce fever in patents. Bradykinines per se may be responsible for the sore throat, which is frequently associated with common cold. The fact that interferon is known to be part of the non-specific innate immune response against viral infections in man has lead to several publications as a number of groups have investigated how much interferon is produced locally during viral infections of the upper-airways. One of the earliest and probably most thorough, in vivo, investigations in man was performed by Cate et al. (Cate, 1969) on volunteers (healthy adult males from federal correctional institutions in USA). The authors were able to demonstrate, that most of the persons involved produced interferon (as demonstrated in nasal washings) during common colds at a level, which at least theoretically should have been enough to block the viral infection, per se. It has been demonstrated in a recent publication, that the immune system also takes “active part” in the spread of the inflammatory actions since experimental evidence supports the notion that rhinovirus may use some of the effector cells from the immune system as a mean for spreading the inflammatory reactions to the lower airways,(Gern, 1996) via initiation of local TNF-alpha production. It is tempting to speculate that the allergic rhinitis is initiated via this mechanism as it has been found that the pathogenesis for asthma is linked to local TNF-alpha production (Broide et al.1992). Several quarters have thus argued that the asthma syndromes are rhinovirus manifestations of post-infectious events triggered by an array of different cytokines in connection with a “switch” between the Th1 vs. Th2 response (Gern, 1999; Winther, 1998; Grünberg, 1999). Generally speaking, air-way infections or allergic rhinitis and/or asthma may pose a serious health problems as it can be potentially life-threatening for susceptible groups such as elderly people with chronic airway problems or persons suffering from a deficient immunity, such as AIDS-patients, cancer patients etc. Thus, simple and effective methods of treating these symptoms/syndromes and possibly also the underlying infections would be of immense importance. Viral and/or other microbial infections are known to initiate a complex inflammatory response (Ginsburg, 1988) from the patient which probably is mediated by several groups of responder cells including the neutrophile granulocytes, which are specifically increased during a cold. The latter represents approximately more than 95% of all the effector cells. Each min. about 6-9 millions neutrophiles enter the upper-airways and slowly pass down the interior surfaces encompassing the upper airways. It may be assumed that the neutrophiles, which are able to release very aggressive enzymes and toxic substances upon proper stimulation will keep the bacterial load of the upper-airways to an acceptable level. The small numbers of S. pyogenes or S. aureus found in nasopharynx, which otherwise is almost sterile, may stimulate the neutrophiles via the so-called super-antigens to a certain degree thereby limiting the numbers of bacteria in said areas (dynamic equilibrium/symbiosis). According to Ihrcke and co-workers (Ihrcke, 1993) the very early steps in a virus infection (or any other abnormality in the cell lining) can be related to the content and metabolism of heparan sulfate proteoglycan (the major proteoglycan associated with intact endothelial cells). The first element of the model derives from the observation that heparan sulfate is released from the intact endothelial lining of blood vessels during the very first step in an inflammatory response initiated by a viral infection. Accordingly, this loss may seriously compromise the vascular integrity and result in a local edema attracting further neutrophiles via the up-regulation of ICAM-1 markers on the endothelial cells increasing the inflammatory response further. Thus, in a separate experiment, activated neutrophiles were able to release 70% of all cell-associated heparan sulfate proteoglycan within one hour via the subsequent release of heparanase. One important function of heparan sulfate is the maintenance of the endothelial cell integrity. Loss of heparan sulfate partially abrogates the barrier properties of the endothelium and contributes to the edema and exudation of plasma proteins that characterise inflammation. It has previously been attempted to treat common cold using flavonoids. WO 02/09699 describes treatment of common cold and similar conditions, such as hayfewer using flavonoids, such as troxerutin or veneruton, either alone or in combination with metals. Flagrant used include peppermint oil. U.S. Pat. No. 6,596,313 describes compositions for oral administration that may be useful for treatment of common cold. The compositions comprise extracts from various plants. The document mentions that menthol may be used as a flagrant. The effect of a composition comprising menthol is however not disclosed. U.S. Pat. No. 6,592,896 describes oral pharmaceutical compositions comprising plant extracts. The document mentions that menthol may be used as a flagrant. The compositions may be useful for treatment of common cold. The effect of a composition comprising menthol is not disclosed. WO 01/03681 describes treatment of viral infection, including infections related to common cold with a variety of flavonoids. WO 01/49285 decsribes a medicament comprising flavonoid(s). The medicament may be useful for treatment of common cold, however this is not demonstrated.
<SOH> SUMMARY OF THE INVENTION <EOH>It is an objective of the present invention to provide new and efficient pharmaceutical compositions for treatment of common cold and similar conditions. Interestingly, the present invention surprisingly discloses that the choice of flagrance is very important. In particular, the present invention demonstrates a surprising effect amongst different commonly used flagrance additives. Interestingly, pharmaceutical compositions comprising flavonoid and purified menthol are more efficient than similar compositions comprising other flagrances in the treatment of common cold and related conditions. Hence, it is a first objective of the present invention to provide pharmaceutical compositions comprising i) one or more purified flavonoids; and ii) purified menthol; and iii) pharmaceutically acceptable expients. It is a second obejctive of the present invention to provide use of one or more purified flavonoids and purified menthol for the preparation of a pharmaceutical composition for the treatment of a clinical condition or symptoms of a clinical condition in an individual in need thereof. It is a third objective of the present invention to provide methods of treatment of a clinical condition in an individual in need thereof, comprising administering to said individual the pharmaceutical composition according to the invention. It is a further objective of the present invention to provide a medicament for treating a clinical condition comprising purified flavonoid and purified menthol as active ingredients.
20050422
20090908
20060706
62410.0
A61K317048
0
SOLOLA, TAOFIQ A
PHARMACEUTICAL COMPOSITIONS COMPRISING FLAVONOIDS AND MENTHOL
SMALL
0
ACCEPTED
A61K
2,005
10,532,377
ACCEPTED
Collapsible hammock stand
A hammock stand has a plurality of legs, support rods, and a cross brace that couples at least one leg to at least one of the support rods such that the hammock stand collapses in a single movement.
1. A hammock stand comprising four legs, four support rods, and a pair of cross braces, wherein the legs, the support rods, and the cross braces are coupled to each other such that the hammock stand collapses in a single movement in which two of the four legs approximate each other as two of the support rods pivot towards each other. 2. The hammock stand of claim 1 wherein a first and a second of the four legs are rotatably coupled to each other. 3. The hammock stand of claim 2 wherein a first support rod is rotatably coupled to the first of the four legs and wherein a second of the support rods is rotatably coupled to the second of the four legs. 4. The hammock stand of claim 3 wherein the second of the four legs is coupled to the first of the support rods via a connector rod. 5. The hammock stand of claim 4 wherein the connector rod releasably engages with the first of the support rods and forms an obtuse angle with the second of the four legs when the hammock stand is in an open configuration. 6. The hammock stand of claim 4 wherein the pair of cross braces is rotatably coupled to each other, and wherein at least one of the cross braces is rotatably coupled to the first of the four legs, and rotatably and slidably coupled to a third of the support rods. 7. The hammock stand of claim 1 further comprising a body support that is coupled to at least two of the four support rods. 8. The hammock stand of claim 1 further comprising a flexible element that couples the first of the four legs with a third of the four legs and that facilitates collapsing of the hammock stand when the flexible element is pulled upwards relative to the ground and when the hammock stand is in an open configuration. 9. The hammock stand of claim 8 wherein the flexible element comprises a sheet of fabric. 10. The hammock stand of claim 9 wherein the sheet of fabric further comprises a handle. 11. A hammock stand comprising: a first leg, a second leg, a third leg, and a fourth leg; a first support rod, a second support rod, a third support rod, and a fourth support rod, wherein the first, second, third, and fourth support rod are rotatably coupled to the first, second, third, and fourth leg, respectively; a first pair of cross braces rotatably coupled to each other, wherein one of the first pair of cross braces is rotatably coupled to the first leg and third support rod and wherein the other of the first pair of cross braces is rotatably coupled to the third leg and first support rod; a second pair of cross braces rotatably coupled to each other, wherein one of the second pair of cross braces is rotatably coupled to the second leg and fourth support rod and wherein the other of the second pair of cross braces is rotatably coupled to the fourth leg and second support rod; and a first connector rod, a second connector rod, a third connector rod, and a fourth connector rod, wherein the first, second, third, and fourth connector rod rotatably couples the first leg and the second support rod, the second leg and the first support rod, the third leg and the fourth support rod, and the fourth leg and the third support rod, respectively. 12. The hammock stand of claim 11 further comprising a body support that is coupled to the first, second, third, and fourth support rod. 13. The hammock stand of claim 12 further comprising a sheet of fabric coupled to the first, second, third, and fourth leg, and that facilitates collapsing of the hammock stand when the sheet of fabric is pulled upwards relative to the ground and when the hammock stand is in an open configuration. 14. The hammock stand of claim 13 wherein the sheet of fabric further comprises a handle. 15. A collapsible hammock stand having a plurality of legs, a plurality of support rods, and at least one pair of cross braces coupling at least one leg to at least one of the support rods such that the hammock stand collapses in a simultaneous front-to-back and side-to-side motion. 16. The collapsible hammock stand of claim 15 wherein at least one leg is coupled to at least one support rod via a connector rod. 17. The collapsible hammock stand of claim 15 having four legs, four support rods, and two pairs of cross braces, wherein the first pair of cross braces couples at least one leg to at least one support rod, wherein the second pair of cross braces couples at least another one of the legs and another one of the support rods, and wherein at least two legs are rotatably coupled to each other. 18. The collapsible hammock stand of claim 17 wherein at least one of the support rods is rotatably coupled to at least one of the legs. 19. The collapsible hammock stand of claim 18 further comprising a body support that is coupled to at least two of the four support rods. 20. The collapsible hammock stand of claim 19 further comprising a sheet of fabric coupled to the first, second, third, and fourth leg, wherein the sheet facilitates collapsing of the hammock stand when the sheet of fabric is pulled upwards relative to the ground and when the hammock stand is in an open configuration.
FIELD OF THE INVENTION The field of the invention is collapsible furniture, especially as it relates to collapsible hammock stands. BACKGROUND OF THE INVENTION Hammocks enjoy great popularity in indoor as well as outdoor settings, and depending on the particular locale and/or type of use, may be set up in a permanent or temporary manner. For example, where a hammock is permanently set up on a patio, hooks or other fasteners may be installed to a post or in a wall to fasten the hammock. Alternatively, a hammock may be fixed to a tree by tying or otherwise coupling a tether to the tree. On the other hand, where a hammock is temporarily used (e.g., for only part of one day), or where permanent attachment of the hammock to a support is not desirable or possible, a hammock may be supported by a hammock stand. There are numerous hammock stands known in the art, however, all or almost all of them suffer from one or more disadvantage. For example, various retailers offer hammock stands with an arched center beam having two or more legs that support the center beam off the ground (see Prior Art FIG. 1). Hammock stands with an arched center beam are often esthetically pleasing and provide relatively good stability. However, when a person inadvertently looses balance and falls off the support, serious injury may occur due-to the position of the center beam. To avoid at least some of the problems with a center beam, tubular assemblies may be employed in which the corresponding end portions of two substantially parallel tubes are coupled to each other via a V-shaped connector in which the tip of the V-shape points upwards at an angle of about 45 degrees (see Prior Art FIG. 2). However, most tubular assemblies are esthetically less attractive and often require relatively level ground for stable support. Moreover, as hammock stands with center beam, most tubular assemblies are relatively space consuming when not in operation. To reduce the space requirements of hammock stands, a hammock stand may be reduced to separate front and back portions, wherein both the front and back portions are independently set up, and wherein the front and back portions may further be folded into a more compact configuration. Examples for such hammock stands can be found in U.S. Pat. No. 201,074 to Wheeler, or U.S. Pat. No. 260,230 to Parker, both of which are incorporated by reference herein. While such stands advantageously save space when not supporting the hammock, they typically require multiple points of attachment or contact to the ground to reliably support a person in a hammock. Alternatively, a hammock stand may also be foldably configured as described in U.S. Pat. No. 838,078 to Carbaugh, wherein a foldable frame is secured with a pair of diagonal braces. While such foldable frames allow a side-to-side reduction in space, such frames do generally not allow for both side-to-side and front-to-back folding operation. Moreover, before an operator can fold such frames, the diagonal braces typically need to be removed. In still further known configurations, hammock frames may also be collapsed. For example, U.S. Pat. No. 5,659,907 to Huang and U.S. Pat. No. 5,983,422 to Bayless describe a configuration in which the hammock frame has a foldable center beam with foldable angled support structures. Alternatively, a collapsible hammock frame may also be configured to include a pair of foldable inverted V-shaped stands that are connected to each other with a foldable lateral support as described in U.S. Pat. No. 5,046,203 to de Cuadros. While such collapsible hammock frames provide at least some space saving when not supporting the hammock, numerous disadvantages still remain. Among other things, all or almost all of the known hammock stands still require substantial space when not in operation. Furthermore, folding and unfolding of such hammock stands is often difficult, especially to an inexperienced or physically challenged user. Therefore, there is still a need to provide improved hammock stands. SUMMARY OF THE INVENTION The present invention is directed to a collapsible hammock stand with a plurality of legs, support rods, and a cross brace that couples at least one leg to at least one of the support rods such that the hammock stand collapses in a single movement. In one aspect of the inventive subject matter, contemplated hammock stands have four legs, four support rods, and a pair of cross braces, wherein the legs, the support rods, and the cross braces are coupled to each other such that the hammock stand collapses in a single movement in which two of the four legs approximate each other as two of the support rods pivot towards each other. Particularly suitable configurations include those in which a first and a second of the four legs are rotatably coupled to each other, and wherein a first support rod is rotatably coupled to the first of the four legs and wherein a second of the support rods is rotatably coupled to the second of the four legs. Such configurations may further include a connector rod that couples the second of the four legs to the first of the support rods. Especially preferred connector rods releasably engage with a support rods and form an obtuse angle with one of four legs when the hammock stand is in an open configuration. In further contemplated aspects of the inventive subject matter, the cross braces are rotatably coupled to each other to form a pair of cross braces, wherein at least one of the cross braces is rotatably coupled to the first of the four legs, and rotatably and slidably coupled to a third of the support rods. Suitable stands may further comprise a body support that is coupled to at least two of the four support rods, and may still further comprise a flexible element that couples the first of the four legs with a third of the four legs and that facilitates collapsing of the hammock stand when the flexible element is pulled upwards relative to the ground (when the hammock stand is in an open configuration). In yet another aspect of the inventive subject matter, contemplated hammock stands will have a plurality of legs, a plurality of support rods, and at least one pair of cross braces coupling at least one leg to at least one of the support rods such that the hammock stand collapses in a simultaneous front-to-back and side-to-side motion. In such configurations, it is generally preferred that at least one leg is coupled to at least one support rod via a connector rod. In particularly preferred configurations, such hammock stands will include four legs, four support rods, and two pairs of cross braces, wherein the first pair of cross braces couples at least one leg to at least one support rod, wherein the second pair of cross braces couples at least another one of the legs and another one of the support rods, and wherein at least two legs are rotatably coupled to each other. At least one of the support rods may be rotatably coupled to at least one of the legs. In a still further aspect of the inventive subject matter, a hammock stand has a first leg, a second leg, a third leg, and a fourth leg, and further includes a first support rod, a second support rod, a third support rod, and a fourth support rod, wherein the first, second, third, and fourth support rod is rotatably coupled to the first, second, third, and fourth leg, respectively; a first pair of cross braces are rotatably coupled to each other, wherein one of the cross braces is rotatably coupled to the first leg and third support rod and wherein the other cross brace is rotatably coupled to the third leg and first support rod; a second pair of cross braces are rotatably coupled to each other, wherein one of the cross braces is rotatably coupled to the second leg and fourth support rod and wherein the other of the cross braces is rotatably coupled to the fourth leg and second support rod; contemplated hammock stands further include a first connector rod, a second connector rod, a third connector rod, and a fourth connector rod, wherein the first, second, third, and fourth connector rod rotatably couples the first leg and the second support rod, the second leg and the first support rod, the third leg and the fourth support rod, and the fourth leg and the third support rod, respectively. Various objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of preferred embodiments of the invention, along with the accompanying drawings in which like numerals represent like components. BRIEF DESCRIPTION OF THE DRAWINGS Prior Art FIG. 1 is a schematic view of a known hammock stand having a center beam. Prior Art FIG. 2 is a schematic view of a known hammock stand having a tubular assembly with a V-shaped connector. FIG. 3 is a photograph showing a perspective view of a hammock frame in a semi-open configuration according to the inventive subject matter. FIG. 4 is a photograph showing a perspective view of a hammock frame in a closed configuration according to the inventive subject matter. FIG. 5 is a photograph showing a perspective view of a hammock frame with a body support and accessory sheet in an open configuration according to the inventive subject matter. DETAILED DESCRIPTION The inventor has discovered that a hammock stand can be manufactured such that the hammock stand can be collapsed in a single motion. As used herein, the term “collapses in a single movement” or “collapses in a single motion” are used interchangeably and refer to a movement in which a user need not interrupt the collapsing motion to fasten or unfasten a connector. Thus, the term “collapses in a single movement” may also include multiple sub-movements, which may or may not be separated by a pause. In one particularly preferred aspect of the inventive subject matter as shown in FIG. 3, a hammock stand 100 has a first leg 110, a second leg 112, a third leg 114, and a fourth leg 116. First and second legs 110 and 112 are rotatably coupled to each other via a hinge (e.g. rivet), and third and fourth legs 114 and 116 are rotatably coupled to each other via a hinge (e.g., rivet), wherein the point of rotation is approximately in the middle of each of the four legs. The hammock stand further includes a first support rod 120, a second support rod 122, a third support rod 124, and a fourth support rod 126, wherein the first, second, third, and fourth support rod are rotatably coupled via a hinge to the first, second, third, and fourth leg, respectively. A first pair of cross braces has cross brace 130 and cross brace 132. Cross brace 130 and cross brace 132 are rotatably coupled to each other (point of rotation is substantially in the middle of each cross brace), wherein cross brace 130 is rotatably coupled to the first leg 110 and rotatably and slidably to the third support rod 124, and wherein cross brace 132 is rotatably coupled to the third leg 114 and rotatably and slidably to the first support rod 120. A second pair of cross braces has cross brace 134 and cross brace 136. Cross brace 134 and cross brace 136 are rotatably coupled to each other (point of rotation is substantially in the middle of each cross brace), wherein cross brace 134 is rotatably coupled to the second leg 112 and rotatably and slidably coupled to the fourth support rod 126, and wherein cross brace 136 is rotatably coupled to the fourth leg 116 and rotatably and slidably coupled to the second support rod 122. Where the cross braces are rotatably coupled to the legs, it is generally preferred that the coupling is via a terminal portion of the legs (e.g., in a pad that contacts the ground). Similarly, where the cross braces are rotatably and slidably coupled to the support rods, it is generally preferred that coupling is via a sliding sleeve that further includes a rotatable connector (e.g., bolt). A first connector rod 140, a second connector rod 142, a third connector rod 144, and a fourth connector rod 146 rotatably couple the first leg 110 and the second support rod 122, the second leg 112 and the first support rod 120, the third leg 114 and the fourth support rod 126, and the fourth leg 116 and the third support rod 124, respectively. It is particularly preferred that one end of the connector rod is rotatably coupled to the leg at (or near) the end that extends beyond the point of rotation and is distal to the ground when the hammock stand is in an open configuration (see FIG. 3). With respect to the other end of the connector rod it is generally preferred that the other end is rotatably coupled to the support rod at a point above the point where the cross brace is rotatably and slidably coupled to the support rod when the hammock stand is in an open configuration. The term “open configuration” as used herein refers to the configuration of the hammock stand in which the ends of the support rods (to which a body support may be attached) are at or near their maximum distance from each other, and in which a user can rest on a body support that is coupled to the hammock stand. Consequently, the term “closed configuration” as used herein refers to the collapsed configuration in which the ends of the support rods are at or near their minimum distance from each other. For further illustration, FIG. 4 depicts an exemplary hammock stand in the closed (or collapsed) configuration. The end of the support rods 120 to 126 may further include a retainer element that is configured to receive a corresponding attachment element from a body support. Thus, it is generally contemplated that the hammock stand according to the inventive subject matter may temporarily or permanently include a body support, and all known types of body supports are contemplated suitable for use herein. For example, contemplated body supports include rope, fabric, or string-type supports, which may be fabricated from natural and/or synthetic materials. With respect to the size of contemplated body supports, it should be recognized that all sizes are suitable, and especially include sizes adapted to support one or more users (e.g. children or adults). Depending on the type of body support, it should be appreciated that the attachment element may vary considerably, and suitable attachment elements include ropes, wires, hooks, rings, a stave, etc. Consequently, the nature and size of the retainer element may vary and particularly contemplated retainer elements are those that functionally cooperate with the attachment element to at least temporarily couple the body support to the hammock stand. Thus, contemplated retainer elements include hooks, locks, snaps, etc. Therefore, while any mode of coupling is contemplated, suitable body supports are typically coupled to two, and more typically to four support rods. In further particularly preferred aspects, contemplated hammock supports will further include a sheet of fabric (optionally including a handle) that is coupled to the first, second, third, and fourth leg (most typically at a point between the point of rotation and the slidable coupling of the cross brace) to facilitate collapsing of the hammock stand when the sheet of fabric is pulled upwards relative to the ground and when the hammock stand is in an open configuration. Alternatively, the sheet may be replaced with a string (which may or may not have a handle) that is coupled to the first and third (and/or second and fourth) leg at a point between the point of rotation and the slidable coupling of the cross brace. With respect to the legs, support rods, connector rods, and cross braces of contemplated hammock stands, it should be appreciated that all of these elements may be manufactured from various materials, including metals, metal alloys, natural and synthetic polymers, and any reasonable combination thereof. However, it is preferred that the legs, support rods, connector rods, and cross braces are manufactured from black anodized aluminum tubing with a wall strength of about 1/32 inch and an outer diameter of approximately ½ inch. Where one of the legs, support rods, connector rods, and cross braces is rotatably or pivotably coupled to another one of the legs, support rods, connector rods, and cross braces, it is generally contemplated that all known manners of rotatably coupling are suitable for use in conjunction with the teachings presented herein. For example, appropriate manners of rotatably coupling include coupling of two elements via a common axis, coupling via a hinge wherein the hinge may or may not have a slidable connection to another element, coupling via a ball bearing, etc. Similarly, where one of the legs, support rods, connector rods, and cross braces are slidably coupled to another one of the legs, support rods, connector rods, and cross braces, all known slidable couplings are contemplated to be appropriate, and include a sliding sleeve, slide rails, guiding rings, etc. Furthermore, where a slidable coupling is employed, it should also be recognized that the sliding motion may be replaced with a telescoping element. Thus, it should be appreciated contemplated couplings between the legs, support rods, connector rods, and/or cross braces may be rotatable and/or slidable. Alternatively, where rotatable and slidable couplings are less desirable, it is contemplated that temporary couplings may be employed. Suitable temporary couplings include snap connectors, connectors that are secured with a pin or other removable element (e.g., screw, nut, etc.). However, it should be recognized that preferred couplings will enable a user to collapse the hammock stand in a single motion. Therefore, in one especially preferred aspect of the inventive subject matter, suitable couplings between the cross braces, legs, and support rods (which may or may not include the connector rods) will result in a quad configuration. The term “quad configuration” as used herein refers to a configurations of at least eight elements in which four pairs of elements are (directly or indirectly) pivotably and/or slidably coupled to each other to allow simultaneous movement of all of the eight elements and wherein the two elements of the pair of elements are rotatably coupled to each other (preferably around a point of rotation located in or near the middle of the element). Consequently, it should be appreciated that a hammock stand may comprise four legs, four support rods, and a pair of cross braces, wherein the legs, the support rods, and the cross braces are coupled to each other such that the hammock stand collapses in a single movement in which two of the four legs approximate each other as two of the support rods pivot towards each other. In particularly preferred configurations (see e.g., FIG. 3), a first and a second of the four legs are rotatably coupled to each other, and in yet further preferred aspects, a first support rod is rotatably coupled to the first of the four legs and a second support rods is rotatably coupled to the second of the four legs, wherein the second of the four legs may be coupled to the first of the support rods via a connector rod. Where contemplated hammock stands include a connector rod, it is especially preferred that the connector rod releasably engages with a support rod (e.g. via a bracket, and most preferably via a bracket that is coupled to the slidable connector between a support rod and a cross brace). In such configurations, the connector rod and the leg form an obtuse angle when the hammock stand is in an open configuration, thereby greatly increasing the stability of the hammock stand. In still further preferred configurations, the pair of cross braces is rotatably coupled to each other (e.g., via a point at or near the middle of the cross brace), and at least one of the cross braces is rotatably coupled to one leg, and rotatably and slidably coupled to the support rod that is on the opposite side of the one leg in the hammock stand. With respect to the body support and the flexible element (e.g., sheet of fabric), the same considerations as described above apply. Therefore, viewed from another perspective, a collapsible hammock stand may have a plurality of legs, a plurality of support rods, and at least one pair of cross braces coupling at least one leg to at least one of the support rods such that the hammock stand collapses simultaneously in a front-to-back and side-to-side motion. In such configurations, it is generally preferred that at least one leg is coupled to at least one support rod via a connector rod, and it is further preferred that such hammock stands include four legs, four support rods, and two pairs of cross braces, wherein the first pair of cross braces couples at least one leg to at least one support rod, wherein the second pair of cross braces couples at least another one of the legs and another one of the support rods, and wherein at least two legs are rotatably coupled to each other (e.g., at least one of the support rods is rotatably coupled to at least one of the legs). Thus, specific embodiments and applications of collapsible hammock stands have been disclosed. It should be apparent, however, to those skilled in the art that many more modifications besides those already described are possible without departing from the inventive concepts herein. The inventive subject matter, therefore, is not to be restricted except in the spirit of the appended claims. Moreover, in interpreting both the specification and the claims, all terms should be interpreted in the broadest possible manner consistent with the context. In particular, the terms “comprises” and “comprising” should be interpreted as referring to elements, components, or steps in a non-exclusive manner, indicating that the referenced elements, components, or steps may be present, or utilized, or combined with other elements, components, or steps that are not expressly referenced.
<SOH> BACKGROUND OF THE INVENTION <EOH>Hammocks enjoy great popularity in indoor as well as outdoor settings, and depending on the particular locale and/or type of use, may be set up in a permanent or temporary manner. For example, where a hammock is permanently set up on a patio, hooks or other fasteners may be installed to a post or in a wall to fasten the hammock. Alternatively, a hammock may be fixed to a tree by tying or otherwise coupling a tether to the tree. On the other hand, where a hammock is temporarily used (e.g., for only part of one day), or where permanent attachment of the hammock to a support is not desirable or possible, a hammock may be supported by a hammock stand. There are numerous hammock stands known in the art, however, all or almost all of them suffer from one or more disadvantage. For example, various retailers offer hammock stands with an arched center beam having two or more legs that support the center beam off the ground (see Prior Art FIG. 1 ). Hammock stands with an arched center beam are often esthetically pleasing and provide relatively good stability. However, when a person inadvertently looses balance and falls off the support, serious injury may occur due-to the position of the center beam. To avoid at least some of the problems with a center beam, tubular assemblies may be employed in which the corresponding end portions of two substantially parallel tubes are coupled to each other via a V-shaped connector in which the tip of the V-shape points upwards at an angle of about 45 degrees (see Prior Art FIG. 2 ). However, most tubular assemblies are esthetically less attractive and often require relatively level ground for stable support. Moreover, as hammock stands with center beam, most tubular assemblies are relatively space consuming when not in operation. To reduce the space requirements of hammock stands, a hammock stand may be reduced to separate front and back portions, wherein both the front and back portions are independently set up, and wherein the front and back portions may further be folded into a more compact configuration. Examples for such hammock stands can be found in U.S. Pat. No. 201,074 to Wheeler, or U.S. Pat. No. 260,230 to Parker, both of which are incorporated by reference herein. While such stands advantageously save space when not supporting the hammock, they typically require multiple points of attachment or contact to the ground to reliably support a person in a hammock. Alternatively, a hammock stand may also be foldably configured as described in U.S. Pat. No. 838,078 to Carbaugh, wherein a foldable frame is secured with a pair of diagonal braces. While such foldable frames allow a side-to-side reduction in space, such frames do generally not allow for both side-to-side and front-to-back folding operation. Moreover, before an operator can fold such frames, the diagonal braces typically need to be removed. In still further known configurations, hammock frames may also be collapsed. For example, U.S. Pat. No. 5,659,907 to Huang and U.S. Pat. No. 5,983,422 to Bayless describe a configuration in which the hammock frame has a foldable center beam with foldable angled support structures. Alternatively, a collapsible hammock frame may also be configured to include a pair of foldable inverted V-shaped stands that are connected to each other with a foldable lateral support as described in U.S. Pat. No. 5,046,203 to de Cuadros. While such collapsible hammock frames provide at least some space saving when not supporting the hammock, numerous disadvantages still remain. Among other things, all or almost all of the known hammock stands still require substantial space when not in operation. Furthermore, folding and unfolding of such hammock stands is often difficult, especially to an inexperienced or physically challenged user. Therefore, there is still a need to provide improved hammock stands.
<SOH> SUMMARY OF THE INVENTION <EOH>The present invention is directed to a collapsible hammock stand with a plurality of legs, support rods, and a cross brace that couples at least one leg to at least one of the support rods such that the hammock stand collapses in a single movement. In one aspect of the inventive subject matter, contemplated hammock stands have four legs, four support rods, and a pair of cross braces, wherein the legs, the support rods, and the cross braces are coupled to each other such that the hammock stand collapses in a single movement in which two of the four legs approximate each other as two of the support rods pivot towards each other. Particularly suitable configurations include those in which a first and a second of the four legs are rotatably coupled to each other, and wherein a first support rod is rotatably coupled to the first of the four legs and wherein a second of the support rods is rotatably coupled to the second of the four legs. Such configurations may further include a connector rod that couples the second of the four legs to the first of the support rods. Especially preferred connector rods releasably engage with a support rods and form an obtuse angle with one of four legs when the hammock stand is in an open configuration. In further contemplated aspects of the inventive subject matter, the cross braces are rotatably coupled to each other to form a pair of cross braces, wherein at least one of the cross braces is rotatably coupled to the first of the four legs, and rotatably and slidably coupled to a third of the support rods. Suitable stands may further comprise a body support that is coupled to at least two of the four support rods, and may still further comprise a flexible element that couples the first of the four legs with a third of the four legs and that facilitates collapsing of the hammock stand when the flexible element is pulled upwards relative to the ground (when the hammock stand is in an open configuration). In yet another aspect of the inventive subject matter, contemplated hammock stands will have a plurality of legs, a plurality of support rods, and at least one pair of cross braces coupling at least one leg to at least one of the support rods such that the hammock stand collapses in a simultaneous front-to-back and side-to-side motion. In such configurations, it is generally preferred that at least one leg is coupled to at least one support rod via a connector rod. In particularly preferred configurations, such hammock stands will include four legs, four support rods, and two pairs of cross braces, wherein the first pair of cross braces couples at least one leg to at least one support rod, wherein the second pair of cross braces couples at least another one of the legs and another one of the support rods, and wherein at least two legs are rotatably coupled to each other. At least one of the support rods may be rotatably coupled to at least one of the legs. In a still further aspect of the inventive subject matter, a hammock stand has a first leg, a second leg, a third leg, and a fourth leg, and further includes a first support rod, a second support rod, a third support rod, and a fourth support rod, wherein the first, second, third, and fourth support rod is rotatably coupled to the first, second, third, and fourth leg, respectively; a first pair of cross braces are rotatably coupled to each other, wherein one of the cross braces is rotatably coupled to the first leg and third support rod and wherein the other cross brace is rotatably coupled to the third leg and first support rod; a second pair of cross braces are rotatably coupled to each other, wherein one of the cross braces is rotatably coupled to the second leg and fourth support rod and wherein the other of the cross braces is rotatably coupled to the fourth leg and second support rod; contemplated hammock stands further include a first connector rod, a second connector rod, a third connector rod, and a fourth connector rod, wherein the first, second, third, and fourth connector rod rotatably couples the first leg and the second support rod, the second leg and the first support rod, the third leg and the fourth support rod, and the fourth leg and the third support rod, respectively. Various objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of preferred embodiments of the invention, along with the accompanying drawings in which like numerals represent like components.
20050421
20081028
20060713
91960.0
A45F324
2
LIU, JONATHAN
COLLAPSIBLE HAMMOCK STAND
SMALL
0
ACCEPTED
A45F
2,005
10,532,410
ACCEPTED
Assembly comprising a filter housing and at least one filter cartridge as well as a filter cartridge for such an assembly
The invention relates to an assembly with a filter housing and at least one filter cartridge. The at least one filter cartridge is tubular, has a tube wall provided with a filter and comprises a central discharge channel with a discharge connection for discharge of filtered medium. The tube wall has a filter through which the medium to be filtered is able to flow transversely to the tube wall. The filter housing has a filter chamber, surrounded by a side wall, in which the at least one filter cartridge is accommodated with the longitudinal direction parallel to the side wall. The invention furthermore is directed to a filter cartridge intended for such an assembly.
1-23. (canceled) 24. An assembly comprising a filter housing and at least one filter cartridge, wherein the at least one filter cartridge is tubular, has a tube wall and a central discharge channel with a discharge connection for discharging filtered medium, wherein the tube wall comprises filter means through which medium to be filtered is able to flow transversely to the tube wall; wherein the filter housing comprises a filter chamber surrounded by a side wall, in which the at least one filter cartridge is accommodated with the longitudinal direction parallel to the side wall; wherein the filter chamber has at least one outlet per filter cartridge to which the discharge connection of the respective filter cartridge is connected; wherein the side wall of the filter chamber is provided with at least one inlet for feeding in the medium to be filtered, which inlet opens into the filter chamber at a level that is traversed by the at least one filter cartridge; and wherein when viewed in the transverse direction of the filter cartridge and at the level of the inlet, the shortest distance (X) from the filter cartridge to the side wall is, viewed in the transverse direction of the filter cartridge and below or above the level of the inlet, greater than the shortest distance (Y) from the filter cartridge to the side wall. 25. The assembly according to claim 24, wherein when viewed in the longitudinal direction of the filter cartridge, the relative enlargement (X minus Y) of the shortest distance from the filter cartridge to the side wall at the level of the inlet extends over a length of approximately the height of the inlet or more. 26. The assembly according to claim 24, wherein the shortest distance X from the filter cartridge to the side wall is defined by the equation: X ≥ 1 2 ⁢ ( A 2 ⁢ Q ) where A=surface area of inlet, and Q=height of the region with larger shortest distance X. 27. The assembly according to claim 24, wherein the shortest distance X from the filter cartridge to the side wall is defined by the equation: X ≥ ( A 2 ⁢ Q ) where A=surface area of inlet, and Q=height of the region with larger shortest distance X. 28. The assembly according to claim 26, wherein the inlet is circular with a diameter D1 and wherein the shortest distance X is given by X≧½ Π ⁢ ⁢ D 1 8 . 29. The assembly according to claim 24, wherein A<B(Y), preferably A≦2B(Y) where: A=surface area of inlet, and B=as a function of Y, the surface area of the internal cross-section of the filter housing minus the sum of the cross-sectional surface areas of the filter cartridges at a level above or below the inlet. 30. The assembly according to claim 24, wherein a single cylindrical filter cartridge is provided that is arranged centrally in the cylindrical filter housing, and where: A < Π 4 ⁢ ( D 3 2 - D 2 2 ) , where A=surface area of inlet D3=internal diameter of filter housing D2=external diameter of filter cartridge. 31. The assembly according to claim 24, where: Y < A 3.5 , where A=surface area of inlet. 32. The assembly according to claim 24, wherein the inlet is circular with diameter D1; and where Y < 0.75 ⁢ ( D 1 4 ) . 33. The assembly according to claim 24, wherein the filter housing is cylindrical with internal diameter D3 and, at least conceptually for the purposes of the design, contains a single centrally arranged cylindrical filter cartridge and wherein the inlet is circular with diameter D1, or at least has a surface area that is equal to a circular surface of diameter D1, and wherein the following applies for the diameter D2 of the filter cartridge, D3 and D1: D12=2(D32−D22). 34. The assembly according to claim 24, wherein: A is less than or equal to the sum of the internal cross-sectional surface areas of the filter cartridges, where A=surface area of inlet. 35. The assembly according to claim 24, wherein the enlargement (X minus Y) of the shortest distance from the filter cartridge to the side wall at the level of the inlet has been obtained by constriction of the tube wall at that level. 36. The assembly according to claim 24, wherein the enlargement (X minus Y) of the shortest distance from the filter cartridge to the side wall at the level of the inlet has been obtained by making the side wall recessed at that level. 37. The assembly according to claim 24, wherein the tube wall is impermeable to the medium to be filtered in the region where the shortest distance from the filter cartridge to the wall has been enlarged. 38. The assembly according to claim 24, wherein the assembly comprises 3, 4 or more of said filter cartridges, which are arranged next to one another, parallel to one another. 39. The assembly according to claim 24, wherein the level of the inlet is located in the region from 25% to 75% of the length of the filter cartridge. 40. The assembly according to claim 24, wherein the filter means are equipped to filter a medium in the form of a fluid. 41. The assembly according to claim 24, wherein the filter means are equipped to filter a gaseous medium. 42. The assembly according to claim 24, wherein the filter cartridge is made as a fine filter on the one side of the inlet and is made as a coarse filter on the other side. 43. The assembly according to claim 42, wherein the fine filter is at least 5 times finer than the coarse filter. 44. A filter cartridge intended for use with a filter housing, wherein the filter cartridge is tubular, has a tubular wall and a central discharge channel with a discharge connection for discharging filtered medium, wherein the tube wall comprises filter means through which medium to be filtered is able to flow transversely to the tube wall; wherein the filter housing comprises a filter chamber surrounded by a side wall, in which the at least one filter cartridge is accommodated with the longitudinal direction parallel to the side wall; wherein the filter chamber has at least one outlet per filter cartridge to which the discharge connection of the respective filter cartridge is connected; wherein the side wall of the filter chamber is provided with at least one inlet for feeding in the medium to be filtered, which inlet opens into the filter chamber at a level that is traversed by the at least one filter cartridge; and wherein when viewed in the transverse direction of the filter cartridge and at the level of the inlet, the shortest distance (X) from the filter cartridge to the side wall is, viewed in the transverse direction of the filter cartridge and below or above the level of the inlet, greater than the shortest distance (Y) from the filter cartridge to the side wall. 45. A diesel engine provided with a fuel filter comprising a filter cartridge, wherein the filter cartridge is tubular, has a tubular wall and a central discharge channel with a discharge connection for discharging filtered medium, wherein the tube wall comprises filter means through which medium to be filtered is able to flow transversely to the tube wall; wherein the filter housing comprises a filter chamber surrounded by a side wall, in which the at least one filter cartridge is accommodated with the longitudinal direction parallel to the side wall; wherein the filter chamber has at least one outlet per filter cartridge to which the discharge connection of the respective filter cartridge is connected; wherein the side wall of the filter chamber is provided with at least one inlet for feeding in the medium to be filtered, which inlet opens into the filter chamber at a level that is traversed by the at least one filter cartridge; and wherein when viewed in the transverse direction of the filter cartridge and at the level of the inlet, the shortest distance (X) from the filter cartridge to the side wall is, viewed in the transverse direction of the filter cartridge and below or above the level of the inlet, greater than the shortest distance (Y) from the filter cartridge to the side wall. 46. The assembly according to claim 26, wherein the inlet is circular with a diameter D1 and wherein the shortest distance X is given by X≧ Π ⁢ ⁢ D 1 8 . 47. The assembly according to claim 30, wherein a single cylindrical filter cartridge is provided that is arranged centrally in the cylindrical filter housing, and where: A = 2 ⁢ Π 4 ⁢ ( D 3 2 - D 2 2 ) . 48. The assembly according to claim 24, wherein the inlet is circular with diameter D1; and where Y < 0.4 ⁢ ( D 1 4 ) . 49. The assembly according to claim 24, wherein the inlet is circular with diameter D1; and where Y < 0.15 ⁢ ( D 1 4 ) .
The present invention relates to an assembly comprising a filter housing and at least one filter cartridge that is tubular, has a tube wall and a central discharge channel with a discharge connection for discharging filtered medium, wherein the tube wall comprises filter means trough which medium to be filtered is able to flow transversely to the tube wall; wherein the filter housing comprises a filter chamber surrounded by a side wall, in which the at least one filter cartridge is accommodated with the longitudinal direction parallel to the side wall; wherein the filter chamber has at least one outlet per filter cartridge to which the discharge connection of the respective filter cartridge is connected; wherein the side wall of the filter chamber is provided with at least one inlet for feeding in the medium to be filtered, which inlet pens into the filter chamber at a level that is traversed by the at least one filter cartridge. Such an assembly is generally known. With this arrangement the inlet via which medium to be filtered enters the filter chamber is oriented in the transverse direction of the filter cartridges located in the filter chamber, i.e. the direction of flow of the medium to be filtered is initially transverse to the longitudinal direction of the filter cartridges. To ensure rapid distribution of incoming medium to be filtered over the filter chamber, the rule of thumb adopted in this case is that the distance from the filter cartridges to the interior of the side wall of the filter chamber must be at least a quarter of the diameter of the inlet. If there are several filter cartridges present in the filter housing, this minimum distance of a quarter of the diameter of the inlet is usually also adopted for the minimum lateral distance between the filter cartridges. The result of the various aspects is that the dimensions of the filter housing are relatively large. The aim of the present invention is to be able to make the filter housing of compact constriction or, in particular in the case of existing filter housings, to increase the filter capacity and/or to improve the filtration result. According to the invention the abovementioned aim is achieved in that, viewed in the transverse direction of the filter cartridge and at the level of the inlet, the shortest distance X from the filter cartridge to the side wall is greater than the shortest distance Y from the filter cartridges to the side wall viewed in the transverse direction of the filter cartridge and below or above the inlet The present invention is based on the insight that the additional space between the wall of the filter housing and the filter cartridge and, respectively, between the filter cartridges themselves, which additional space ensures a good, uniform and rapid distribution of the medium to be filtered over the filter chamber, is not needed in the entire filter housing, but that it suffices to provide this additional space essentially at the level of the inlet. This is because, as the Applicant has found, as soon as the filter medium has distributed over the cross-section of the filter chamber, the additional space between the wall of the filter chamber and the cartridges, and between the cartridges themselves, is no longer needed, or at least is not needed to the same degree as at the location of the inlet According to an advantageous embodiment, as the Applicant has found by experimentation, it suffices, viewed in the longitudinal direction of the filter cartridge, if the enlargement of the shortest distance from the filter cartridge to the side wall at the level of the inlet extends over a length of approximately the height of the inlet, although this enlargement of the shortest distance can also extend over a greater length. According to an advantageous embodiment of the invention, X is given by: X ≥ 1 2 ⁢ ( A 2 ⁢ Q ) where A=surface area of inlet and Q=height of the region with larger shortest distance X. If X≧A/4Q a significant proportion of the medium to be filtered is distributed over the filter chamber via the zone with the relatively larger shortest distance X, so that the conventional distance adopted for Y can decrease very appreciably. According to the invention, Y can be reduced to a minimum if X is given by: X≧A/2Q. If the inlet is circular, A can be given by A = Π 4 ⁢ D 1 2 , which in the previous two equations then results in X ≥ Π ⁢ ⁢ D 1 16 ⁢ ⁢ and ⁢ ⁢ X ≥ Π ⁢ ⁢ D 1 8 ⁢ ⁢ for ⁢ ⁢ Q = D 1 . According to a further advantageous embodiment of the invention, Y is given by the following relationship: A<B(Y), preferably A≦2B(Y) where: A=surface area of inlet B(Y)=as a function of Y, the surface area of the internal cross-section of the filter housing minus the sum of the cross-sectional surface areas of the filter cartridges at a level above or below the inlet. In this way it is possible to design the free space available for guiding the medium to be filtered away in the axial direction of the filter cartridge as a minimum, which again enables a reduction in the dimensions of the filter housing or, optionally, enlargement of the filter. In the case of a single cylindrical filter cartridge arranged centrally in a cylindrical filter housing, these equations become A < Π 4 ⁢ ( D 3 2 - D 2 2 ) , in ⁢ ⁢ particular ⁢ ⁢ A < 2 ⁢ Π 4 ⁢ ( D 3 2 - D 2 2 ) where A=surface area of inlet D3=internal diameter of filter housing D2=external diameter of filter cartridge, and D3−D2=Y. If the inlet is circular with diameter D1, it has been found according to the invention that Y can be taken as Y < 0.75 ⁢ D 1 4 without any problem, which immediately yields 25% or more reduction compared with the value for Y according to the state of the art However, according to the invention it has been found that Y can also safely be taken as Y < 0.4 ⁢ D 1 4 , which signifies 60% or more reduction compared with the state of the art. One can, according to the invention usually take Y < 0.15 ⁢ D 1 4 without any problem, which thus signifies a reduction of more than 85% in Y compared with the state of the art. Even reductions of more than 95% in Y can be achieved. If the filter housing is cylindrical with internal diameter D3 and a centrally arranged cylindrical filter cartridge of diameter D2 is assumed and it is realised that D3−D2=Y, the minimum value for Y for a circular inlet of diameter D1 can be calculated from D12=2(D32−D22). According to the invention, this design values can very readily be maintained as a minimum value for all designs, provided that D3 is the diameter of a circle having a surface area equivalent to the internal cross-sectional surface area of the filter housing mid D1 is a correspondingly equivalent diameter for the inlet Be area and, for simplicity, a central cylindrical filter cartridge is assumed for the purposes of the calculations. It is then possible to take several filter cartridges instead of just one and to continue to use the value for Y calculated for a single filter cartridge. In the general sense, it is pointed out that wherever a certain diameter of a circular shape is assumed, it is ely well possible to convert a noncircular surface to a circular surface of specific diameter. So that the filtered medium can also be discharged reliably and well without stagnation of the feed it is highly preferable if A is taken as: A≦sum of the internal cross-sectional surface areas of the filter cartridges. It is pointed out that in particular in the case of several filter cartridges which, as a consequence of, for example, their shaping, such as a cylindrical shape, inherently leave a gap between them in the transverse direction, it is even conceivable that the filter cartridges locally come into contact with the wall of the filter chamber. This will, however, result in some loss of available filter surface. However, the design criteria from the state of the art did not permit this. According to a further embodiment of the invention, it is advantageous if the enlargement of the shortest distance from the filter cartridge to the side wall at the level of the inlet has been obtained by constriction of the tube wall of the filter cartridge at that level. This is practical in order to be able to convert existing filter installations to an assembly according to the invention without adapting the filter housing. For this purpose it is then necessary only to adapt the filter cartridge, which already has to be replaced from time to time. However, depending on the circumstances, according to the invention it is possibly also highly advantageous if the enlargement of the shortest distance from the filter cartridge to the side wall at the level of the inlet is obtained by making the side wall recessed at that level. In this case it is then not so much the filter cartridge that is adapted as the inward-facing section of the side wall of the filter chamber. As will be clear, it is also conceivable according to the invention to obtain the enlargement of the shortest distance from the filter cartridge to the side wall at the level of the inlet by both a constriction of the tube wall of the filter cartridge at that level and by making the side wall of the filter chamber recessed at that level. Making the wall of the filter chamber recessed can be useful if the tube wall has insufficient thickness to enable this to be adequately constricted for the desired effect According to a further advantageous embodiment of the invention, the tube wall of the filter cartridge is made impermeable to the medium to be filtered and more generally completely closed in the region where the shortest distance from the filter cartridge to the wall has been enlarged. This prevents the medium to be filtered from being forced directly through the wall of the filter cartridge under the influence of the pressure at which it is fed to the filter chamber, which would have an adverse effect on the filter result According to an advantageous embodiment of the invention, the assembly comprises 3, 4 or more of said filter cartridges, which are arranged next to one another, parallel to one another. According to the further advantageous embodiment, the level of the inlet is located in the legion from 25% to 75% of the length of the filter cartridge. So that the assembly according to the invention can be used to filter a fluid, it is preferable according to the invention if the filter means are equipped to filter a medium in fluid form. So that the assembly according to the invention can be used to filter a gas, it is preferable if the filter means are equipped to filter a gaseous medium. According to a further advantageous embodiment of the invention, the filter cartridge is made as a fine filter on the one side of the inlet and as a coarse filter on the other side. The terms fine filter and coarse filter are used here as relative with respect to one another, which amounts to the fine filter retaining both the particles retained by the coarse filter and also smaller particles. Preferably, the fine filter is at least 5 times finer tan the coarse filter, for example the fine filter allows particles up to 3 μm through and the coarse filter allows particles up to 25 μm through, which means that the fine filter is approximately 8.3 times as fine as the coarse filter. According to a further aspect, the invention relates to a filter cartridge intended for an assembly according to the invention. More specifically, according to the further aspect, the invention relates to the filter cartridge as defined in the assembly according to the invention. According to yet a further aspect, the invention relates to a diesel engine provided with a fuel filter or lubricant filter comprising an assembly or a filter cartridge according to the invention. The present invention will be explained in more detail below with reference to illustrative embodiments shown m the drawing. In the drawing: FIG. 1 shows, diagrammatically, a filter cartridge according to the invention, the left-hand half as a front view and the right-hand half in cross-section; FIG. 2 shows diagrammatic longitudinal sectional view of an assembly according to the invention; FIG. 3 shows a diagrammatic cross-sectional view according to the lines III-III from FIG. 2; and FIG. 4 shows across-sectional view corresponding to FIG. 3 of an assembly according to the state of the art. FIG. 1 shows a filter cartridge 1 according to the invention. This filter cartridge 1 is tubular and except for the constriction 37 of the tube wall essentially does not differ from conventional filter cartridges. The filter cartridge 1 is tubular, has a top closure 2 and a discharge connection 12 at the bottom. The filter cartridge has an inner wall 8, 10, 11, which is closed and impermeable at the location of 8 and is permeable to the medium to be filtered at the location of 10 and 11. The filter cartridge furthermore has an outer wall 3 and 4, and also 8, which simultaneously acts as inner wall and outer wall at the location of the constriction 37. The outer wall 3 and 4 consists of a fine mesh or finely perforated metal sheet. The inner wall 10 and 11 can be constructed correspondingly to the outer wall 3, 4. Filter means 5 are present between the inner wall 10 and outer wall 3 and there are corresponding filter means 6 between the inner wall 11 and outer wall 4. The filter means 5 and 6 can be of a wide variety of diverse types and can, for example, be made up of filter papers finely folded into pleats, the fold lines of the pleats then extending in the longitudinal direction L of the filter cartridge 1. Furthermore, the outer wall 3, 4 and inner wall 10, 11 can also act as filter means. Precisely how the inner wall 10, 11, the outer wall 3, 4 and the filter means 5, 6 are constructed is of minor importance for the filter cartridge according to the invention; specifically this can be carried out in a wide variety of ways provided that the filter cartridge is of the type trough which, as is indicated by means of arrows 30, flow takes place essentially transversely to the longitudinal diction L, with filtering effect. A discharge channel 9 for discharging filtered medium allowed through by the tube wall 3, 4, 5, 6, 10, 11 and 8 (which is impermeable) is provided centrally in the filter cartridge 1. In an advantageous embodiment of the invention provision is made that a portion of the filter cartridge, for example the portion 3 located above the constriction 8, is made as a fine filter and another portion, for example the portion 4 located below the constriction 8, is made as a coarse filter. What is achieved by this means is ta a portion of the flow is finely f which improves the overall filter result As has been stated, the filter cartridge 1 according to the invention differs from filter cartridges from the state of the art in respect of the constriction 37. The constriction 37 is a zone where the filter means 5, 6 have been omitted and where the outer wall 3, 4 is interrupted and the inner wall 8 is closed. The constriction 37 is delimited at its bottom and top by means of an annular dish 7, which annular dish 7 prevents medium to be filtered from being able to flow into the filter means 5 and 6 via the constriction 37 in the longitudinal direction L of the filter cartridge 1. The constriction 37 is constricted over a distance of Π/8 D1, where the distance D1 is the effective diameter of the inlet of the filter housing which is still to be discussed. Viewed in the longitudinal direction L, the filter cartridge as shown in FIG. 1 has a length H. This length is subdivided into a bottom zone of a ¼H, a top zone with a length of a ¼H and an intermediate zone with a length ½H. According to the invention, the constriction 37 is preferably provided in the intermediate zone with a length of a ½H. This can be, as shown in FIG. 1, at the bottom of said intermediate zone with length a ½, at the top of said zone or also somewhere in between, for example in the middle of said zone. FIG. 2 shows an assembly according to the invention in longitudinal section. A cross-section at the location of the arrows m in FIG. 2 is shown in FIG. 3. With reference to FIGS. 2 and 3, the assembly according to the invention comprises, in accordance with the illustrative embodiment shown, a filter housing 20 with a filter chamber 35, which is delimited by a side wall 22, atop wall 21 and a bottom wall 26 provided with outlets. In the example shown, 4 filter cartridges 1 arranged parallel to one another are provided in the filter chamber 35. These filter cartridges 1 are each connected via a discharge connection 12 to an outlet 36 in the bottom watt 26. Below the bottom wall 26 there is a collection chamber 24 on which a connection stub 25 for discharging filtered medium is fitted The filter housing 20 is furthermore provided with a connection stub 27 for the feed of medium to be filtered. This connection stub 27 has an inlet 23 with a diameter D1 opening into the filter chamber 35. This diameter D1 corresponds to the length Q of the constriction 37 viewed in the longitudinal direction L. Before now proceeding with the description of the assembly according to the invention, a comparable conventional assembly will now first be explained in more detail with reference to the cross-section in FIG. 4. This conventional assembly has a filter housing 20 assumed to be essentially identical, which by means of a side wall 22 encloses a filter chamber 35 in which 4 conventional filter cartridges 40 are arranged. These filter cartridges 40 are essentially identical to filter cartridge 1 from FIG. 1, with the understanding that in the case of the filter cartridge 40 the constriction 37 is lacking, that is to say the outer walls 3, 4 are a complete whole and uninterrupted, as are also the filter means 5 and 6 and the inner wall 10, 11, which is still permeable at the location of the constriction. In the case of such conventional assemblies the conventional teaching is that the filter cartridges are so arranged in the filter housing 20 that the smallest distance from the outer wall of the filter cartridge to the inner wall of the filter chamber 35 is at least ¼ D1 (see FIG. 4), where D1 is the diameter of the inlet 23, via which the medium to be filtered flows into the filter chamber 35. As will be clear, this means that, viewed in the cross-sectional direction—perpendicular to longitudinal direction L—the dimensions of the filter housing 20 will be significantly larger than the minimum space required for the filter cartridges 40 for mere accommodation in the filter chamber 35. After all, an additional space of ¼ D1 all round is required to be able to disperse the medium to be filtered through the filter chamber 35 sufficiently quickly. The Applicant has now arrived at the insight that it surfaces to create the additional space only at the location of the level 31 where the inlet 23 opens into the filter chamber 35. In accordance with the invention, this requisite additional space could be created by providing the side wall 22 at the location of the level 31 on the inside with a recess of a specific depth in the radial direction of the tube wall 22, which is not shown. However, this means that the tube wall usually has to be made significantly thicker, which will not lead directly to a more compact construction However, the advantage in this case is that the filter chamber 35 could be filled with more or larger filter elements; after all, the filter elements may even be able to come into contact with the side wall 22. More or larger filter elements lead to a higher filtering capacity and/or to a better filter result. However, according to the invention it is, rather, preferable, optionally as a supplementary measure to the local recessing of the side wall of the filter housing, to provide the filter cartridges 1 with a constriction 37 at the level 31, as has already been discussed with reference to FIG. 1. If the constriction 37 has a depth of approximately Π/8 D1, where D1 is the diameter of the inlet 23, the filter cartridges 1 can then, as is shown in FIG. 3, each have a line of contact 28 with the side wall 22 of the filter housing and, at the same time, have a line of contact or virtually a line of contact with adjacent filter cartridges, in accordance with FIG. 4. That is to say the distance 29 from FIG. 3 can be reduced to approximately 0. The constriction of approximately Π/8 D1 of each filter cartridge can then yield an appreciable reduction in the diameter of the filter housing 20. It is again pointed out that the diameter of the filter housing in FIG. 3 and the diameter of the filter housing in FIG. 4 have been kept the same as one another and that the diameters of the filter cartridges 1 and 40 have also been kept the same as one another. The reason for this is, in particular, further to clarify the difference between FIGS. 3 and 4 as explained above. It is pointed out that the configuration in FIG. 3 with a mutual spacing of 29 of somewhat less than ¼ D also yields advantages compared with the state of the art as shown in FIG. 4. Specifically, the filtration result is found to be already improved. It will be possible to obtain a major advantage if either the diameter of the filter housing 20 in FIG. 3 is reduced or the diameter of the filter cartridges is increased or optionally an additional, fifth filter cartridge is placed centrally in the filter chamber 35. The filtering capacity increases as a result of increasing the diameter of the filter cartridges 1 or optionally placing an additional, fifth filter cartridge centrally in the middle. For filter clarification, in FIG. 2 the shortest distance between the filter cartridge 1 and the side wall 22 is also indicated by X at the level of the inlet 23, which level extends over the zone indicated by 31, and this smallest distance is indicated by Y for the zone 32 above zone 31 and also for the zone 33 below zone 31. For better understanding, the concept on which the invention is based will be explained in yet more detail with reference to the diagrammatic sketch in FIG. 5: The surface area A of the inlet 23 can be determined as A = Π 4 ⁢ D 1 2 ( 1 ) in the case of a circular feed pipe. This equation also applies if the circular feed pipe joins the filter housing at an angle instead of at right angles; after all the point at issue is the effective surface area of the passageway. If the feed pipe is not circular, equation (1) can still be used if the value that yields an equivalent surface area A is taken for D1. In order to prevent the inflowing medium being retarded when entering the filter housing it is best to ensure that the surface area of the passageway available or flow immediately on entry is equal to or greater than A. The Applicant has reached the insight that the medium can be allowed to flow from the inlet, initially without displacement thereof in the direction L, around the filter cartridge. (The state of the art assumes an immediate deflection of the flow at right angles with respect to the inflow direction indicated by arrow “in”). The surface area available for flow then consists of two rectangular surfaces each with dimensions X×Q. For Q=D1 and a cylindrical filter housing with internal diameter D3 and a centrally arranged cylindrical filter cartridge with constricted diameter D4, this results in A = 2 ⁢ ( X × Q ) = 2 ⁢ ( ( D 3 - D 4 ) × D 1 ) ( 2 ) A = Π 4 ⁢ D 1 2 ( 1 ) Π 8 ⁢ D 1 = ( D 3 - D 4 ) ( 3 ) i . e . ⁢ Π 8 ⁢ D 1 = X . ( 4 ) For further optimisation it is then best to ensure that in the zones above and below the constriction 37 the surface area available for flow, viewed perpendicularly to the longitudinal direction 1, is once again at least equal to A. In the illustrative embodiment shown this means that A is equated to 2 annular surfaces each with dimensions Π 4 ⁢ ( D 3 2 - D 2 2 ) i.e. this gives A = 2 ⁢ Π 4 ⁢ ( D 3 2 - D 2 2 ) ( 5 ) A = Π 4 ⁢ D 1 2 ( 1 ) D 3 - D 2 = Y . ( 6 ) For a given D1 and given D3 or D2, Y can then be easily determined. As will be clear, Y can, however, also be determined as a function of D1, without knowing D3 and D2. This Y value can then be used as minimum value in the design, including in the case of non-circular filter cartridges or multiple filter cartridges. With regard to multiple filter cartridges it is pointed out that Y can then be even further reduced by more accurate calculation.
20050422
20081104
20060112
63230.0
B01D2958
1
KIM, SUN U
A FILTER CARTRIDGE AND AN ASSEMBLY OF A FILTER HOUSING AND AT LEAST ONE SUCH FILTER CARTRIDGE
UNDISCOUNTED
0
ACCEPTED
B01D
2,005
10,532,484
ACCEPTED
Continuously variable ratio transmission unit and method of assembly thereof
A continuously variable ratio transmission unit is disclosed which comprises a housing (116) and input (102, 106) and output (100) discs paired to define first and second toroidal cavities. The discs (100, 102, 106) are mounted to the housing for rotation about a common axis. First (110) and second (112) rollers—or more typically first and second sets of rollers—are respectively arranged in the first and second cavities and serve to transmit drive between the input and output discs. First (130) and second (148, 150, 152) actuators act on the respective rollers. The first actuator is coupled to a first carrier part (126) which can be mated with the housing introducing it to the housing along a direction generally parallel to the variator axis. The second actuator is coupled to a second carrier part (146) which can be mated with the housing by introducing the second carrier part to the housing along a direction non-parallel to the variator axis.
1. A continuously variable ratio transmission unit (“variator”) comprising a housing, a first input/output disc pair defining a first variator cavity, a second input/output disc pair defining a second variator cavity, the discs being mounted to the housing for rotation about a common variator axis, at least one first roller disposed in the first variator cavity and at least one second roller disposed in the second variator cavity, the rollers serving in use to transmit drive between the input and output discs, a first actuator for applying a biasing force to the first roller and a second actuator for applying an adjustable biasing force to the second roller, wherein the first actuator is coupled to a first carrier part, the housing and the first carrier part being formed such that the first carrier part can be mated with the housing by introducing the first carrier part to the housing along a direction substantially parallel to the variator axis, and the second actuator is coupled to a second carrier part, the housing and the second carrier part being formed such that the second carrier part can be mated with the housing by introducing the second carrier part to the housing along a direction non-parallel to the variator axis. 2. A variator as claimed in claim 1 comprising at least three second rollers each acted on by a respective second actuator, wherein the second actuators all lie on the same side of a notional plane containing the variator axis. 3. A variator as claimed in claim 2 comprising at least three first rollers each acted on by a respective first actuator, wherein the first actuators are angularly spaced about the variator axis and are thus disposed to either side of the said plane. 4. A variator as claimed in claim 2 wherein the second actuators comprise actuator housings which are co-planar. 5. A variator as claimed in claim 3 wherein the first actuators are spaced at equal angular intervals about the variator axis. 6. A variator as claimed in claim 1 wherein the actuators are hydraulic and the first carrier part comprises a plate lying around the variator axis, circumferentially extending fluid supply conduits being formed in or adjacent said plate for feeding fluid to/from the first actuators. 7. A variator as claimed in claim 6 wherein a back plate lies adjacent the first carrier part, the fluid supply conduits being formed between faces of the first carrier part and the back plate. 8. A variator as claimed in claim 1 wherein the housing provides an axially facing recess which receives the first carrier part. 9. A variator as claimed in claim 1 wherein the housing provides a radially facing recess which receives the second carrier part. 10. A method of constructing a continuously variable ratio transmission unit (“variator”) comprising a housing, a first input/output disc pair defining a first variator cavity, a second input/output disc pair defining a second variator cavity, the discs being mounted to the housing for rotation about a common variator axis, at least one first roller disposed in the first variator cavity and at least one second roller disposed in the second variator cavity, a first actuator for applying a biasing force to the first roller and a second actuator for applying an adjustable biasing force to the second roller, the method comprising constructing the first actuator on a first carrier part and advancing the first carrier part in a direction along the variator axis to thereby mate the first carrier part to the housing, constructing the second actuator on a second carrier and advancing the second carrier part along a direction non-parallel to the variator axis to thereby mate the second carrier part to the housing. 11. (canceled)
The present invention relates to a continuously variable ratio transmission unit (“variator”) and to a method of assembly thereof. The general construction of variators of toroidal-race, rolling-traction type will be familiar to the skilled person. Typically two toroidal cavities are defined between facing surfaces of a set of variator discs all of which are mounted for rotation about a common axis. Drive is transmitted between the discs by a set of rollers in both of the cavities and the inclination of the rollers with respect to the discs is able to change in accordance with changes in variator drive ratio. A biasing force, along a direction transverse to the disc axis, is applied to each roller by an actuator which in existing designs is of hydraulic type. Fabrication and in particular assembly of existing variators is somewhat complex. The discs, actuators and rollers are typically all mounted in a housing and assembling the various parts inside the housing is in current prototypes a somewhat time consuming process not easy to automate or adapt to production line techniques. A first object of the present invention is to provide a variator which is capable of straightforward assembly. The need to provide for hydraulic fluid supply to the several actuators has meant some complication in the machining of the variator's components, particularly the housing. The applicant has previously proposed, in order to simplify construction, to form passages for the fluid supply between confronting faces of a multi-part casing—see its published International Patent Application PCT/GB99/02968. Nonetheless an additional or alternative object of certain embodiments of the present invention is to provide, in a variator, a means of fluid supply to the hydraulic actuators which is straightforward in fabrication and assembly. The shape of the variator housing is in many cases a crucial design issue. The current need is for variators which can be installed in existing motor vehicle designs. Hence in rear wheel drive cars the variator is to be installed in the transmission tunnel. Both excessive length and width of the variator could be problematic, and in particular laterally projecting “lobes” needed in existing designs to accommodate the roller control actuators, create installation difficulties. An additional or alternative object of the present invention is to provide a variator whose external shape is suited to installation in a motor vehicle. In accordance with a first aspect of the present invention there is a continuously variable ratio transmission unit (“variator”) comprising a housing, a first input/output disc pair defining a first variator cavity, a second input/output disc pair defining a second variator cavity, the discs being mounted to the housing for rotation about a common variator axis, at least one first roller disposed in the first variator cavity and at least one second roller disposed in the second variator cavity, the rollers serving in use to transmit drive between the input and output discs, a first actuator for applying a biasing force to the first roller and a second actuator for applying an adjustable biasing force to the second roller, wherein the first actuator is coupled to a first carrier, the housing and the first carrier being formed such that the first carrier can be mated with the housing by advancing the first carrier in a direction along the variator axis, and the second actuator is coupled to a second carrier, the housing and the second carrier being formed such that the second carrier can be mated with the housing by advancing the second carrier along a direction non-parallel to the variator axis. In accordance with a second aspect of the present invention there is a method of constructing a continuously variable ratio transmission unit (“variator”) comprising a housing, a first input/output disc pair defining a first variator cavity, a second input/output disc pair defining a second variator cavity, the discs being mounted to the housing for rotation about a common variator axis, at least one first roller disposed in the first variator cavity and at least one second roller disposed in the second variator cavity, a first actuator for applying a biasing force to the first roller and a second actuator for applying an adjustable biasing force to the second roller, the method comprising constructing the first actuator on a first carrier and advancing the first carrier in a direction along the variator axis to thereby mate the first carrier to the housing, constructing the second actuator on a second carrier and advancing the second carrier along a direction non-parallel to the variator axis to thereby mate the second carrier to the housing. In accordance with a third aspect of the present invention there is a continuously variable ratio transmission unit (“variator”) comprising a variator housing, a first input/output disc pair defining a first variator cavity, a second input/output disc pair defining a second variator cavity, the discs being mounted to the housing for rotation about a common axis, three first rollers disposed in the first variator cavity and three second rollers disposed in the second cavity, the rollers serving in use to transmit drive between the input and output discs, each of the first rollers being operably coupled to a respective first actuator and each of the second rollers being operably coupled to a respective second actuator, the actuators each serving to apply to their associated rollers an adjustable biasing force and each being mounted to the variator housing, the second actuators all being arranged to one side of a plane containing the variator axis and the first actuators being angularly spaced about the axis and thus disposed to either side of the said plane. Specific embodiments of the present invention will now be described, by way of example only, with reference to the accompanying drawings in which: FIG. 1 is a somewhat schematic illustration of major components of a variator of known general type; FIG. 2 is a simplified perspective illustration of a variator constructed according to the present invention, a variator housing being shown broken away so that interior components of the variator can be seen and certain components being omitted for the sake of clarity; FIG. 3 is a view along a radial direction of the same variator, the housing again being shown broken away to reveal interior components; FIG. 4 is an exploded, perspective illustration of parts of the same variator viewed from one end and to one side thereof; FIG. 5 is a perspective illustration of a first sub-assembly of the variator; and FIG. 6 is a section in an axial plane through an actuator used in the variator. The general construction of a toroidal-race, rolling traction type variator will firstly be described with reference to FIG. 1. Here, two input discs 12, 14 are mounted upon a drive shaft 16 for rotation therewith and have respective part toroidal surfaces 18, 20 facing toward corresponding part toroidal surfaces 22, 24 formed upon a central output disc 26. Two toroidal cavities are thus formed by opposing surfaces of the input and output discs. The designation “input” and “output” with regard to the discs is somewhat arbitrary since torque can be transmitted across the variator in either direction (from “input” to “output” or vice versa). A single output disc 26 with two part toroidal faces 22, 24 is shown but two discs, typically back-to-back, can serve the same function. The output disc 26 is journalled such as to be rotatable independently of the shaft 16. Drive from an engine or other prime mover is transferred between input and output discs via a set of rollers disposed in the toroidal cavities. A single representative roller 28 is shown but typically three such rollers are provided in each cavity. An end load applied across the input discs 12, 14 by a hydraulic end load arrangement 15 provides pressure between rollers and discs to enable the transfer of drive. The discs are coupled to further parts of the transmission, typically an epicyclic mixer, as is well known in the art and described e.g. in European patent 185463. Each roller is journalled in a respective carriage 30 which is itself coupled to a hydraulic actuator 32 whereby an adjustable translational force can be applied to the roller/carriage combination. As well as being capable of translational motion the roller/carriage combination is able to rotate about an axis determined by the hydraulic actuator 32 to change the “tilt angle” of the roller and to move the contacts between rollers and discs, thereby varying the variator transmission ratio, as is well known to those skilled in the art. The illustrated variator is of the type known in the art as “torque control”. The hydraulic actuator 32 exerts a controlled force on the roller/carriage and for equilibrium this must be balanced by the reaction force upon the roller resulting from the torques transmitted between the disc surfaces 18, 20, 22, 24 and the roller 28. The axis determined by the actuator 32 is angled to the plane perpendicular to the variator axis. This angle is referred to as the “castor angle”. The well known result of this arrangement is that in use each roller automatically moves and precesses to the location and tilt angle required to transmit a reaction torque determined by the biasing force from the actuator 32. Reaction torque, in this context, means the sum of the torques input to and output from the variator. The force from the actuator 32 is controlled by means of a hydraulic circuit through which fluid is supplied to the actuators at a variable pressure. The present invention is however, applicable to variators of so-called “ratio control” type in which roller position is sensed and adjusted to provide a chosen ratio. In FIG. 2 onward the variator's output disc is seen at 100. A first input disc 102 (half of which is omitted from FIG. 2 for clarity) defines with the output disc 100 a first toroidal variator cavity 104 and a second input disc 106 defines with the output disc 100 a second toroidal variator cavity 108. A set of first rollers 110 is disposed in the first toroidal cavity. A set of second rollers 112 (omitted from FIG. 2 but seen in FIG. 3) is disposed in the second toroidal cavity. In the illustrated embodiment there are three first rollers 110 and three second rollers 112. The discs 100, 102, 106 are journalled about a variator axis defined by a main shaft, which again is omitted from FIG. 2 for the sake of representational clarity but passes through bores labelled 114 in FIG. 3. The rollers, discs and shaft are all contained within a housing 116. In the present embodiment the housing is a cast and machined metal structure. The shape of the housing is well, suited to incorporation into the tunnel of a conventional rear wheel drive motor car, its end 118 which lies toward the car's engine in use being relatively wide but leading via a tapering, frusto-conical transition region 120 to a narrower section 122. This housing shape creates potential difficulties in assembly of the variator but such problems are avoided in the illustrated embodiment by breaking down some major variator components into a set of sub-assemblies, as will now be explained. A first sub-assembly 123 is illustrated separately from the housing and other variator components in FIG. 5 and comprises a first carrier part 124 having in the present embodiment a plate 126 with a circular perimeter and a concentric circular cut-away 128. Regularly spaced about the plate 126 are three actuator housings 130 respectively defining three roller control cylinders which are not seen in FIG. 5 but one of which can be discerned at 132 in FIG. 3. In the illustrated embodiment the actuator housings 130 are integral with the plate 126, these parts being formed by a single casting. However it will be apparent that, for convenience of manufacture, these parts could be formed by separate components and bolted or otherwise fastened together. A preferred manufacturing technique is to form the actuator housings from aluminum, the cylinder bores being hard anodised and not requiring a cylinder liner. In the illustrated example the three actuator housings 130 are equally angularly spaced about the variator axis (i.e. are at 120° intervals). A circle indicated at 134 in FIG. 5 is the centre circle of the first toroidal cavity in the assembled variator. As the first rollers 110 and their associated piston rods 136 and pistons 138 (seen in FIG. 3) move, the centres of the rollers are constrained by the variator discs to move along the circle 134. The actuator housings 130 are aligned to urge the rollers approximately along respective tangents to the circle 134, although it can be seen in FIG. 3 that the line from the roller centre 140 to the piston centre 142 is inclined to the plane of the circle 134 (i.e. to the plane perpendicular to the variator axis) this inclination being the aforementioned castor angle. A second sub-assembly of the variator comprises a second carrier part formed as a carrier block 146. The carrier block 146 carries the actuator housings 148, 150, 152 associated with the three second rollers 112. Housing 152 is in the background and is largely hidden in FIG. 3. Note that whereas the first carrier part lies around the variator axis, the carrier block 146 lies to one side of the axis. To put this in more precise geometric terms, the block 146 and the actuator housings 148, 150, 152 in the present example all lie to one side of a plane containing the variator axis. Placing three actuators to one side of the variator axis is not new in itself, having been disclosed in the applicant's aforementioned International Patent Application PCT/GB99/02968, which shows suitable actuator orientation and the full disclosure of which is hereby incorporated herein by reference. As in PCT/GB99/02968, the actuator housings 148, 150, 152 associated with the second toroidal cavity are all intersected by a common plane parallel to the variator axis and can be referred to in this sense as being “co-planar”. Two of the actuator housings 148, 150 are juxtaposed in this arrangement but are separated along the direction of the variator axis. The orientations of the second actuator housings 148, 150, 152 result in the rollers being equally angularly spaced about the variator axis even though their actuators are not. To receive the first carrier part 124, the variator housing 116 has an axially facing recess 154 (see FIG. 4) which is circular and concentric with the variator axis. To receive the second carrier part 146, the variator housing has a radially facing rectangular recess in a region 156. Assembly of the variator is particularly straightforward. The two sub-assemblies referred to above can be assembled before the carrier parts 124, 146 are mated to the housing 116, after which second carrier part 146 is advanced along a direction non-parallel to the housing—in the illustrated embodiment this direction is generally radial with respect to the variator axis—and so mated with the housing. The first carrier part is advanced along a direction generally parallel to the variator axis and is thereby introduced to its recess 156 and mated with the housing 116. The arrangement of the actuator housings not only allows for convenient assembly but also enables them to be arranged in the bell-mouthed housing 116 in a space-saving manner. At the wider region of the housing 116, the first actuator housings 130 associated with the first toroidal cavity are at regular angular intervals about the variator axis making good use of the extra width and height available here. At the narrower region of housing the placement of the second actuator housings 148, 150, 152 allows them to be fitted into the available space. The illustrated arrangement provides for fluid supply to the roller control actuators in a constructionally convenient manner. In FIG. 4 it can be seen that the first carrier part forms a manifold for the fluid supply by virtue of two generally circumferentially extending channels 158, 160 formed in the rear face of the plate 126 and communicating with the actuators themselves through axial bores such as 162. One of the channels 158 conducts fluid to a working chamber of each actuator to urge the rollers in one direction (clockwise) while the other of the channels 160 conducts fluid to an opposed working chamber of each actuator to urge the rollers in an opposite direction (anti-clockwise). The two channels 158, 160 are connected to different regions of a hydraulic control circuit (not itself illustrated) which applies two different adjustable pressures thereto in order to control the variator. A back plate 164 covers the rear face of the plate 126 and confines fluid in the channels 158, 160. Of course the channels could be machined in the back plate rather than, or as well as, the plate 126 if desired. The second carrier part 146 can also form a manifold, by virtue of channels formed within the part 146 or in its surface, for distribution of hydraulic fluid. Looking now at FIG. 6, the construction of one of the actuators used in the variator will now be described. The actuator housing is in this drawing indicated at 700 and is formed by an aluminum casting with a hard anodised bore 702 forming a cylinder to receive a piston 704. A piston rod 706 connects the piston to a carriage 708 carrying the variator roller 710. The required seal between piston and cylinder is maintained by a seal 705 in an annular recess in the piston and some “swashing”—angular movement of the axis of the piston/piston rod—is permitted without loss of this seal. It can be seen in the drawing that the piston/piston rod assembly is slightly angled to the cylinder as a result of this swashing, which is necessary in order to permit the centre of the roller 710 to follow a path which is an arc of a circle, corresponding to the centre circle of the toroidal cavity in which the roller runs. The actuator is double-acting, having opposed working chambers 714, 716 on opposite sides of the piston 704. It is necessary to maintain a seal where the piston rod 706 emerges from the cylinder despite the lateral movement of the piston rod in this region resulting from its swashing motion and this is achieved by a floating seal arrangement 714 received in an annular recess 716 and capable of limited lateral movement The seal arrangement comprises a ring 718 formed in this embodiment of plastics and carrying an “L” section sealing band 720 biased radially inwardly by a first pre-stressed resilient loop 722 to form a seal against the piston rod 706 and also biased along an axial direction by a second pre-stressed resilient loop 724. Lateral movement of the piston rod 706 displaces the seal arrangement 714 in its recess 716 but does not impair the seal provided. Ports 726, 728 are provided in the casting forming the actuator housing for fluid supply to the chambers 714, 716.
20060109
20091229
20060720
99031.0
F16H1538
0
JOYCE, WILLIAM C
CONTINUOUSLY VARIABLE RATIO TRANSMISSION UNIT AND METHOD OF ASSEMBLY THEREOF
UNDISCOUNTED
0
ACCEPTED
F16H
2,006
10,532,552
ACCEPTED
Self-latching device
A self-latching sash latch device for use with a sliding closure. The latch device has a primary bolt (15) which in use engages with a strike (12). The primary bolt (15) is coupled to an operating element (13) whereby the primary bolt is moveable from a latching position to a retracted position. A retainer (38) retains the primary bolt (15) in the retracted position. A secondary bolt (16) is moveable with or independent of the primary bolt (15) and is engageable with the retainer (38) to release the retainer and enable the primary bolt (15) to move from a retracted position to the latching position.
1. A sash latch device of a self-latching type including a primary bolt for, in use, engagement with a strike, the primary bolt being coupled to an operating element whereby the primary bolt is moveable from a latching position to a retracted position, retaining means to retain the primary bolt in the retracted position and an activation means operable to release the retaining means to enable the primary bolt to move from the retracted position to the latching position. 2. A latch device as claimed in claim 1 wherein the activation means is a secondary bolt moveably carried by the primary bolt. 3. A latch device as claimed in claim 2 wherein the primary bolt is biased by biasing means to move to the latching position. 4. A latch device as claimed in claim 3 wherein the secondary bolt includes an engagement surface which, in use, is engageable with an abutment surface whereby the secondary bolt moves relative to the primary bolt to cause the retaining means to move to a release position. 5. A latch device as claimed in claim 4 wherein the secondary bolt includes a second engagement surface which, in use, is engageable with an abutment surface to cause the secondary bolt to move and cause the retaining means to move to the release position. 6. A latch device as claimed in claim 4 or 5 in combination with a strike wherein the abutment surface is formed by at least one surface of a wall of the strike. 7. A latch device as claimed in claim 5 wherein the secondary bolt is slidingly located in the primary bolt. 8. A latch device as claimed in claim 5 wherein the primary bolt is slidingly mounted in a chassis which is removably coupled to a base. 9. A latch device as claimed in claim 8 further including a cover removably mounted to the chassis. 10. A self-latching sash latch device including a latch body having a primary bolt, a strike, the primary bolt being mounted for movement in said body between a latching position where, in use, the primary bolt engages in a latching configuration with the strike and a retracted position, and an operating element operatively coupled to the primary bolt to enable the primary bolt to be moved from the latching position to the retracted position, a retaining means to retain the primary bolt in the retracted position and a release member moveable with or independent of the primary bolt to effect release of the retaining means to release the primary bolt and enable it to move from the retracted position to the latching position. 11. A latch device as claimed in claim 10 wherein the primary bolt is mounted for sliding movement between the latching and retracted positions and the release member is a secondary bolt mounted with the primary bolt such that movement of the secondary bolt relative to the primary bolt can occur. 12. A latching device as claimed in claim 11 wherein the secondary bolt has a leading end which has a first engagement surface which is exposed for contact with a part of the strike when the primary bolt is moved to the retracted position by the operating element, whereby contact between the first engagement surface and said part of the strike during relative movement between the body and strike causes the secondary bolt to move to the position where it effects release of the retaining means. 13. A latch device as claimed in claim 12 wherein the first engagement surface is a surface, which is inclined relative to the direction in which the secondary bolt is moveable. 14. A latch device as claimed in claim 12 or 13 wherein said strike has a wall which overlaps an engagement portion of the primary bolt when the primary bolt is in the latching position and the latch device is in a latching configuration. 15. A latch device as claimed in claim 12, wherein the secondary bolt has a second engagement surface which is engageable with said part of the strike upon relative movement between the body and strike occurring in an opposite direction. 16. A latch device as claimed in claim 12 wherein the primary bolt and the release means are independently biased by separate biasing means. 17. A latch device as claimed in claim 16 wherein the retaining means is a spring clip engageable with an abutment of the primary bolt. 18. A latch device as claimed in claim 17 wherein the release member is moveable to a position where it moves the spring clip out of engagement with the abutment to thereby release the retaining means. 19. A latch device as claimed in claims 8 or 18 further including limiting means engageable with the primary bolt when in the latching position. 20. A latch device as claimed in claim 18 further including limit release means engageable with the primary bolt when in the latching position operable by the operating element to release the limiting means to free the primary bolt for movement from the latching position to the retracted position. 21. A latch device as claimed in claims 1 or 10 further including indicator means moveable in response to movement of the primary bolt to provide an indication visually apparent from externally of the body of the latch device being in a latching or non-latching configuration. 22. A latch device as claimed in claim 21 wherein the indicator means comprises an elongate member with a distal end slidingly engaged in an opening in an external surface of the body. 23. A latch device as claimed in claim 22 wherein there is further provided one or more cover elements to cover the opening but moveable to enable said distal end to become visible. 24. A latch device as claimed in claim 23 wherein the cover elements comprise a pair of flaps carried by legs, the legs being moveable apart by movement of the elongate member to cause the flaps to move away from covering the opening. 25. A latch device as claimed in claim 22, 23 or 24 wherein the distal end includes a knob. 26. (canceled) 27. (canceled)
BACKGROUND TO THE INVENTION This invention relates to a latch device and more particularly one which is self-latching. The latch device is primarily intended for the latching of a sliding window sash in the closed position in a window frame. Currently there are a number of self-latching window sash latches available on the market. In most cases the latch operates after the window has been physically closed. Thus when the latch has reached the same level as the strike it latches the window in the closed position. To open the window an operating member e.g. a pull lever is operated and is held in the “open” position until such time as the latch has been lifted or slid past the strike. The operating member is then released. One problem with this type of latch device arises when disengaging the latch from the strike. As described above the action of opening the window involves holding the operating member and at the same time physically lifting or moving the window. Not only is this action awkward to perform but also it can be very difficult to perform on large windows, windows without finger grips, windows with more than one latch and windows which have limited/restricted access. A second problem is related to security and safety. With known latches there is no indication once the window sash has been moved to its fully closed position as to whether the latch has in fact successfully engaged with the strike. Thus a window thought to be latched may, in fact, be unlatched which can give rise to potential safety and security risks. SUMMARY OF THE INVENTION An object of the present invention is thus to provide a sash latch device that self-latches when the window sash is moved to the closed position. A further object of the present invention is to provide a sash latch device which self-latches and provides an indication if the latch has not completely self-latched. It is yet a further object of the present invention to provide a sash latch device, which permits the latch to be activated such that after activation the user can use both hands to pull or slide the window sash into an open position. Broadly according to one aspect of the invention there is provided a sash latch device of a self-latching type including a primary bolt for, in use, engagement with a strike, the primary bolt being coupled to an operating element whereby the primary bolt is moveable from a latching position to a retracted position, retaining means to retain the primary bolt in the retracted position and an activation means operable to release the retaining means to enable the primary bolt to move from the retracted position to the latching position. Broadly according to a second aspect of the invention there is provided a self-latching sash latch device including a latch body having a primary bolt, a strike, the primary bolt being mounted for movement in said body between a latching position where, in use, the primary bolt engages in a latching configuration with the strike and a retracted position, and an operating element operatively coupled to the primary bolt to enable the primary bolt to be moved from the latching position to the retracted position, a retaining means to retain the primary bolt in the retracted position and a release member moveable with or independent of the primary bolt to effect release of the retaining means to release the primary bolt and enable it to move from the retracted position to the latching position. Preferably the latch includes an indicator element which projects from the latch to indicate that the primary bolt is not in its latching position. BRIEF DESCRIPTION OF THE DRAWINGS In the following more detailed description of the present invention in its preferred forms, reference will be made to the accompanying drawings in which: FIG. 1 is a perspective view of the latch device according to a first embodiment of the invention, FIG. 2 is a front elevation view of the latch device shown in FIG. 1, FIG. 3 is an exploded perspective view of the latch device in FIGS. 1 and 2, FIG. 4 is a top perspective view of the first embodiment of the latch device with the cover removed and the latch device in the closed position with a strike, FIG. 5 is an underside view of the arrangement shown in FIG. 4, FIG. 6 is a cross sectional view of the latch device according to the first embodiment when mounted with a section of a window sash, FIG. 7 is an exploded view of a second embodiment of the latch device, FIG. 8 is a sectional view of the second embodiment, FIG. 9 is an underside view of the second embodiment but with the base removed, FIG. 10 is an underside view of a third embodiment of the latch device according to the invention, the latch being in the “locked” position, FIG. 11 is a view similar to FIG. 10 but showing the latch in the “unlocked” position, and FIG. 12 is a view similar to views 10 and 11 but showing a fourth embodiment with the latch in the “locked” position. DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION The sash latch device according to the present invention includes a cover 10 of suitable plastic or die cast zinc construction. The cover 10 is able to be mounted onto a chassis 11 in e.g. a slide dip fashion. The chassis 11 is preferable of die cast zinc construction. A latch element, as hereinafter described, is engageable with a strike 12. A button 13 or operating member is provided with cover 10 for operation of the latch element. The latch device further includes a base 14, which in the preferred form is plastic. According to the present invention the latch element comprises a primary bolt 15 and a secondary bolt 16. These components can be made from a suitable plastic or metal. The primary bolt 15 is located in an opening 17 in the chassis 11 such that projecting edges 18 of the primary bolt 15 slidingly engage with shoulders 19 at each side of opening 17. The primary bolt 15 is held in place in the chassis 11 by a base 14. The base 14 preferably clip mounted onto the chassis 11 by two pairs of spring clips 20 which, as shown in e.g. FIG. 4, clip over opposed edges of an aperture 21 in the chassis 11. The primary bolt 15 has a passageway 22 in which the secondary bolt 16 is slidingly engaged. A pair of springs 23 and 23a are provided for biasing the primary bolt 15 and the secondary bolt 16 to a “projecting” or latching position. One end of a spring 23 is located in a bore 24 in the secondary bolt 16. The other spring 23 is located in a recess 25 in the primary bolt 15. Each of primary bolt 15 and secondary bolt 16 have a projecting lug 26 and 26a respectively, which slidingly engage in respective slots 27 and 27a in the floor of base 14. Thus with the secondary bolt 16 located in passageway 22 of the primary bolt 15 and the primary bolt 15 held in position in opening 17 in the chassis 11, by the clip fastening of base 14 to the chassis 11 the free ends of the springs 23 and 23a engage against a surface formed by wall 28 of the chassis 11. The primary and secondary bolts 15/16 are thus always biased to a projecting position (see for example FIG. 5) as will hereinafter become apparent. Attached to or forming part of the primary bolt 15 is an indicator 29. This is an elongate member which is slidingly engaged through an opening 30 in wall 28. Opening 30 is aligned with an opening 31 in cover 10 when the cover 10 is clipped onto the chassis 11. The button 13 has a downwardly projecting spigot 32 which engages through an elongate slot 33 in the top of the cover 10. Spigot 32 engages in an opening 34 in the primary bolt 15. In use, the chassis 11 (after primary/secondary bolts 15/16 and base 14 have been clipped into place) is fastened to a section of a window sash S. This is achieved by mechanical fasteners such as screws, bolts etc. engaging through openings 42 in the chassis 11. Once the chassis 11 has been fastened into place the cover 10 is clipped over the chassis 11 which results in the button 13 engaging with the primary bolt 15. In a conventional manner, the strike 12 is mounted to another section which forms the opposing part of a sash or window frame as the case may be. In FIG. 6 the strike 12 is shown fastened to a part of a fixed window frame W though equally in a double sliding sash arrangement the strike 12 would be fitted to the second sash. To further describe the invention the latch and its associated strike 12 are considered to be mounted to the sash S and frame W with the primary bolt 11 projecting into the strike 12 (see for example FIG. 6). Because of the presence of the wall 39 or overhang of the strike 12 sash S is not able to move relative to frame W. However, if a sliding action is applied to the push button 13 so that it moves in the direction of arrow A (see FIG. 6) the primary bolt 15 will be moved so that the beak portion 43 of primary bolt 15 clears the wall 39. This means that the beak 43 of the primary bolt 15 moves out of the cavity 37 in the strike 12. This movement, however, also results in the secondary bolt 16 engaging a trigger clip 38 to thereby release the primary bolt 15. As shown in FIG. 3 trigger clip 38 is formed as an integral part of base 14 and extends on an upward incline to a distal or terminal end. Consequently, the primary bolt 15 moves back to its projecting position in preparation for self-latching with the strike when the window is closed. When the primary bolt 15 is moved in the direction of arrow A it comes into engagement with the trigger spring clip 38 in the base 14. As a result the primary bolt is held in the retracted position. This therefore enables the user to use both hands to cause the sash S to be moved relative to the frame W. The secondary bolt 16 has a double inclined leading edge formed by oppositely inclined surfaces 35 and 36. When primary bolt 15 is retracted the secondary bolt still protrudes into cavity 37. However, as the sash S is opened surface 35 of the secondary bolt 16 contacts the edge of wall 39. This causes the secondary bolt 16 to be pushed back into the primary bolt 15 for a distance sufficient to enable the secondary bolt 16 to clear the strike 12. When the window is moved back to the closed position the leading surface 36 of secondary bolt 16 comes into engagement with wall 39. This causes the secondary bolt 16 to be moved (in the direction of arrow A) relative to primary bolt 15. In the event that the primary bolt 15 has been held in the retracted position (by someone holding the primary bolt 15 when opening the window) the movement of secondary bolt 16 results in secondary bolt engaging with the trigger clip 38. This activates the clip to cause release of the primary bolt 15. The beak 43 can thus contact the edge of wall 39 such that when the sash is moved to the fully closed position the beak may enter the cavity 37. The latching device therefore self-latches when the latch reaches the same level as the strike. Consequently during both opening and closing of the window the secondary bolt 16 can cause release of the primary bolt. This ensures that the primary bolt 15 will always self latch. As shown in the drawings the chassis 11 also has a pair of protrusions 40 which are parallel and spaced apart. These correspond in position with two cavities 41 one of which is located either side of the main cavity 37 of strike 12. As the window S is closed these protrusion 40 (whose geometry is such as to accommodate window tolerance variance) come into contact with the corresponding cavities 41 in the strike 12. They thereby align the latch to the strike in the horizontal, vertical and lateral planes. Referring now to FIGS. 7, 8 and 9 a second embodiment of the latch device is illustrated. This embodiment of the invention incorporates an anti-tamper feature which prevents the primary bolt 15 from being forcibly retracted through manipulation from outside of the dwelling (i.e. the bolt being pushed back from striking engagement by use of a blade etc.). According to this embodiment of the invention the button 13 must be used in order for the latch to be moved to an unlocked position. The anti-tamper feature includes an anti-tamper clip 43 which is situated in the base 14. As the base 14 is in the preferred form of plastic construction the anti-tamper clip 43 can be integrally formed with the base 14. The anti-tamper clip 43 has the function of preventing the primary bolt 15 from retracting. This is achieved by the distal end 43 of the clip 43 engaging against edge 44 of the primary bolt 15. In this form of the invention the button 13 which is clipped into cover 10 and is slidingly moveable has a profiled or sloping end 45 on the spigot 32. The spigot 32 engages in an opening in the primary bolt 15 as previously described but in this embodiment the opening 34′ is elongate. Consequently a lost motion in bolt 15 is achieved. Thus if the primary bolt 15 is tampered with the bolt will slide back and engage with the anti-tamper clip 43 but the button 13 will not move because of the lost motion. The anti-tamper clip 43 is moved out of the way of the primary bolt 15 by the profiled end 45 of the button 13 sliding over the clip 43 hence pushing the clip clear of the primary bolt. The button 13 then continues to retract the primary bolt 15 in the normal manner. In the form of the invention as illustrated the primary bolt 15, if forced back by external manipulation, moves approximately 1.5 mm before it is stopped by the anti-tamper clip 43. As indicated above the button 13 does not move during this movement of the primary bolt 15. As a result there is no “redundant” travel of the button 13 during normal operation. Therefore, the anti-tamper feature is not readily discernable to the user as it is a feature which only comes into effect if attempts are made to forcibly open the latch from the outside. It is believed that the present invention addresses the problems previously identified and associated with known self-latching window sash latches. It achieves these objectives as follows: The action to disengage the latch from the strike is a “once-off” finger motion which results in the sliding movement of the button 13. Once this motion is completed the primary bolt 15 is held in the retracted position which, therefore, allows the user to remove his or her hands from the latch without the primary bolt 15 re-engaging in the strike 12. The user therefore has both hands free to open the window sash. The latch provides clear visual indication of whether the strike has been successfully engaged. Thus if the indicator 29 is protruding from opening 31 in cover 10 this is an indication that the primary bolt 15 has not moved back to its fully projecting position i.e. has not fully latched. The indication is visible from a distance and allows a user to quickly assess if the window is secure. The latch according to the present invention provides the above identified features without introducing additional steps to its operation. It retains all the benefits of a self-latching latch while providing features not normally available with self-latching latch devices. The combination of self-latching, indication and hands free operation is achieved by having the secondary bolt, the trigger spring clip 38 and primary bolt 15 all dependant on each other for timing, position and overall function. This, however, is achieved in a straight forward and operationally effectively manner. As disclosed herein the present invention can incorporate an indicator, which indicates whether the latch is in the locked or unlocked position. Currently there are a number of window hardware products available on the market and some of these have a method of indicating if the window is latched or not. These however suffer from deficiencies which include one or more of the following, namely, the need for additional parts (which leads to additional cost both in parts and assembly),not clear contrast between open and closed, difficulty in ascertaining if a latch is partially open or closed and the indicator being visible from outside the window (which can result in a security risk). In a further version of the present invention as shown in FIGS. 10-12, the invention provides an indicator which does not require additional components, is clear and obviously open or shut and cannot be seen from outside the window. The indicator therefore deals with the deficiencies associated with currently known indicators. As shown in FIG. 10, the base 14 has moulded into it, two legs 51 which are located spaced apart and side by side. The shape and thickness of these legs 51 is designed so that the legs act like hinged springs. The distal ends of the legs 51 have integrally moulded therewith flaps 52. As can be seen in FIG. 10, these flaps 52 obstruct the opening 31 in the cover 10. As previously disclosed, the primary bolt 15 has a protrusion 53 extending from the back of it. In one form of the invention the protrusion 53 is moulded as part of the primary bolt 15. When the primary bolt 15 is disengaged from the strike 12, the protrusion 53 pushes its way through the flaps 52 so that the distal end 54 of the protrusion 53 shows (with contrasting colour) through the window 31. The design of the legs 51 and the protrusion 53 ensure that the flaps 52 open very quickly, because the flaps are either side of the protrusion 53 and the hinge in a plane perpendicular to the direction of movement of the protrusion. As a consequence, there is nearly instant colour contrast between the distal end 54 of the protrusion 53 and the surrounding material of the cover 10. The indicator does not require additional components as the features are incorporated as part of existing components of the self-latching lock. Because the protrusion is designed to minimise time from open to closed and vice versa, it is easy to identify whether the lock is latched or not. Because the indicator is positioned at the front side (facing internally of the latch) it makes it very difficult to see from outside the window, thus, the indicator is not readily visible, which if it were, could result in a security risk. FIG. 12 shows a different version of the arrangement shown in FIGS. 10 and 11. According to this version, the legs 51 are no longer attached at one end and free at the other. Legs 51 are, as can be seen from FIG. 12, attached to the base 14 about two-thirds of the way down the length of the leg. A further difference is that the protrusion 53 still retains a knob 54 at its extreme or distal end. However, it additionally has a wider extended knob 55 at the base of the protrusion. According to this arrangement, the legs have a pivotal hinging point rather than a just one hinge. This allows the knob 54 at the distal end of the protrusion 53, to open the flaps 52 and the legs 51 in the “bolt retraction stroke”. However, on the “bolt engagement stroke” the knob 55 contacts the legs 51 in the area 56 below the pivot point 57, thereby closing the legs 51 and hence flaps 52. The advantage of using this arrangement is that the indicator is not reliant on the memory or spring of the plastic to close the flaps (the hinge may deteriorate over time and return the flaps to the closed position, leaving them partially opening and thereby reducing the effectiveness of the indicator). The protrusion 54 opens and closes the flaps 52 mechanically every time, thereby ensuring the flaps are positively opened or closed.
<SOH> BACKGROUND TO THE INVENTION <EOH>This invention relates to a latch device and more particularly one which is self-latching. The latch device is primarily intended for the latching of a sliding window sash in the closed position in a window frame. Currently there are a number of self-latching window sash latches available on the market. In most cases the latch operates after the window has been physically closed. Thus when the latch has reached the same level as the strike it latches the window in the closed position. To open the window an operating member e.g. a pull lever is operated and is held in the “open” position until such time as the latch has been lifted or slid past the strike. The operating member is then released. One problem with this type of latch device arises when disengaging the latch from the strike. As described above the action of opening the window involves holding the operating member and at the same time physically lifting or moving the window. Not only is this action awkward to perform but also it can be very difficult to perform on large windows, windows without finger grips, windows with more than one latch and windows which have limited/restricted access. A second problem is related to security and safety. With known latches there is no indication once the window sash has been moved to its fully closed position as to whether the latch has in fact successfully engaged with the strike. Thus a window thought to be latched may, in fact, be unlatched which can give rise to potential safety and security risks.
<SOH> SUMMARY OF THE INVENTION <EOH>An object of the present invention is thus to provide a sash latch device that self-latches when the window sash is moved to the closed position. A further object of the present invention is to provide a sash latch device which self-latches and provides an indication if the latch has not completely self-latched. It is yet a further object of the present invention to provide a sash latch device, which permits the latch to be activated such that after activation the user can use both hands to pull or slide the window sash into an open position. Broadly according to one aspect of the invention there is provided a sash latch device of a self-latching type including a primary bolt for, in use, engagement with a strike, the primary bolt being coupled to an operating element whereby the primary bolt is moveable from a latching position to a retracted position, retaining means to retain the primary bolt in the retracted position and an activation means operable to release the retaining means to enable the primary bolt to move from the retracted position to the latching position. Broadly according to a second aspect of the invention there is provided a self-latching sash latch device including a latch body having a primary bolt, a strike, the primary bolt being mounted for movement in said body between a latching position where, in use, the primary bolt engages in a latching configuration with the strike and a retracted position, and an operating element operatively coupled to the primary bolt to enable the primary bolt to be moved from the latching position to the retracted position, a retaining means to retain the primary bolt in the retracted position and a release member moveable with or independent of the primary bolt to effect release of the retaining means to release the primary bolt and enable it to move from the retracted position to the latching position. Preferably the latch includes an indicator element which projects from the latch to indicate that the primary bolt is not in its latching position.
20050422
20080805
20060216
75571.0
E05C110
1
MERLINO, ALYSON MARIE
SELF-LATCHING DEVICE
UNDISCOUNTED
0
ACCEPTED
E05C
2,005
10,532,605
ACCEPTED
Method of degrading hardly degradable protein
Disclosed is an agent for digesting a protein highly resistant to denaturation and degradation, comprising as an active ingredient an enzyme exhibiting an activity of digesting a protein highly resistant to denaturation and degradation and having the following properties: (a) activity and substrate specificity: hydrolyzing a peptide bond of a protein highly resistant to denaturation and degradation; (b) molecular weight: 31,000 (determined by SDS-polyacrylamide gel electrophoresis using a homogeneous gel having a gel concentration of 12%); (c) isoelectric point: pI 9.3 (determined by polyacrylamide gel isoelectric focusing electrophoresis); (d) optimum pH: pH 9.0 to 10.0; and (e) optimum temperature for activity: 60 to 70° C.
1. An agent for digesting a protein highly resistant to denaturation and degradation, comprising as an active ingredient an enzyme exhibiting an activity of digesting a protein highly resistant to denaturation and degradation and having the following properties: (a) activity and substrate specificity: hydrolyzing a peptide bond of a protein highly resistant to denaturation and degradation; (b) molecular weight: 31,000 (determined by an SDS-polyacrylamide gel electrophoresis using a homogeneous gel having a gel concentration of 12%); (c) isoelectric point: pI 9.3 (determined by polyacrylamide gel isoelectric focusing electrophoresis); (d) optimum pH: pH 9.0 to 10.0; and (e) optimum temperature for activity: 60 to 70° C. 2. The agent according to claim 1, wherein the enzyme has the following property: (g) exhibiting an activity of 2 U/g or more as the activity of digesting a protein highly resistant to denaturation and degradation (determined as an activity of digesting keratin azure. 3. The agent according to claim 1, wherein the enzyme has the following property: (h) derived from a microorganism belonging to genus Bacillus. 4. An agent for digesting a protein highly resistant to denaturation and degradation, comprising as an active ingredient an enzyme selected from the group consisting of (X) an enzyme comprising the amino acid sequence of SEQ ID NO: 2; (Y) a modified enzyme exhibiting an activity of digesting a protein highly resistant to denaturation and degradation, and comprising an amino acid sequence in which one or plural amino acids are deleted, substituted, or added in the amino acid sequence of SEQ ID NO: 2; and (Z) a homologous enzyme exhibiting an activity of digesting a protein highly resistant to denaturation and degradation, and comprising an amino acid sequence having an 85% or more homology with the amino acid sequence of SEQ ID NO: 2. 5. The agent according to claim 1, wherein the protein highly resistant to denaturation and degradation is a pathogenic prion protein. 6. A method for digesting a protein highly resistant to denaturation and degradation, comprising the step of bringing the protein highly resistant to denaturation and degradation into contact with the agent or enzyme according claim 1. 7. Use of the enzyme according to claim 1, in the manufacture of an agent for digesting a protein highly resistant to denaturation and degradation. 8. An agent for detoxifying a pathogenic prion protein in a subject which may be contaminated with a pathogenic prion protein, comprising as an active ingredient the enzyme according to claim 1. 9. A method for detoxifying a pathogenic prion protein, comprising the step of bringing a subject which may be contaminated with a pathogenic prion protein into contact with the enzyme according to claim 1. 10. A method for detoxifying a pathogenic prion protein, comprising the step of bringing a subject which may be contaminated with a pathogenic prion protein into contact with the enzyme according to claim 1, without preheating the subject. 11. A method for detoxifying a pathogenic prion protein, comprising the step of bringing a subject which may be contaminated with a pathogenic prion protein into contact with the enzyme according to claim 1, without preheating the subject at 90° C. or more. 12. Use of the enzyme according to claim 1, in the manufacture of an agent for detoxifying a pathogenic prion protein. 13. The agent according to claim 2, wherein the enzyme has the following property: (h) derived from a microorganism belonging to genus Bacillus. 14. The agent according to claim 2, wherein the protein highly resistant to denaturation and degradation is a pathogenic prion protein. 15. The agent according to claim 3, wherein the protein highly resistant to denaturation and degradation is a pathogenic prion protein. 16. The agent according to claim 4, wherein the protein highly resistant to denaturation and degradation is a pathogenic prion protein. 17. A method for digesting a protein highly resistant to denaturation and degradation, comprising the step of bringing the protein highly resistant to denaturation and degradation into contact with the agent or enzyme according to claim 2. 18. A method for digesting a protein highly resistant to denaturation and degradation, comprising the step of bringing the protein highly resistant to denaturation and degradation into contact with the agent or enzyme according to claim 3. 19. A method for digesting a protein highly resistant to denaturation and degradation, comprising the step of bringing the protein highly resistant to denaturation and degradation into contact with the agent or enzyme according to claim 4. 20. A method for digesting a protein highly resistant to denaturation and degradation, comprising the step of bringing the protein highly resistant to denaturation and degradation into contact with the agent or enzyme according to claim 5.
TECHNICAL FIELD The present invention relates to an agent for digesting a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein) and a method for digesting the protein. Background Art A pathogenic prion protein seems to be involved in such diseases as scrapie in sheep or mice, Creutzfeldt-Jakob disease (CJD) in humans, and bovine spongiform encephalopathy (BSE; popularly known as mad cow disease) in cattle give rise to nervous symptoms such as dysstasia or dysbasia. It is noted that human consumption of beef infected with the pathogenic prion protein may cause a variant Creutzfeldt-Jakob disease (vCJD) by infection. In particular, BSE is an extremely serious disease in the light of a safe supply of beef for human consumption. Such diseases may develop when the pathogenic prion protein transferred into the human body from the outside causes a conformational change of a normal prion protein generally located in the brain [Nature, (Great Britain), 1994, Vol. 370, p. 471 (non-patent reference 1)]. To prevent the development of disease by an infection of the pathogenic prion protein, it is necessary to digest and detoxify the pathogenic prion protein as a cause thereof to the extent that the disease does not develop. However, the pathogenic prion protein is believed to be extremely stable when subjected to a commonly used sterilizing treatment (such as boiling) and exhibits little or no loss of infectivity by the sterilizing treatment. Further, although the pathogen is a protein, it is not difficult to digest the pathogen completely with a conventional protease. Under these circumstances, a method for digesting the pathogenic prion protein efficiently and a method for preventing the diseases from developing by infection are desired. As a method for digesting a protein highly resistant to denaturation and degradation such as a pathogenic prion protein, for example, Japanese Unexamined Patent Publication (Kokai) No. 6-46871 (patent reference 1) discloses a method for digesting keratin-containing proteins highly resistant to conventional proteases, using keratinase, a protease, derived from Bacillus licheniformis PWD-1. The publication discloses that keratinase is used in digesting keratin-containing proteins (for example, animal hair, human hair, or feathers), but neither discloses nor suggests any effects of the keratinase on a pathogenic prion protein. In this connection, a DNA encoding the keratinase derived from Bacillus licheniformis PWD-1 was obtained [Unexamined International Publication (Kohyo) No. 10-500863 (patent reference 2)]. Further, U.S. Pat. No. 6,613,505 (patent reference 3) discloses that the keratinase derived from Bacillus licheniformis PWD-1 is used in digesting a pathogenic prion protein highly resistant to denaturation and degradation. However, to reduce or digest the pathogenic prion protein by the method disclosed in U.S. Pat. No. 6,613,505, two of treatment step, that is, a heat treatment as a pretreatment, and an enzyme treatment, are necessary. In this method, an apparatus for heating is necessary, and thus it is not easy to carry out the method in common facilities without such an apparatus for heating. Further, the two-step procedures are complicated. Furthermore, International Publication No. 02/053723 (patent reference 4) discloses that a heat-resistant protease is used in digesting a pathogenic prion protein. However, it discloses that when a pathogenic prion protein was digested by a protease derived from Bacillus thermoproteolytics Rokko described in Examples thereof, the pathogenic prion protein was not sufficiently digested with the protease alone, but was sufficiently digested with the protease in the presence of sodium dodecyl sulfate. In addition, a neutral salt is necessary to activate the protease. Further, the protease requires a metal ion, and thus when a chelating agent is present in a reaction, the activity is remarkably decreased. (non-patent reference 1) Nature, (Great Britain), 1994, Vol. 370, p. 471 (patent reference 1) Japanese Unexamined Patent Publication (Kokai) No. 6-46871 (patent reference 2) Unexamined International Publication (Kohyo) No. 10-500863 (patent reference 3) U.S. Pat. No. 6,613,505 (patent reference 4) International Publication No. 02/053723 DISCLOSURE OF THE INVENTION An object of the present invention is to provide an enzyme produced at a low cost and exhibiting a high activity of digesting a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein) in comparison with known proteases; an agent for digesting a protein highly resistant to denaturation and degradation and an agent for detoxifying a pathogenic prion protein, containing the enzyme as an active ingredient; and a method for digesting a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein) and a method for detoxifying a pathogenic prion protein, using the enzyme or the agent. The present inventors found an enzyme exhibiting an extremely high activity of digesting a protein strongly resistant to denaturation and degradation (particularly a pathogenic prion protein) derived from a microorganism belonging to genus Bacillus, in comparison with enzymes known to digest a protein highly resistant to denaturation and degradation. The enzyme which may be used in the present invention exhibited excellent properties, as shown in Examples described below, in comparison with the above-mentioned enzymes previously reported to be used in digesting a pathogenic prion protein, for example, the enzyme (keratinase) prepared from Bacillus licheniformis PWD-1 disclosed in U.S. Pat. No. 6,613,505, and the enzyme prepared from Bacillus thermoproteolyticus Rokko disclosed in International Publication No. 02/053723. Particularly, it was found that the enzyme which may be used in the present invention exhibited an extremely high activity of digesting a pathogenic prion protein in comparison with the enzyme prepared from Bacillus licheniformis PWD-1 (see Examples 7 and 8). Further, it was surprisingly found that the protein was digested without a thermal treatment described in U.S. Pat. No. 6,613,505 (see Examples 7 and 8). In comparison with the enzyme prepared from Bacillus thermoproteolyticus Rokko, it was found that the enzyme which may be used in the present invention exhibited an extremely high activity of digesting a pathogenic prion protein (see Examples 9 to 11). Further, it was surprisingly found that the protein exhibited an excellent activity of digesting a pathogenic prion protein regardless of the presence of sodium dodecyl sulfate (see Examples 9 to 11). Further, the present inventors provided an agent for digesting a protein highly resistant to denaturation and degradation and an agent for detoxifying a pathogenic prion protein, containing the newly found enzyme as an active ingredient, and further found a method for digesting a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein) and a method for detoxifying a pathogenic prion protein, using the enzyme or the agent. The present invention relates to: [1] an agent for digesting a protein highly resistant to denaturation and degradation, comprising as an active ingredient an enzyme exhibiting an activity of digesting a protein highly resistant to denaturation and degradation and having the following properties: (a) activity and substrate specificity: hydrolyzing a peptide bond of a protein highly resistant to denaturation and degradation, (b) molecular weight: 31,000 (determined by an SDS-polyacrylamide gel electrophoresis using a homogeneous gel having a gel concentration of 12%), (c) isoelectric point: pI 9.3 (determined by polyacrylamide gel isoelectric focusing electrophoresis), (d) optimum pH: pH 9.0 to 10.0, and (e) optimum temperature for activity: 60 to 70° C.; [2] the agent of [1], wherein the enzyme has the following property: (g) exhibiting an activity of 2 U/g or more as the activity of digesting a protein highly resistant to denaturation and degradation (determined as an activity of digesting keratin azure; [3] the agent of [1] or [2], wherein the enzyme has the following property: (h) derived from a microorganism belonging to genus Bacillus; [4] an agent for digesting a protein highly resistant to denaturation and degradation, comprising as an active ingredient an enzyme selected from the group consisting of (X) an enzyme comprising the amino acid sequence of SEQ ID NO: 2; (Y) a modified enzyme exhibiting an activity of digesting a protein highly resistant to denaturation and degradation, and comprising an amino acid sequence in which one or plural amino acids are deleted, substituted, or added in the amino acid sequence of SEQ ID NO: 2; and (Z) a homologous enzyme exhibiting an activity of digesting a protein highly resistant to denaturation and degradation, and comprising an amino acid sequence having an 85% or more homology with the amino acid sequence of SEQ ID NO: 2; [5] the agent of [1] to [4], wherein the protein highly resistant to denaturation and degradation is a pathogenic prion protein; [6] a method for digesting a protein highly resistant to denaturation and degradation, comprising the step of bringing the protein highly resistant to denaturation and degradation into contact with the agent or enzyme of [1] to [5]; [7] use of the enzyme of [1] to [5], in the manufacture of an agent for digesting a protein highly resistant to denaturation and degradation; [8] an agent for detoxifying a pathogenic prion protein in a subject which may be contaminated with a pathogenic prion protein, comprising as an active ingredient the enzyme of [1] to [5]; [9] a method for detoxifying a pathogenic prion protein, comprising the step of bringing a subject which may be contaminated with a pathogenic prion protein into contact with the enzyme of [1] to [5] or the agent of [8]; [10] a method for detoxifying a pathogenic prion protein, comprising the step of bringing a subject which may be contaminated with a pathogenic prion protein into contact with the enzyme of [1] to [5] or the agent of [8], without preheating the subject; [11] a method for detoxifying a pathogenic prion protein, comprising the step of bringing a subject which may be contaminated with a pathogenic prion protein into contact with the enzyme of [1] to [5] or the agent of [8], without preheating the subject at 90° C. or more; and [12] use of the enzyme of [1] to [5], in the manufacture of an agent for detoxifying a pathogenic prion protein. BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a graph showing the optimum pH and stable pH of a purified enzyme used in the present invention at 37° C. FIG. 2 is a graph showing the optimum temperature of a purified enzyme used in the present invention at pH 9.0. FIG. 3 shows the results in which the mouse pathogenic prion protein was digested with a purified enzyme used in the present invention. FIG. 4 shows the results in which the mouse pathogenic prion protein was digested with enzyme composition A used in the present invention. FIG. 5 shows the results in which the sheep pathogenic prion protein was digested with enzyme composition A used in the present invention. FIG. 6 shows the results in which the mouse pathogenic prion protein was digested with enzyme composition A used in the present invention. FIG. 7 shows the results in which the hamster pathogenic prion protein (strain Sc237) was digested with enzyme composition A′ used in the present invention or thermoase for comparison. FIG. 8 shows the results in which the hamster pathogenic prion protein (strain Sc237) was digested in the presence of SDS with enzyme composition A′ used in the present invention or thermoase for comparison. FIG. 9 shows the results in which the hamster pathogenic prion protein (strain Sc237) stuck on polystyrene was digested with enzyme composition A′ used in the present invention or thermoase for comparison. BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be explained in detail hereinafter. The enzyme used in the present invention exhibits an activity of digesting a protein highly resistant to denaturation and degradation, that is, a hydrolytic activity of peptide bonds in the protein highly resistant to denaturation and degradation. The term “protein highly resistant to denaturation and degradation” as used herein means a protein which is not easily digested with a commonly used protease such as proteinase K or trypsin. More particularly, it means a protein which is not completely digested when treated with 1 μg/mL of proteinase K at 37° C. for 1 hour. As the protein highly resistant to denaturation and degradation, there may be mentioned, for example, a pathogenic prion protein, keratin, collagen, or elastin. The term “pathogenic prion protein” as used herein means a protein which is involved in the onset of, for example, scrapie, CJD, or BSE, more particularly, a prion protein conformationally changed from a normal prion generally located in the brain. The pathogenic prion protein includes a protein derived from, for example, a human, hamster, mouse, bovine, or sheep. The normal prion protein and the pathogenic prion protein have the same amino acid sequence, but different tertial structures. In the normal prion protein, the content of the α-helix structure in which the polypeptide chain of the prion protein takes a spiral form is high, and the content of the β-sheet structure in which the polypeptide chain takes a plane form is low. In construct, the pathogenic prion protein contains a high content of the β-sheet structure (Pan, PNAS ,90, 10962, 1993). In addition, each prion protein derived from the above animals has a high homology among the amino acid sequences thereof, and shows the same property in which a conformational change of the normal prion protein causes the change to the pathogenic prion protein highly resistant to denaturation and degradation. The pathogenic prion protein considered to be a pathogen of the above diseases is extremely stable when subjected to a general sterilizing treatment such as boiling, and thus exhibits little or no loss of infectivity by such a sterilizing treatment. Further, while the normal prion protein is easily digested, and thus a half life thereof in the body is approximately 2 hours, the pathogenic prion protein has a half life of 24 hours or more, and is highly resistant to digestion. When the digestibilities of the normal and pathogenic prion proteins to conventional proteases such as commercially available proteinase K were evaluated, it was reported that the normal prion protein was easily digested and was sensitive, but the pathogenic prion protein exhibited a low digestibility and was highly resistant to digestion (Prusiner, Science, 252, 1515, 1991). It is considered that the difference in digestibility is due to the difference in the tertial structures as described above. The normal prion protein may be distinguished from the pathogenic prion protein, for example, by utilizing the difference in digestibility to a protease. For example, a tissue derived from an animal which may be contaminated with the pathogenic prion protein is homogenized to prepare a homogeneous suspension. The suspension is treated with a commonly used protease such as proteinase K, and analyzed by Western blotting (Burnette, Anal. Biochem., 112, 195, 1981) to detect the prion protein. When no band is detected, it may be judged that the tissue contains only the normal prion protein. When a protein band resistant to the protease is detected, it may be judged that the tissue contains the pathogenic prion protein. The term “activity of digesting a protein highly resistant to denaturation and degradation” as used herein means a hydrolytic activity of peptide bonds in the protein highly resistant to denaturation and degradation. As a unit of the “activity of digesting a protein highly resistant to denaturation and degradation”, two different units are used herein. In the first unit, “1 unit” of an enzyme is defined as an amount of the enzyme which can generate a product corresponding to 1 μmol of glycine per minute, when a suspension containing 0.5% (as a final concentration) of keratin powder (derived from human hair; Nacalai Tesque) is treated with the enzyme at pH 8.0 and 60° C. for 1 hour. In the second unit, “1 unit” of an enzyme is defined as 0.001 of an amount of absorbance changed, when a suspension containing 0.8% (as a final concentration) of keratin azure (Sigma) is treated with the enzyme at pH 8.0 and 37° C. for 16 hours, and an amount of a pigment released to a supernatant of the reaction mixture per minute is measured at an absorbance of 595 nm. In this connection, the keratin azure is a compound in which an azo pigment is bound to keratin (for example, keratin derived from wool). The keratin azure is widely used as a substance for measuring an activity (i.e., a keratinase activity) of digesting keratin, a protein highly resistant to denaturation and degradation, because an azo-pigment-bound amino acid or an azo-pigment-bound peptide released by digesting peptide bonds in keratin can be spectroscopically measured. The “activity of digesting a pathogenic prion protein” as used herein means a hydrolytic activity of peptide bonds in the pathogenic prion protein. A degree or strength of the “activity of digesting a pathogenic prion protein” may be judged, for example, by analyzing a digestion of the pathogenic prion protein contained in a suspension containing 1% of a brain tissue derived from a mouse suffering from scrapie. More particularly, a brain tissue derived from a mouse infected with the pathogenic prion protein is homogenized to prepare a homogeneous suspension, and the suspension is treated with an enzyme or enzyme composition to be judged. Proteins contained in the reaction mixture are separated by electrophoresis, and the prion protein is detected by Western blotting. When no band is detected, the result shows that the enzyme or enzyme composition to be judged exhibits an extremely high activity of digesting a pathogenic prion protein. When a protein band resistant to the protease is detected and the band is thin, the result shows that the enzyme or enzyme composition exhibits a moderate activity of digesting a pathogenic prion protein. When the protein band is dense, the result shows that the enzyme or enzyme composition exhibits a low activity of digesting a pathogenic prion protein. Protein Exhibiting an Activity of Digesting a Protein Highly Resistant to Denaturation and Degradation (Particularly a Pathogenic Prion Protein) In the present invention, for example, an enzyme having the following properties may be used. (a) Activity and Substrate Specificity The enzyme hydrolyzes one or more peptide bonds of a protein, particularly one or more peptide bonds of a protein highly resistant to denaturation and degradation (such as a pathogenic prion protein). As to the substrate specificity, the enzyme exhibits high activities of digesting casein, collagen, elastin, and keratin, as well as the pathogenic prion protein. (b) Molecular Weight The molecular weight determined by an SDS-polyacrylamide gel electrophoresis using a 12% homogeneous gel (i.e., a homogeneous gel in which a concentration of polyacrylamide is 12%) is approximately 31,000. The molecular weight determined by an SDS-polyacrylamide gel electrophoresis using a 15% homogeneous gel (i.e., a homogeneous gel in which a concentration of polyacrylamide is 15%; such as a gel manufactured by ATTO) is approximately 26,000. (c) Isoelectric Point The isoelectric point (pI) determined by a polyacrylamide gel isoelectric focusing electrophoresis is approximately 9.3. (d) Optimum pH and Stable pH The optimum pH, evaluated by an activity of digesting keratinazure as an index, is approximately pH 9.0 to 10.0. The enzyme exhibits a stable activity at approximately pH 7.0 to 12.0, and a high activity at approximately pH 8.0 to 10.5. (e) Optimum Temperature for Activity The optimum temperature for activity, evaluated by an activity of digesting keratin azure as an index, is approximately 60 to 70° C. (f) Deactivating pH The enzyme was inactivated at approximately pH 5 or less, when evaluated by an activity of digesting keratinazure as an index. In Table 1, the above properties of the enzyme which may be used in the present invention are shown in comparison with those of a known protease exhibiting an activity of digesting a protein highly resistant to denaturation and degradation (keratinase derived from Bacillus licheniformis PWD-1). TABLE 1 Enzyme used in the present invention Known protease Activity and substrate specificity ++ + pathogenic prion protein casein + + collagen + + elastin + + keratin + + Molecular weight 31,000 33,000 Isoelectric point 9.3 7.25 Optimum pH 9.0 to 10.0 7.5 Optimum temperature 60 to 70° C. 50° C. In another embodiment of the present invention, an enzyme comprising the amino acid sequence of SEQ ID NO: 2, or a modified or homologous enzyme thereof may be used. The “enzyme comprising the amino acid sequence of SEQ ID NO: 2” includes, for example, an enzyme consisting of the amino acid sequence of SEQ ID NO: 2; a fusion enzyme consisting of an amino acid sequence in which an appropriate marker sequence is added to the N-terminus and/or the C-terminus of the polypeptide consisting of the amino acid sequence of SEQ ID NO: 2, and exhibiting an activity of digesting a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein); a fusion enzyme consisting of the polypeptide consisting of the amino acid sequence of SEQ ID NO: 2 and a partner for fusion, and exhibiting an activity of digesting a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein); and an enzyme consisting of an amino acid sequence in which a presequence (signal sequence) or a fragment thereof is added to the N-terminus of the amino acid sequence of SEQ ID NO: 2. In addition, a fusion enzyme consisting of an amino acid sequence in which an appropriate marker sequence and/or an appropriate partner for fusion is further added to the amino acid sequence in which a presequence is added to the N-terminus of the amino acid sequence of SEQ ID NO: 2, is included in the “enzyme comprising the amino acid sequence of SEQ ID NO: 2”. As the presequence, a naturally-occurring presequence or an artificially designed sequence may be used. As the naturally-occurring presequence, not only a presequence derived from Bacillus licheniformis (particularly a presequence of a Bacillus licheniformis derived enzyme capable of digesting a protein highly resistant to denaturation and degradation), but also a presequence derived from organisms other than Bacillus licheniformis, may be used. As the marker sequence, for example, a sequence for easily carrying out a confirmation of polypeptide expression, a confirmation of intracellular localization thereof, or a purification thereof may be used. As the sequence, there may be mentioned, for example, a FLAG tag, a hexa-histidine tag, a hemagglutinin tag, or a myc epitope. As the partner for fusion, there may be mentioned, for example, a polypeptide for purification [for example, glutathione S-transferase (GST) or a fragment thereof], a polypeptide for detection [for example, hemagglutinin or β-galactosidase αpeptide (LacZ α), or a fragment thereof], or a polypeptide for expression (for example, a signal sequence). In the above fusion polypeptide, an amino acid sequence which can be specifically digested with a protease such as thrombin or factor Xa may be optionally inserted between the polypeptide consisting of the amino acid sequence of SEQ ID NO: 2 and the marker sequence or the partner for fusion. The term “modified enzyme” as used herein means a protein comprising an amino acid sequence in which one or plural (for example, one or several) amino acids are deleted, substituted, or added in the amino acid sequence of SEQ ID NO: 2, and exhibiting an activity of digesting a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein). In this connection, the number of amino acids to be modified, such as “deleted, substituted, or added”, is preferably 1 to 30, more preferably 1 to 10, most preferably 1 to 6. The “modified enzyme” includes a protein comprising an amino acid sequence in which one or plural (for example, one or several) amino acids are conservatively substituted in the amino acid sequence of SEQ ID NO: 2, and exhibiting an activity of digesting a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein). The term “conservative substitution” as used herein means that one or plural amino acid residues contained in a protein are replaced with different amino acids having similar chemical properties so that the activities of the protein are not substantially changed. As the conservative substitution, there may be mentioned, for example, a substitution of a hydrophobic residue for another hydrophobic residue, or a substitution of a polar residue for another polar residue having the same charge. Amino acids which have similar chemical properties and can be conservatively substituted with each other are known to those skilled in the art. More particularly, as nonpolar (hydrophobic) amino acids, there may be mentioned, for example, alanine, valine, isoleucine, leucine, proline, tryptophan, phenylalanine, or methionine. As polar (neutral) amino acids, there may be mentioned, for example, glycine, serine, threonine, tyrosine, glutamine, asparagine, or cysteine. As basic amino acids having a positive charge, there may be mentioned, for example, arginine, histidine, or lysine. As acidic amino acids having a negative charge, there may be mentioned, for example, aspartic acid or glutamic acid. The term “homologous protein” as used herein means a protein comprising an amino acid sequence having an 85% or more (preferably 90% or more, more preferably 95% or more, still further preferably 98% or more, most preferably 99% or more) homology with the amino acid sequence of SEQ ID NO: 2, and exhibiting an activity of digesting a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein). The term “homology” as used herein means a value obtained by a known program for a homology search, BLAST (Basic local alignment search tool; Altschul, S. F. et al., J. Mol. Biol., 215, 403-410, 1990; obtained from National Center for Biotechnology Information). The enzyme comprising the amino acid sequence of SEQ ID NO: 2, or the modified or homologous enzyme thereof exhibits an activity of digesting a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein) of preferably 2 U/g or more, more preferably 2 to 500 U/g, still further preferably 10 to 500 U/g, most preferably 20 to 500 U/g, as an activity of digesting keratin azure. When an activity of digesting keratin powder is used as an index, it is preferably 1 U/g or more, more preferably 1 to 5000 U/g, most preferably 5 to 3000 U/g. An origin of the enzyme used in the present invention is not particularly limited, so long as it is an enzyme having the above-mentioned physical and chemical properties, an enzyme comprising the amino acid sequence of SEQ ID NO: 2, or a modified or homologous enzyme thereof. For example, enzymes derived from animals, plants, or microorganisms may be used. An enzyme produced by an microorganism belonging to genus Bacillus is preferable, an enzyme produced by Bacillus licheniformis is more preferable, and an enzyme produced by Bacillus licheniformis MSK-103 (FERM BP-08487) is most preferable. Further, a mutant derived from the microorganisms may be used. Deposit of Microorganism Bacillus licheniformis MSK-103 (FERM BP-08487) was domestically deposited in the International Patent Organism Depositary National Institute of Advanced Industrial Science and Technology (Address: AIST Tsukuba Central 6, 1-1, Higashi 1-chome Tukuba-shi, Ibaraki-ken 305-8566 Japan) on Oct. 16, 2002, and was transferred to an international deposit on Sep. 16, 2003. The international deposit number (a number in parenthesis [ ] following the international deposit number is a domestic deposit number) is FERM BP-08487 [FERM P-19068]. As the enzyme used in the present invention, subtilisins may be used, and subtilisin DY (WO98/30682) is preferable. The enzyme used in the present invention may be obtained by isolating and purifying the enzyme of interest from a microorganism, for example, as described in Example 1. Alternatively, it may be obtained by expressing a polynucleotide encoding the protein of interest in an appropriate host by genetic engineering techniques, and isolating and purifying the produced protein, as described below. To obtain the enzyme used in the present invention from a microorganism producing the enzyme, the microorganism may be cultivated under the conditions suitable for the microorganism, and the obtained broth, supernatant, or microorganism may be treated by known separation and purification techniques. Hereinafter procedures of the microorganism cultivation and the protein purification will be explained in accordance with an embodiment using Bacillus licheniformis MSK-103 (FERM BP-08487) as the microorganism producing the enzyme used in the present invention. A culture medium [1% polypeptone, 0.2% yeast extract, and 0.1% magnesium sulfate heptahydrate (pH 7.0)] is autoclaved by a conventional method, and the medium is inoculated with Bacillus licheniformis MSK-103 (FERM BP-08487). A cultivation is carried out at 37-50° C. under aeration and agitation for 24-72 hours. The resulting broth is centrifuged at approximately 3000 G to obtain a supernatant containing the enzyme used in the present invention. If necessary, the supernatant is concentrated 2 to 50-fold with an ultrafilter (5,000 to 30,000-molecular-weight cutoff) to obtain a concentrated supernatant containing the enzyme used in the present invention. The above supernatant or the above concentrated supernatant contains various substances other than the enzyme used in the present invention, and thus the enzyme used in the present invention may be further purified, for example, by the following procedures. The above supernatant or concentrated supernatant is filtered with a microfilter membrane (pore size=approximately 0.45 μm) to remove microorganisms. Ammonium sulfate is added to the resulting sterile filtrate, to a final concentration of 1 mol/L, and a buffer agent (Tris-HCl) is further added to pH 8.5 and a final concentration of 50 mmol/L. For a further purification by a hydrophobic chromatography, the prepared solution is adsorbed to a phenyl Sepharose column, and eluted by a linear gradient with ammonium sulfate (1 mol/L to 0 mol/L) in a Tris-HCl buffer, to obtain a fraction containing the enzyme used in the present invention. The fraction is concentrated 20 to 30-fold with an ultrafilter (5,000 to 10,000-molecular-weight cutoff), and a gel filtration chromatography is carried out, for example, using Superdex 75 (Pharmacia) gel. The concentrated solution is developed through the gel with a phosphate buffer (0.025 mol/L, pH 7.0) containing 0.1 mol/L sodium chloride as an eluent, to obtain the enzyme used in the present invention. According to the above purification procedures, the enzyme used in the present invention can be purified as a band by an electrophoretic analysis. Polynucleotide Encoding Protein having an Activity of Digesting a Protein Highly Resistant to Denaturation and Degradation (Particularly a Pathogenic Prion Protein) The polynucleotide encoding the enzyme used in the present invention may be obtained, for example, by the following procedures. When a certain amino acid sequence is given, a nucleotide sequence encoding the amino acid sequence can be easily determined. Therefore, those skilled in the art can select various nucleotide sequences encoding the enzyme used in the present invention. The term “polynucleotide” as used herein includes DNA and RNA, preferably DNA. The polynucleotide encoding the enzyme used in the present invention may be typically selected from the group consisting of: (i) a polynucleotide comprising the nucleotide sequence of SEQ ID NO: 1 (preferably a polynucleotide consisting of the nucleotide sequence of SEQ ID NO: 1); (ii) a polynucleotide comprising a nucleotide sequence in which one or plural (for example, one or several) nucleotides are deleted, substituted, or added in the nucleotide sequence of SEQ ID NO: 1, and encoding a protein exhibiting an activity of digesting a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein); and (iii) a polynucleotide hybridizing under stringent conditions to a polynucleotide consisting of the nucleotide sequence of SEQ ID NO: 1, and encoding a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein). In the polynucleotide described in the above item (ii), the number of nucleotides to be deleted, substituted, or added is, for example, 1 to 50, preferably 1 to 30, more preferably 1 to 18, most preferably 1 to 9. The term “under stringent conditions” in the above item (iii) means the conditions in which a probe comprising the nucleotide sequence of SEQ ID NO: 1 is hybridized to a polynucleotide encoding the above-mentioned homologous protein, but the probe is not hybridized to that encoding keratinase derived from Bacillus licheniformis PWD-1 (U.S. Pat. No. 6,613,505) or a protease (such as thermoase) derived from Bacillus thermoproteolyticus Rokko. More particularly, in accordance with a protocol attached to an ECL direct DNA/RNA labeling and detection system (Amersham), after a polynucleotide to be tested is prehybridized at 42° C. for an hour, a labeled probe having the full-length of the nucleotide sequence of SEQ ID NO: 1 is added, and hybridization is carried out at 42° C. for 15 hours. After the hybridization, a washing treatment with 0.4 or less×SSC (1×SSC; 15 mmol/L sodium citrate, 150 mmol/L sodium chloride) containing 0.4% SDS and 6 mol/L urea at 42° C. for 20 minutes is repeated twice, and a washing treatment with 5×SSC at room temperature for 10 minutes is carried out twice. The polynucleotide encoding the enzyme used in the present invention includes a naturally-occurring polynucleotide. Further, the whole can be synthesized. Furthermore, the synthesis may be carried out using part of the naturally-occurring polynucleotide. Typically, the polynucleotide may be obtained by screening a genomic library derived from Bacillus licheniformis MSK-103 (FERM BP-08487) in accordance with an ordinary method commonly used in genetic engineering, for example, using an appropriate DNA probe designed on the basis of information of a partial amino acid sequence. Expression Vector and Transformed Microorganism The enzyme comprising the amino acid sequence of SEQ ID NO: 2, or the modified or homologous enzyme thereof, which may be used in the present invention, may be produced by an expression vector comprising a nucleotide sequence encoding the enzyme so that the nucleotide sequence may be replicated and the enzyme may be expressed. The expression vector can be constructed on the basis of a self-replicating vector (such as a plasmid), which exists as an extrachromosomal element and can replicate independently of the replication of chromosomes. Alternatively, the expression vector may be a vector which is integrated into the genome of the host microorganism and replicated together with chromosomes, when the host is transformed with the vector. The construction of the vector can be carried out by ordinary procedures or methods commonly used in genetic engineering. To express a protein having a desired activity by transforming a host microorganism with the expression vector, it is preferable that the expression vector contains, for example, a polynucleotide capable of controlling the expression, or a genetic marker to select transformants, in addition to the polynucleotide encoding the enzyme used in the present invention. The polynucleotide capable of controlling the expression includes, for example, a promoter, a terminator, or a polynucleotide encoding a signal peptide. The promoter is not particularly limited, so long as it shows a transcriptional activity in a host microorganism. The promoter can be obtained as a polynucleotide which controls the expression of a gene encoding a protein the same as or different from that derived from the host microorganism. The genetic marker can be appropriately selected in accordance with the method for selecting a transformant. As the genetic marker, for example, a drug resistance gene or a gene complementing an auxotrophic mutation can be used. The enzyme used in the present invention may be prepared by a microorganism transformed with the above expression vector. A host-vector system which can be used in the present invention is not particularly limited. For example, a system utilizing E. coli, Actinomycetes, yeasts, or filamentous fungi, or a system for the expression of a fusion protein using such a microorganism can be used. Transformation of a microorganism with the expression vector can be carried out in accordance with an ordinary method. The transformant is cultivated in an appropriate medium, and the resulting host cells or culture is used to obtain the isolated enzyme used in the present invention. The transformant can be cultivated under the conditions commonly used in the cultivation thereof. Further, after the cultivation, the enzyme of interest can be collected in accordance with an ordinary method in the art. The optimum process for producing the enzyme used in the present invention may be carried out by using preferably a microorganism belonging to genus Bacillus, more preferably Bacillus licheniformis, most preferably Bacillus licheniformis MSK-103 (FERM BP-08487) or a mutant thereof. Enzyme Composition, and Agent for Digesting a Protein Highly Resistant to Denaturation and Degradation and Agent for Detoxifying a Pathogenic Prion Protein The enzyme composition or enzyme agent used in the present invention comprises at least an enzyme (hereinafter referred to as “enzyme used in the present invention”) selected from the group consisting of the enzyme having the above-mentioned physical and chemical properties (including the enzyme obtained by a microorganism); the enzyme comprising the amino acid sequence of SEQ ID NO: 2, and the modified or homologous enzyme thereof; and the enzyme by cultivating the above-mentioned host cell. The enzyme composition used in the present invention is not particularly limited, so long as it contains as an active ingredient the enzyme used in the present invention. The enzyme composition may be produced by mixing the active ingredient with a carrier or diluent commonly used in preparing an enzyme composition, such as fillers (for example, lactose, sodium chloride, or sorbitol), surfactants, or antiseptics, in a desired form such as powder or liquid. The content of the enzyme in the enzyme composition is not particularly limited, so long as an activity thereof is sufficient for the purpose. The content may be 0.01 to 99% by weight, preferably 0.1 to 80% by weight. With respect to an activity of digesting a protein highly resistant to denaturation and degradation, it is preferable that the enzyme composition exhibits 2 U/g or more (more preferably 2 to 500 U/g, still further preferably 10 to 500 U/g, most preferably 20 to 500 U/g) as an activity of digesting keratin azure, or 1 U/g or more (more preferably 1 to 5000 U/g, most preferably 5 to 3000 U/g) as an activity of digesting keratin powder. The amount of the enzyme is sufficient to digest a pathogenic prion protein contained in 1 mL of a 1% suspension containing a brain tissue derived from a mouse suffering from scrapie. In addition to the enzyme used in the present invention, the enzyme composition used in the present invention may further contain at least one of enzymes other than the enzyme used in the present invention, such as a protease (for example, keratinase), lipase, cellulase, or xylanase. The use of the enzymes other than the enzyme used in the present invention is expected to develop the efficiency in digesting a pathogenic prion protein, in comparison with the enzyme composition containing the enzyme used in the present invention alone. The enzyme used in the present invention exhibits an activity of digesting a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein). Therefore, the enzyme used in the present invention, or the enzyme composition used in the present invention containing the enzyme is useful as an active ingredient for an agent for digesting a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein), or as an active ingredient for an agent for detoxifying a pathogenic prion protein in a subject which may be contaminated with the pathogenic prion protein. The agent of the present invention may contain as an active ingredient the enzyme used in the present invention alone, or together with an appropriate carrier and/or diluent. As the carrier or diluent, a conventional carrier or diluent which does not suppress or inhibit an activity of the enzyme used in the present invention, such as fillers (for example, lactose, sodium chloride, sodium sulfate, or sorbitol), surfactants, or antiseptics, can be used. While the form of the agent of the present invention is not particularly limited, a foaming agent, which may be rapidly dissolved in water while foaming, is preferable. The formulation and preparation of the foaming agent are not particularly limited, but a conventional method may be used. The foaming agent may be prepared, for example, by mixing sodium bicarbonate, sodium percarbonate, or the like with an acid, such as citric acid, malic acid, or succinic acid, or by further adding thereto a mobilization agent such as silicic anhydride or other binders. Method for Digesting a Protein Highly Resistant to Denaturation and Degradation (Particularly a Pathogenic Prion Protein) The enzyme or enzyme composition used in the present invention may be used alone, or in the form of the above-mentioned agent of the present invention, to digest a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein), or to detoxify a pathogenic prion protein in a subject which may be contaminated with the pathogenic prion protein. Therefore, the present invention includes a method for digesting a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein), using the enzyme or enzyme composition used in the present invention, and a method for detoxifying a pathogenic prion protein in a subject which may be contaminated with the pathogenic prion protein, using the enzyme or enzyme composition used in the present invention. The method of the present invention for digesting a protein highly resistant to denaturation and degradation comprises at least the step of bringing the enzyme or enzyme composition used in the present invention into contact with a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein) or a subject to be digested which may contain the same. The method of the present invention for detoxifying a pathogenic prion protein comprises at least the step of bringing the enzyme or enzyme composition used in the present invention into contact with a subject to be detoxified which may be contaminated with a pathogenic prion protein. As the subject to be digested or the subject to be detoxified (hereinafter collectively and simply referred to as “subject to be treated”), there may be mentioned, for example, feed which may contain a pathogenic prion protein (for example, meat and bone meal, or compost), instruments or equipment on which surfaces may be contaminated with a pathogenic prion protein (for example, instruments or equipment for slaughter, examination, or operations), or facilities in which a pathogenic prion protein may be present (for example, a slaughterhouse, a cowshed where BSE was present, or a laboratory for infection). The subject to be treated may be used without preheating or with preheating (for example, at approximately 100° C. or more, preferably at 95° C. or more, more preferably at 90° C. or more, most preferably at 80° C. or more) before contact with the enzyme used in the present invention. According to the method of the present invention, a sufficient digestion or detoxification can be carried out without the preheating, and thus it is preferable that the subject to be treated is used without preheating (for example, at approximately 100° C. or more, at 95° C. or more, at 90° C. or more, or at 80° C. or more) before contact with the enzyme used in the present invention. When the preheating is not carried out, an additional apparatus for heating is not necessary, and procedures can be simplified. The procedure of bringing the enzyme or enzyme composition used in the present invention into contact with the subject to be treated is not particularly limited and may be appropriately selected in accordance with the subject to be treated, so long as a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein), which may be contained in the subject to be treated, may be digested by the activity of the enzyme used in the present invention, i.e., an activity of digesting a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein). For example, when the subject to be treated is feed which may contain a pathogenic prion protein, the contact may be carried out, for example, by uniformly mixing the enzyme or enzyme composition used in the present invention with the feed, or by spraying the feed with an aqueous solution containing the enzyme used in the present invention. When the subject to be treated is an instrument on which a surface may be contaminated with a pathogenic prion protein, there may be mentioned, for example, a method of immersing the instrument in an aqueous solution containing the enzyme used in the present invention, a method of spraying the instrument with an aqueous solution containing the enzyme used in the present invention, or a method of washing the surface of the instrument with a washing tool (for example, a cloth, sponge, or brush) having an aqueous solution containing the enzyme used in the present invention. When the subject to be treated is a facility in which a pathogenic prion protein may be present, the contact may be carried out, for example, by spraying an aqueous solution containing the enzyme used in the present invention. It is preferable that the contact of the subject to be treated with the enzyme or enzyme composition used in the present invention is carried out under the conditions in which the enzyme used in the present invention may exhibit a sufficient activity of digesting a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein). For example, pH 7 to 12 is preferable. The contact may be carried out preferably at 20 to 80° C., more preferably 40 to 80° C. The content of the enzyme used may be appropriately selected in accordance with the content of a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein) in the subject to be treated. For example, to digest a pathogenic prion protein contained in 1 mL of a 1% suspension containing a brain tissue derived from a mouse suffering from scrapie, it is preferable to use the enzyme composition containing 0.5 to 10 μg of the enzyme used in the present invention; the enzyme composition containing 2 U/g or more (more preferably 2 to 500 U/g, still further preferably 10 to 500 U/g, most preferably 20 to 500 U/g), as an activity of digesting keratin azure, of the enzyme used in the present invention; or the enzyme composition containing 1 U/g or more (more preferably 1 to 5000 U/g, most preferably 5 to 3000 U/g), as an activity of digesting keratin powder, of the enzyme used in the present invention. When the content of the enzyme is less than 0.5 μg, or the activity is less than 2 U/g or more (as an activity of digesting keratin azure) or less than 1 U/g (as an activity of digesting keratin powder), a complete digestion of the above content of the pathogenic prion protein becomes difficult. When the content of the enzyme is more than 10 μg, or the activity is more than 500 U/g or more (as an activity of digesting keratin azure) or more than 5000 U/g (as an activity of digesting keratin powder) to completely digest the above content of the pathogenic prion protein, it is not practically preferable from the viewpoint of production costs. EXAMPLES The present invention now will be further illustrated by, but is by no means limited to, the following Examples. Example 1 Preparation of Purified Enzyme In this example, cultivation and purification were carried out to obtain a purified enzyme used in the present invention as follows. Culture medium A [1% polypeptone (Wako Pure Chemical Industries), 0.2% yeast extract (Difco), and 0.1% magnesium sulfate heptahydrate (Wako Pure Chemical Industries)(pH 7.0)] was autoclaved by a conventional method, and the medium A (200 mL) was inoculated with Bacillus licheniformis MSK-103 (FERM BP-08487). A cultivation was carried out at 37° C. under aeration and agitation for 72 hours. The resulting broth was centrifuged at 3000 G for 20 minutes to obtain a supernatant containing an enzyme used in the present invention. The supernatant was concentrated 20-fold with an ultrafilter (5,000-molecular-weight cutoff) to obtain a concentrated supernatant containing the enzyme used in the present invention. The concentrated supernatant was filtered with a microfilter membrane (pore size=0.45 μm) to remove microorganisms. To the resulting sterile filtrate, ammonium sulfate was added to a final concentration of 1 mol/L, and a buffer agent (Tris-HCl) was further added to pH 8.5 and a final concentration of 50 mmol/L. For a further purification by a hydrophobic chromatography, the prepared solution was adsorbed to a phenyl Sepharose column, and eluted by a linear gradient with ammonium sulfate (1 mol/L to 0 mol/L) in a Tris-HCl buffer, to obtain a fraction containing the enzyme used in the present invention. The fraction was concentrated 20-fold with an ultrafilter (5,000-molecular-weight cutoff), and a gel filtration chromatography was carried out using Superdex 75 (Pharmacia) gel. The concentrated solution was developed through the gel with a phosphate buffer (0.025 mol/L, pH 7.0) containing 0.1 mol/L sodium chloride as an eluent, to obtain the enzyme used in the present invention. As a result, 20 μg of purified enzyme used in the present invention was obtained. Example 2 Confirmation of Physical and Chemical Properties of the Enzyme (1) Activity and Substrate Specificity Activities of the purified enzyme obtained in Example 1 to various substrates (casein, collagen, elastin, and keratin) were examined. The results are shown in Table 2. As shown in Table 2, the enzyme exhibited a high activity of digesting each substrate, particularly keratin. In this connection, the “1 unit (U)” of digestion activities compared in Table 2 is defined as an amount of the enzyme which can develop ninhydrin corresponding to 1 μmol of glycine per minute, under the following conditions: Concentration of the substrate: 0.5% pH: 9.0 Temperature: 60° C. TABLE 2 Substrate Digestion activity (U) casein 326677 collagen 36958 elastin 10501 keratin 7187 (2) Molecular Weight An SDS-polyacrylamide gel electrophoresis using a 12% homogeneous gel (Tefco) was carried out to determine a molecular weight of the purified enzyme prepared in Example 1. As a result, the molecular weight of the enzyme capable of digesting a pathogenic prion protein was approximately 31,000. Another SDS-polyacrylamide gel electrophoresis using a 15% homogeneous gel (ATTO) was carried out to determine a molecular weight of the purified enzyme prepared in Example 1. As a result, the molecular weight of the enzyme capable of digesting a pathogenic prion protein was approximately 26,000. In this connection, Protein Molecular Weight Standard (Bio-Rad) was used as a standard marker in this example. (3) Isoelectric Point A polyacrylamide gel isoelectric focusing electrophoresis using an LKB electrophoresis system was carried out to determine an isoelectric point (pI) of the purified enzyme prepared in Example 1. As a result, the isoelectric point of the enzyme capable of digesting a pathogenic prion protein was 9.3. In this connection, each isoelectric point of standard samples used in this example is shown in Table 3. TABLE 3 Standard sample Isoelectric point trypsinogen 9.30 lentil lectin basic band 8.65 lentil lectin neutral band 8.45 lentil lectin acidic band 8.15 horse myoglobin basic band 7.35 horse myoglobin acidic band 6.85 human carbonic anhydrase B 6.55 horse carbonic anhydrase B 5.80 β-lactoglobulin A 5.20 soybean trypsin inhibitor 4.55 amyloglucosidase 3.50 (4) Optimum pH and Stable pH The optimum pH at 37° C. of purified enzyme prepared in Example 1, determined by an activity of digesting keratinazure (Sigma) as an index, was pH 9.0 to 10.0, as shown in FIG. 1. The stable pH at 37° C. of the enzyme was pH 7.0 to 12.0, preferably pH 8.0 to 10.5, as shown in FIG. 1. (5) Optimum Temperature The optimum temperature at pH 9.0 (i.e., optimum pH), determined by an activity of digesting keratin azure as an index, was 60 to 70° C., as shown in FIG. 2. Example 3 Cloning of Enzyme Gene and Determination of Amino Acid Sequence Thereof In this example, a gene encoding the purified enzyme prepared in Example 1 was cloned, and the nucleotide sequence of the gene was determined to confirm the amino acid sequence of the enzyme. To purify the enzyme, the culture medium A (see Example 1) was inoculated with Bacillus licheniformis MSK-103 (FERM BP-08487). A cultivation was carried out at 37° C. for 3 days, and the resulting broth was centrifuged to obtain a supernatant. The supernatant was concentrated approximately 20-fold with Pellicon XL (cut 5000; Millipore), and was adjusted to a solution containing 1 mol/L magnesium sulfate and 0.05 mol/L Tris-HCl (pH8.5). The prepared solution was applied to a phenyl Sepharose column (Phenyl Sepharose FF; low sub, 26×300 mm; Amersham Bioscience), and eluted by a linear concentration gradient with ammonium sulfate (1 mol/L to 0 mol/L) in a 0.05 mol/L Tris-HCl buffer (pH8.5), to obtain a fraction eluted with 0 mol/L of ammonium sulfate. The fraction was concentrated with Pellicon XL (cut 5000) followed by Ultrafree 15 (Ucut5000; Millipore). The concentrated solution was applied to Superdex (Superdex75pg; 16×600 mm; Amersham Bioscience), and eluted with a phosphate buffer (0.05 mol/L, pH 7.0) containing 0.1 mol/L sodium chloride to obtain a fraction having a molecular weight of approximately 31 kDa. It was confirmed by SDS-PAGE that the fraction contained, as a single substance, a protein having a molecular weight of approximately 31 kDa. The purified protein was subjected to SDS-PAGE, and transferred to a polyvinylidene difluoride (PVDF) membrane (Immobilon PSQ; Millipore), to blot the protein on the PVDF membrane. The PVDF membrane was washed with water and air-dried, and then was used to analyze the amino acid sequence of the protein by a protein sequencer (Model 492; Applied Biosystems). As a result, the following amino acid sequence was obtained: N-terminal amino acid: AQTVPYGIPLI (the sequence consisting of the 1st to 11th amino acids in the amino acid sequence of SEQ ID NO: 2) It was found that the obtained amino acid sequence is the same sequence as those of keratinase derived from Bacillus licheniformis PWD-1 [Lin, X. et.al., Appl. Environ. Microbiol (1995) 61, 1469-1474] and subtilisin carlsberg derived from Bacillus licheniformis [Jacobs, M. et.al., Nucleic Acid Res. (1985) 13, 8913-8926]. Next, a partial fragment was amplified by PCR, and was used as a probe to clone a gene of interest as follows. Genomic DNA derived from Bacillus licheniformis MSK-103 (FERM BP-08487) was prepared in accordance with a method of Wilson et al. [Wilson, C. R., J. Bacteriol. (1985) 163, 445-453]. A PCR using the genome DNA as a template and a combination of the following primers was carried out to amplify a partial fragment of a gene encoding the enzyme capable of digesting an abnormal prion. The PCR was carried out by using Takara Taq (Takara Bio) as an enzyme for PCR, and by performing a heat denaturation at 94° C. for a minute, followed by repeating a cycle consisting of reactions at 94° C. for 30 seconds, at 48° C. for 30 seconds and at 68° C. for 2 minutes 30 times, to amplify the DNA of interest. Primer PDE-2 for partial fragment amplification: 5′-agagcggcggaaaagtggac-3′ (SEQ ID NO: 3) Primer PDE-5 for partial fragment amplification: 5′-cctgcgccaggagccatgac-3′ (SEQ ID NO: 4) As a result, a fragment of approximately 700 bp was amplified. The amplified DNA fragment was used as a probe to clone the full-length of the gene of interest from a genomic library derived from Bacillus licheniformis MSK-103 (FERM BP-08487) as follows. Genomic DNA derived from Bacillus licheniformis MSK-103 (FERM BP-08487) was partially digested with restriction enzyme Sau IIIA1, and the fragments were ligated into an EMBLIII vector (Stratagene). A commercially available packaging kit (MaxPlax Lambda packaging extract; Epicentre technologies) was used to form phage particles containing the constructs. The obtained phage library was screened by using a commercially available screening kit (DIG high prime DNA labeling and detection starter kit; Roche) to obtain 100 positive clones from approximately 10000 plaques. DNAs were purified from 10 positive clones, an SphI fragment of approximately 4.1 kb, which was contained in 4 positive clones thereamong, was subcloned into pUC119 to construct pUC-PDE4. The size of the SphI fragment accorded with a result of a Southern analysis of Bacillus licheniformis MSK-103 (FERM BP-08487) using the PCR product as a probe. The plasmid pUC-PDE4 was used to determine the DNA sequence thereof by a shotgun sequence method using a DNA sequencer (model 3730XL; Applied Biosystems). As a result, the plasmid contained the full-length of the gene encoding the enzyme capable of digesting an abnormal prion, and the nucleotide sequence of the coding region was that of SEQ ID NO: 1. As a result, it was confirmed that the amino acid sequence of the purified enzyme obtained in Example 1 is completely identical to that of subtilisin DY (WO98/30682). Further, the second highest homology was 81% in a kerA gene derived from Bacillus licheniformis (by a BLAST search). Example 4 Preparation of Enzyme Composition To obtain an enzyme composition used in the present invention, the culture medium A (200 mL) described in Example 1 was inoculated with Bacillus licheniformis MSK-103 (FERM BP-08487). A cultivation was carried out at 37° C. under aeration and agitation for 48 hours. The obtained broth was centrifuged at 3000G for 30 minutes to obtain a supernatant containing the enzyme used in the present invention. The supernatant was concentrated 30-fold with an ultrafilter (5,000-molecular-weight cutoff) to obtain a concentrated supernatant. The concentrated supernatant was filtered with a microfilter (pore size=0.45 μm) to remove microorganisms. As a result, a solution of enzyme composition A containing the enzyme used in the present invention was obtained. The enzyme composition A exhibited an activity of digesting keratinazure, and the activity was 285 U/g. The solution of the enzyme composition A was lyophilized to obtain powder of enzyme composition A′. Culture medium B [0.01% yeast extract (Difco), 1% feather meal (ITOCHU FEED MILLS CO., LTD), 0.01% magnesium chloride (Wako Pure Chemical Industries), 0.04% dipotassium hydrogen phosphate (Wako Pure Chemical Industries), 0.03% potassium dihydrogen phosphate (Wako Pure Chemical Industries), 0.05% sodium chloride (Wako Pure Chemical Industries), and 0.05% ammonium chloride (Wako Pure Chemical Industries)(pH 7.0)] was autoclaved, and the medium B (40 mL) was inoculated with Bacillus licheniformis PWD-1 (ATCC-53757). A cultivation was carried out at 37° C. under aeration and agitation for 48 hours. The resulting broth was centrifuged at 3000 G for 30 minutes to obtain a supernatant. The supernatant was concentrated 18-fold with an ultrafilter (5,000-molecular-weight cutoff) to obtain a concentrated supernatant. The concentrated supernatant was filtered with a microfilter (pore size=0.45 μm) to remove microorganisms. As a result, a solution of enzyme composition B for comparison was obtained. Example 5 Digestion of Mouse Pathogenic Prion Protein with Purified Enzyme In this example, the purified enzyme used in the present invention prepared in accordance with the method described in Example 1, and a commercially available protease (subtilisin carlsberg; Sigma) were used to evaluate an activity of digesting a pathogenic prion protein. In this connection, an activity of an enzyme preparation (proteinase K; Wako Pure Chemical Industries) was used as a standard. As a substrate used in this example, the brain derived from a mouse infected with the pathogenic prion protein [CLINICAL AND DIAGNOSTIC LABORATORY IMMUNOLOGY, (USA), American Society for Microbiology (Asm), March in 1995, p. 172-176] was used to prepare a 5% homogenate [2% N-sodium lauroyl sarcosinate, and 10 mmol/L Tris-HCl buffer (pH 7.5)], and the 5% homogenate was diluted to a final concentration of 1% with 50 mmol/L Tris-HCl buffer (pH 8.3). An enzyme reaction was carried out by mixing the 1% brain homogenate with an equal volume of the purified enzyme solution, the commercially available protease solution, or the enzyme preparation solution, and incubating each mixture at 37° C. for 1 hour. The concentrations of the purified enzyme, the commercially available protease, and the enzyme preparation were 1 μg/mL and 0.2 μg/mL, as a final concentration in each reaction mixture during the enzyme reaction. An aliquot of each reaction mixture after the enzyme reaction was used to carry out a sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) using a electrophoresis system (ATTO) and an SDS-polyacrylamide gel (10% gel; ATTO). Proteins in the polyacrylamide gel after SDS-PAGE were transferred to a polyvinylidene difluoride (PVDF) membrane (Millipore) by a blotting system (ATTO) in accordance with a protocol attached thereto. The pathogenic prion protein bound to the PVDF membrane was labeled by an antibody-antigen method using an anti-prion-protein rabbit antibody as the first antibody, and a horseradish-peroxidase-labeled anti-rabbit-IgG goat antibody (Zymed) as the second antibody. The pathogenic prion protein was detected by a commercially available labeling and detecting kit (ECL+Plus Western Blotting Detection System; Amersham Bioscience) in accordance with a protocol attached thereto. In this connection, the anti-prion-protein rabbit antibody used as the first antibody was prepared as follows. A peptide (PrP94-112) consisting of 20 amino acids in which cystein (Cys) was added to an N-terminal sequence of a core fragment P27-30 of sheep scrapie prion protein was synthesized, and a rabbit was immunized with the peptide conjugated to Keyhole limpet hemocyanin (KLH) as an immunogen. The obtained rabbit antiserum was subjected to a protein A column to purify the antibody of interest. The antibody reacts to not only sheep prion protein but also hamster, mouse, and bovine prion proteins. The results are shown in FIG. 3. When using proteinase K as a standard, or subtilisin carlsberg as a commercially available protease, bands resistant to proteases, which indicated the presence of the pathogenic prion protein, were detected even at the concentration of 1 μg/mL. The molecular weight of the band not digested at all was 32 kDa, and those of partially-digested bands (three bands) were 30 kDa, 25-26 kDa, and 20-21 kDa. In contrast, when using the purified enzyme used in the present invention, a band was detected at 0.2 μg/mL, but almost all the pathogenic prion proteins contained in the 1% brain homogenate were digested at 1 μg/mL. Example 6 Digestion of Mouse Pathogenic Prion Protein with Enzyme Composition In this example, the solution of enzyme composition A used in the present invention prepared in accordance with the method described in Example 4 was used to evaluate an activity of digesting mouse pathogenic prion protein. In this connection, an activity of an enzyme preparation (proteinase K; Wako Pure Chemical Industries) was used as a standard. As a substrate, the same substrate used in Example 5 (i.e., 1% brain homogenate derived from a mouse infected with the pathogenic prion protein) was used. An enzyme reaction was carried out by mixing the 1% brain homogenate with an equal volume of the enzyme composition solution or the enzyme preparation solution, and incubating each mixture at 37° C. for 1 hour. The concentrations of the enzyme preparation were 50 μg/mL, 25 μg/mL, 12.5 μg/mL, and 6.25 μg/mL, as a final concentration. As to the enzyme composition A, the original solution was diluted to 1, ½, ¼, ⅛, and 1/16. The diluted solutions exhibited 285 U/g, 143 U/g, 71 U/g, 36 U/g, and 18 U/g as an activity of digesting keratin azure, respectively. An aliquot of each reaction mixture after the enzyme reaction was used to detect the pathogenic prion protein in accordance with the method described in Example 5. The results are shown in FIG. 4. When using proteinase K as a standard, bands resistant to proteases, which indicated the presence of the pathogenic prion protein, were detected even at a high concentration of 50 μg/mL. In contrast, when using the enzyme composition used in the present invention, a band was slightly detected at 18 U/g as an activity of digesting keratin azure (diluted to 1/16; a 1.875-fold concentrated solution of the broth), but the pathogenic prion protein was completely digested at 36 U/g (diluted to ⅛; a 3.75-fold concentrated solution of the broth) or more. Example 7 Digestion of Sheep Pathogenic Prion Protein with Enzyme Composition In this example, the solution of enzyme composition A used in the present invention and the solution of enzyme composition B (containing keratinase derived from Bacillus licheniformis PWD-1) for comparison, each being prepared in accordance with the method described in Example 4, were used to evaluate an activity of digesting sheep pathogenic prion protein. In this connection, an activity of an enzyme preparation (proteinase K; Wako Pure Chemical Industries) was used as a standard. As a substrate used in this example, the brain derived from a sheep infected with the pathogenic prion protein was used to prepare a 5% homogenate [2% N-sodium lauroyl sarcosinate, and 10 mmol/L Tris-HCl buffer (pH 7.5)], and the 5% homogenate was diluted to a final concentration of 1% with 50 mmol/L Tris-HCl buffer (pH 8.3). An enzyme reaction was carried out by mixing the 1% brain homogenate with an equal volume of the enzyme composition solution or the enzyme preparation solution, and incubating each mixture at 37° C. for 1 hour. The concentrations of the enzyme preparation were 50 μg/mL, 10 μg/mL, 2 μg/mL, and 0.4 μg/mL, as a final concentration. As to the enzyme composition A used in the present invention, the original solution was diluted to 1, ½, ¼, and ⅛. The diluted solutions exhibited 285 U/g, 143 U/g, 71 U/g, and 36 U/g as an activity of digesting keratin azure, respectively. As to the enzyme composition B for comparison, the original solution was diluted to 1, ½, ¼, and ⅛. The diluted solutions exhibited 37 U/g, 19 U/g, 9 U/g, and 5 U/g. An aliquot of each reaction mixture after the enzyme reaction was used to detect the pathogenic prion protein in accordance with the method described in Example 5. The results are shown in FIG. 5. When using proteinase K as a standard, bands resistant to proteases, which indicated the presence of the pathogenic prion protein, were detected at the concentrations of 10 μg/mL or less. When using the enzyme composition B for comparison, the pathogenic prion protein was not digested at any concentration. In contrast, when using the enzyme composition A used in the present invention, the pathogenic prion protein was almost completely digested at any concentration. In addition, it was found that the enzyme of the present invention can digest a pathogenic prion protein derived from a different species and having a different amino acid sequence with a minor variation. Example 8 Digestion of Mouse Pathogenic Prion Protein with Enzyme Composition Bacillus licheniformis PWD-1 was cultivated in accordance with the method described in Example 4 for preparing the enzyme composition A used in the present invention (i.e., using the medium A), and an enzyme composition C for comparison was prepared in accordance with the method described in Example 4 for preparing the enzyme composition A. Further, Bacillus licheniformis DSM-8782 was cultivated in accordance with the method described in Example 4 for preparing the enzyme composition A used in the present invention (i.e., using the medium A), and an enzyme composition D for comparison was prepared in accordance with the method described in Example 4 for preparing the enzyme composition A. Furthermore, Bacillus licheniformis DSM-8782 was cultivated in accordance with the method described in Example 4 for preparing the enzyme composition B for comparison (i.e., using the medium B), and an enzyme composition E for comparison was prepared in accordance with the method described in Example 4 for preparing the enzyme composition B. In Table 4, the relationships of the enzyme compositions to the strains and the media are shown. The medium B is a medium for inducing keratinase [Japanese Unexamined Patent Publication (Kokai) No. 6-46871]. TABLE 4 Enzyme composition Strain Medium A FERM BP-08487 A B PWD-1 B C PWD-1 A D DSM-8782 A E DSM-8782 B The resulting enzyme composition A used in the present invention and four enzyme compositions B to E for comparison were used to compare the activity of digesting mouse pathogenic prion protein, in accordance with the procedures described in Example 7, except that a final concentration of each enzyme composition was concentrated 18-fold with respect to each supernatant. The results are shown in FIG. 6. As shown in FIG. 6, the pathogenic prion protein was not digested by the enzyme compositions B to E for comparison, but was completely digested by the enzyme composition A used in the present invention. Example 9 Comparative Test to Thermoase (1) The enzyme composition A′ used in the present invention prepared in accordance with the procedures described in Example 4, and thermoase (DAIWA KASEI K.K.), as an enzyme for comparison, derived from Bacillus thermoproteolyticus Rokko disclosed in WO02/053723 were used to evaluate the activity of digesting hamster pathogenic prion protein (strain Sc237). As a substrate used in this example, the brain derived from a mouse infected with hamster-type pathogenic prion protein (strain Sc237) was used to prepare a 1% brain homogenate [50 mmol/L Tris-HCl buffer (pH 8.3)]. The Sc237-type pathogenic prion protein was accumulated in the brain of the mouse. Each enzyme solution was prepared by dissolving the enzyme composition A′ or thermoase in a 50 mmol/L Tris-HCl buffer (pH8.3). The concentrations of each solution were 4, 8, 16, and 32 U/mL (as a final concentration) as an activity of digesting keratin powder. The enzyme reaction was carried out by mixing the 1% brain homogenate with an equal volume of each enzyme solution, and incubating the mixture at 37° C. for 20 hours. An aliquot of each reaction mixture after the enzyme reaction was used to detect the pathogenic prion protein in accordance with the method described in Example 5. The results are shown in FIG. 7. When using the enzyme solution containing thermoase, bands resistant to proteases, which indicated the presence of the pathogenic prion protein, were detected at any concentration. In contrast, when using the enzyme composition used in the present invention, the pathogenic prion protein was completely digested below the levels of detection by Western blotting, at any concentration. Example 10 Comparative Test to Thermoase (2) WO02/053723 discloses that an activity of thermoase in digesting a protein (a pathogenic prion protein derived from BSE) is increased in the presence of sodium dodecyl sulfate (SDS). In this example, an activity of digesting hamster pathogenic prion protein was evaluated under such conditions. The enzyme composition A′ used in the present invention prepared in accordance with the procedures described in Example 4, and the thermoase solution used in Example 9 were used to evaluate the activity of digesting hamster pathogenic prion protein (strain Sc237). As a substrate used in this example, the brain derived from a mouse infected with hamster-type pathogenic prion protein (strain Sc237) was used to prepare a 1% brain homogenate [50 mmol/L Tris-HCl buffer (pH 8.3) containing 0.1, 1, or 4% SDS (final concentrations of SDS in the following reaction=0.05, 0.5, or 2%)]. The Sc237-type pathogenic prion protein was accumulated in the brain of the mouse. The enzyme reaction was carried out by mixing the 1% brain homogenate with an equal volume of each enzyme solution, and incubating the mixture at 37° C. for 20 hours. The concentration of each solution was 4 U/mL (as a final concentration) as an activity of digesting keratin powder. An aliquot of each reaction mixture after the enzyme reaction was used to detect the pathogenic prion protein in accordance with the method described in Example 5. The results are shown in FIG. 8. In FIG. 8, lane 1 is thermoase (4 U/mL; 0.05% SDS), lane 2 is thermoase (4 U/mL; 0.5% SDS), lane 3 is thermoase (4 U/mL; 2% SDS), and lane 4 is the enzyme composition A ′ solution (4 U/mL; 2% SDS). When using the enzyme solution containing thermoase, bands resistant to proteases, which indicated the presence of the pathogenic prion protein, were detected even at the final concentration of 2% SDS. In contrast, when using the enzyme composition used in the present invention, the pathogenic prion protein was completely digested below the levels of detection by Western blotting, at any concentration. As described above, it is found that the enzyme used in the present invention exhibits an excellent activity of digesting a pathogenic prion protein even in the presence of SDS, in comparison with thermoase. Example 11 Washing Model Test Using Microplate To evaluate the effects on washing instruments contaminated with a pathogenic prion protein, a model test was carried out as follows. The enzyme composition A′ used in the present invention prepared in accordance with the procedures described in Example 4, and the thermoase solution used in Example 9 were used to evaluate the activity of digesting hamster pathogenic prion protein (strain Sc237) stuck on polystyrene. As a substrate used in this example, the brain derived from a mouse infected with a hamster-type pathogenic prion protein (strain Sc237) was used to prepare a 1% brain homogenate [50 mmol/L Tris-HCl buffer (pH 8.3)]. The Sc237-type pathogenic prion protein was accumulated in the brain of the mouse. As a control, a normal brain not infected with the abnormal prion protein was used to prepare a 1% brain homogenate [50 mmol/L Tris-HCl buffer (pH 8.3)]. Each 1% brain homogenate (25 μL/well) of normal or Sc237-infected hamster was added to a polystyrene microplate (IMMUNO MODULE; Nunc), and the plate was completely dried at room temperature for one day. To carry out a washing treatment of the resulting microplate using enzyme solutions, the enzyme composition A′ and thermoase were diluted to 7.5 U/mL and 15 U/mL (as an activity of digesting keratin powder) with 50 mmol/L Tris-HCl buffer (pH8.3) to prepare a washing solution A (7.5 U/mL) and washing solution B (15 U/mL), respectively. The enzyme reaction was carried out by adding 100 μL/well of each washing solution, and incubating the plate at 37° C. for 1 hour under shaking at 100 rpm. Each washing solution was removed, and each well was washed twice with approximately 300 μL of PBS. A denature treatment was carried out by adding 100 μL/well of 6 mol/L guanidine hydrochloride (Wako Pure Chemical Industries) and allowing the plate to stand at room temperature for 1 hour. Each well was washed three times with approximately 300 μL of PBS to remove guanidine hydrochloride. Blocking was carried out by adding 300 μL/well of 5% skimmed milk (Amersham) and allowing the plate to stand at room temperature for 1 hour. Each well was washed twice with approximately 300 μL of 0.05% Tween 20-PBS. The pathogenic prion protein bound to the microplate was labeled by an antibody-antigen method using an anti-prion-protein mouse antibody (3F4; Chemicon International) as the first antibody, and a horseradish-peroxidase-labeled anti-mouse-IgG goat antibody (Zymed) as the second antibody. The prion protein remaining in each well of the microplate was detected by a luminescent reaction using a commercially available labeling and detecting kit (Super Signal West Dura; Amersham Bioscience) in accordance with a protocol attached thereto. The amount of luminescence was recorded by a light capture (AE-6962; ATTO), and an image analysis was carried out by a software for image analysis (CS Analyzer; ATTO). The results are shown in FIG. 9. When using the enzyme composition used in the present invention, a residual rate of the pathogenic prion protein was less than 10% at the concentration of 7.5 U/mL, and the rate was less than approximately 1% at the concentration of 15 U/mL. In contrast, when using thermoase, the rate was 40% or more at any concentration. As a result, it was found that the enzyme used in the present invention exhibits an excellent activity of washing away a pathogenic prion protein. INDUSTRIAL APPLICABILITY The enzyme used in the present invention exhibits an excellent activity of digesting a protein highly resistant to denaturation and degradation (particularly a pathogenic prion protein) in comparison with known proteases. Therefore, according to the enzyme used in the present invention or the enzyme composition used in the present invention containing the enzyme, a pathogenic prion protein can be efficiently digested. Further, the enzyme used in the present invention can be produced at a low cost. According to the enzyme or the enzyme composition, contamination in a subject which may be contaminated with a pathogenic prion protein can be removed. The enzyme is useful as an active ingredient for an agent of the present invention for digesting or detoxifying a pathogenic prion protein. Free Test in Sequence Listing Features of “Artificial Sequence” are described in the numeric identifier <223> in the Sequence Listing. More particularly, the nucleotide sequence of SEQ ID NO: 3 is primer PDE-2, and the nucleotide sequence of SEQ ID NO: 4 is primer PDE-5. Although the present invention has been described with reference to specific embodiments, various changes and modifications obvious to those skilled in the art are possible without departing from the scope of the appended claims.
<SOH> Background Art <EOH>A pathogenic prion protein seems to be involved in such diseases as scrapie in sheep or mice, Creutzfeldt-Jakob disease (CJD) in humans, and bovine spongiform encephalopathy (BSE; popularly known as mad cow disease) in cattle give rise to nervous symptoms such as dysstasia or dysbasia. It is noted that human consumption of beef infected with the pathogenic prion protein may cause a variant Creutzfeldt-Jakob disease (vCJD) by infection. In particular, BSE is an extremely serious disease in the light of a safe supply of beef for human consumption. Such diseases may develop when the pathogenic prion protein transferred into the human body from the outside causes a conformational change of a normal prion protein generally located in the brain [Nature, (Great Britain), 1994, Vol. 370, p. 471 (non-patent reference 1)]. To prevent the development of disease by an infection of the pathogenic prion protein, it is necessary to digest and detoxify the pathogenic prion protein as a cause thereof to the extent that the disease does not develop. However, the pathogenic prion protein is believed to be extremely stable when subjected to a commonly used sterilizing treatment (such as boiling) and exhibits little or no loss of infectivity by the sterilizing treatment. Further, although the pathogen is a protein, it is not difficult to digest the pathogen completely with a conventional protease. Under these circumstances, a method for digesting the pathogenic prion protein efficiently and a method for preventing the diseases from developing by infection are desired. As a method for digesting a protein highly resistant to denaturation and degradation such as a pathogenic prion protein, for example, Japanese Unexamined Patent Publication (Kokai) No. 6-46871 (patent reference 1) discloses a method for digesting keratin-containing proteins highly resistant to conventional proteases, using keratinase, a protease, derived from Bacillus licheniformis PWD-1. The publication discloses that keratinase is used in digesting keratin-containing proteins (for example, animal hair, human hair, or feathers), but neither discloses nor suggests any effects of the keratinase on a pathogenic prion protein. In this connection, a DNA encoding the keratinase derived from Bacillus licheniformis PWD-1 was obtained [Unexamined International Publication (Kohyo) No. 10-500863 (patent reference 2)]. Further, U.S. Pat. No. 6,613,505 (patent reference 3) discloses that the keratinase derived from Bacillus licheniformis PWD-1 is used in digesting a pathogenic prion protein highly resistant to denaturation and degradation. However, to reduce or digest the pathogenic prion protein by the method disclosed in U.S. Pat. No. 6,613,505, two of treatment step, that is, a heat treatment as a pretreatment, and an enzyme treatment, are necessary. In this method, an apparatus for heating is necessary, and thus it is not easy to carry out the method in common facilities without such an apparatus for heating. Further, the two-step procedures are complicated. Furthermore, International Publication No. 02/053723 (patent reference 4) discloses that a heat-resistant protease is used in digesting a pathogenic prion protein. However, it discloses that when a pathogenic prion protein was digested by a protease derived from Bacillus thermoproteolytics Rokko described in Examples thereof, the pathogenic prion protein was not sufficiently digested with the protease alone, but was sufficiently digested with the protease in the presence of sodium dodecyl sulfate. In addition, a neutral salt is necessary to activate the protease. Further, the protease requires a metal ion, and thus when a chelating agent is present in a reaction, the activity is remarkably decreased. (non-patent reference 1) Nature, (Great Britain), 1994, Vol. 370, p. 471 (patent reference 1) Japanese Unexamined Patent Publication (Kokai) No. 6-46871 (patent reference 2) Unexamined International Publication (Kohyo) No. 10-500863 (patent reference 3) U.S. Pat. No. 6,613,505 (patent reference 4) International Publication No. 02/053723
<SOH> BRIEF DESCRIPTION OF DRAWINGS <EOH>FIG. 1 is a graph showing the optimum pH and stable pH of a purified enzyme used in the present invention at 37° C. FIG. 2 is a graph showing the optimum temperature of a purified enzyme used in the present invention at pH 9.0. FIG. 3 shows the results in which the mouse pathogenic prion protein was digested with a purified enzyme used in the present invention. FIG. 4 shows the results in which the mouse pathogenic prion protein was digested with enzyme composition A used in the present invention. FIG. 5 shows the results in which the sheep pathogenic prion protein was digested with enzyme composition A used in the present invention. FIG. 6 shows the results in which the mouse pathogenic prion protein was digested with enzyme composition A used in the present invention. FIG. 7 shows the results in which the hamster pathogenic prion protein (strain Sc237) was digested with enzyme composition A′ used in the present invention or thermoase for comparison. FIG. 8 shows the results in which the hamster pathogenic prion protein (strain Sc237) was digested in the presence of SDS with enzyme composition A′ used in the present invention or thermoase for comparison. FIG. 9 shows the results in which the hamster pathogenic prion protein (strain Sc237) stuck on polystyrene was digested with enzyme composition A′ used in the present invention or thermoase for comparison. detailed-description description="Detailed Description" end="lead"?
20050818
20100817
20060622
62825.0
A61K3848
0
ARIANI, KADE
METHOD OF DEGRADING HARDLY DEGRADABLE PROTEIN
UNDISCOUNTED
0
ACCEPTED
A61K
2,005
10,532,714
ACCEPTED
Pack sealing method and device
A pack sealing method and device in which a slit tubular member (16) is slidably fitted around a wrapped portion of a pack (8) (a bag or envelope made of a diverse material while having a diverse size and a diverse shape) formed as a portion of the pack (8) near an opening (4) of the pack (8) is wrapped around a rod member (14), in a state in which a diverse liquid, gaseous, and solid material or object is put into the pack (8) through the opening (4). The rod member (14′) is fixedly bonded to the inner or outer surface of the pack (8) or separate from the pack (8). Where the pack (8) is a zipper pack provided with a zipper, this zipper functions as the rod member.
1. A method for sealing a pack, comprising the steps of: fixedly bonding a rod member to an outer surface of the pack; wrapping a portion of the pack around the rod member; and slidably fitting a slit tubular member around the rod member wrapped by the pack portion such that the pack extends through a slit formed at the tubular member, thereby sealing the pack. 2. A method for sealing a pack, comprising the steps of: fixedly bonding a rod member to an inner surface of the pack; wrapping a portion of the pack around the rod member; and slidably fitting a slit tubular member around the rod member wrapped by the pack portion such that the pack extends through a slit formed at the tubular member, thereby sealing the pack. 3. A method for sealing a zipper pack provided at an opening thereof with a zipper including male and female zipper members, comprising the steps of: coupling the male and female zipper members of the zipper; wrapping a portion of the zipper pack around the zipper; and slidably fitting a slit tubular member around the zipper wrapped by the pack portion such that the pack extends through a slit formed at the tubular member, thereby sealing the zipper pack. 4. A pack sealing device including a rod member, a tubular member adapted to be slidably fitted around the rod member, a squeeze gap defined between the rod member and the tubular member, a slit formed at the tubular member to extend in a longitudinal direction of the tubular member, an inclined guide formed at one end of the rod member, and another inclined guide formed at one end of the tubular member, wherein: the tubular member has a circular cross-sectional shape; and the rod member is formed, at one end thereof, with a bent portion extending inclinedly toward the slit of the tubular member in a state, in which the rod member is fitted in the tubular member, a horizontal extension formed to extend horizontally from an end of the bent portion opposite to the rod member, and a semicircular protrusion formed at an end of the horizontal extension opposite to the bent portion. 5. The pack sealing device according to claim 4, wherein the pack sealing device further includes at least one ring provided at an outer surface of the tubular member. 6. The pack sealing device according to claim 4 or 5, wherein the rod member is formed, at one end thereof, with a protruded stopper having a vertical surface and an inclined surface. 7. The pack sealing device according to claim 4 or 5, wherein the rod member is made of a hard material, and provided, at an outer surface thereof, with a plurality of grooves uniformly spaced apart from one another by a small distance and adapted to allow the rod member to be flexible. 8. The pack sealing device according to claim 4 and 5, wherein: the rod member is fixedly bonded to an outer surface of a pack to be sealed; and the tubular member is separably coupled to the rod member. 9. The pack sealing device according to claim 4 and 5, wherein: the rod member is fixedly bonded to an inner surface of a pack to be sealed; and the tubular member is separably coupled to the rod member. 10. The pack sealing device according to claim 4 or 5, wherein the rod member has a cross-sectional shape selected from a group consisting of circular, semicircular, oval, rectangular, diamond, trapezoidal, and polygonal cross-sectional shapes. 11. The pack sealing device according to claim 4 or 5, wherein: the rod member is fixedly bonded to an inner surface of a pack to be sealed; the tubular member is separably coupled to the rod member; and the rod member has flat portions of a reduced thickness at both ends thereof, respectively. 12. The pack sealing device according to claim 4 or 5, wherein: the rod member is fixedly bonded to an outer surface of a pack, to be sealed, near one corner portion of the pack such that it extends inclinedly; and the tubular member is separably coupled to the rod member.
TECHNICAL FIELD The present invention relates to a pack sealing method and device for sealing the opening of a pack adapted to contain diverse liquid, gaseous, and solid materials or objects, in a state in which such a material or object is put into the pack through the opening. BACKGROUND ART Generally, where food and drink, in particular, food, is stored or packed in a sealed or vacuum state so that it cannot come into contact with air or oxygen, it is possible to prevent the food from being oxidized or rotting, to considerably lengthen the storage period of the food, and to maintain the freshness and intrinsic smell of the food for a prolonged period of time. For such a purpose, a zipper pack has been proposed in which a zipper consisting of female and male zipper members is provided at an opening of the pack, so as to conveniently seal the opening. However, this zipper pack has a problem in that the seal may be easily collapsed by external pressure. Also, there are problems of a difficulty in manufacture and an increase in manufacturing cost. Also, a hinged sealing device has been proposed which has two members hingably connected to each other, and adapted to clamp the opening portion of a pack therebetween. However, this hinged sealing device cannot provide a reliable seal. Furthermore, it is inconvenient to use this sealing device. In particular, there is a problem caused by the structure of the sealing device in that the seal at the middle portion of the sealing device is weak. Meanwhile, general vinyl packs made of a polyethylene (PE) film or polypropylene (PP) film can be inexpensively and easily manufactured. However, such a vinyl pack does not have a dense structure, so that smell molecules of the contents in the vinyl pack may pass through the vinyl pack, thereby emitting foul odors. When the opening of such a vinyl pack is widened to put a material into the vinyl pack, it may not be maintained in the widened state. For this reason, where a soup containing solids is to be put into the vinyl pack, there is a problem in that the liquid or solids of the soup may be smeared on the outer surface of the vinyl pack around the opening or flow along the outer surface of the vinyl pack, thereby staining the vinyl pack. Such a problem is mainly caused by the fact that both the general vinyl pack and the vacuum vinyl pack have an insufficient rigidity to maintain the opened state of their openings, or they have no means for maintaining the opened state of their openings. DISCLOSURE OF THE INVENTION An object of the invention is to provide a pack sealing method and device in which a pack sealing means is slidably fitted around a folded or wrapped portion of a pack (a bag or envelope made of a diverse material while having a diverse size and a diverse shape) formed as the opening of the pack is folded or wrapped in a state in which a diverse liquid, gaseous, and solid material or object is put into the pack through the opening, so that a desired seal for the pack is conveniently and reliably achieved. In accordance with the present invention, a rod member included in a pack sealing device is formed at or bonded to the inner or outer surface of a pack, to be sealed, near an opening of the pack or at a middle portion of the pack. A desired portion of the pack is wrapped around the rod member. In this state, a slit tubular member included in the pack sealing device is slidably fitted around the rod member wrapped by the pack portion. Thus, the pack is reliably sealed by the pack sealing device. In accordance with the present invention, at least one ring may be formed at the outer surface of the tubular member to connect a string such as a necklace to the pack sealing device. In this case, the user may wear the pack containing desired contents on the neck via the string to carry the pack or hang the pack on a wall to store the pack. In accordance with the present invention, the rod member of the pack sealing device may be formed, at one end thereof, with a bent portion, so as to more easily achieve the coupling of the pack to the pack sealing device. A protruded stopper may also be formed at the one end of the rod member, so as to prevent the sealed pack from being separated from the pack sealing device by an external force. In addition, a semicircular protrusion may be formed at the tip of the rod member, so as to guide the pack to be easily slidably fitted in the pack sealing device. Where the rod member is attached to the pack while being made of a hard material, a plurality of grooves are formed at the outer surface of the rod member such that they are spaced apart from one another by a small distance in accordance with the present invention, so as to allow the rod member to be flexible. On the other hand, where the pack to be sealed by the pack sealing device is a zipper pack, the tubular member is slidably fitted around the zipper wrapped by a portion of the zipper pack, so as to seal the zipper pack. A plurality of grooves may be formed at the outer surface of the tubular member such that they are spaced apart from one another by a small distance, so as to allow the tubular member to be flexible. In the pack sealing device according to the present invention, the slit tubular member is slidably fitted around the rod member wrapped by a portion of the pack. A slit is formed at the tubular member to extend in a longitudinal direction of the tubular member. A squeeze gap is defined between the rod member and the tubular member in order to fit a portion of the pack, to be sealed, in a squeezed fashion. In accordance with the cooperation of the rod member and tubular member, the pack inserted into the squeeze gap is sealed in a squeezed state. Since most of the facing surfaces of the rod member and tubular member serve to squeeze the pack, a firm squeeze is achieved, thereby providing a reliable seal for the pack. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view illustrating a pack and a pack sealing device according to an embodiment of the present invention; FIG. 2 is a perspective view illustrating the appearance of the pack sealing device according to the embodiment of the present invention; FIG. 3 is a perspective view illustrating a tubular member included in the pack sealing device according to the embodiment of the present invention; FIG. 4 is a perspective view illustrating a rod member included in the pack sealing device according to the embodiment of the present invention; FIG. 5 illustrates, in the form of front and side views, the tubular member of the pack sealing device according to the embodiment of the present invention; FIG. 6 illustrates, in the form of front and side views, the rod member of the pack sealing device according to the embodiment of the present invention; FIG. 7 is a cross-sectional view illustrating the pack sealing device according to the embodiment of the present invention; FIGS. 8 and 9 are cross-sectional views illustrating a pack sealing device according to another embodiment of the present invention; FIG. 10 is a cross-sectional view illustrating a procedure for sealing a pack by use of the pack sealing device according to the embodiment of the present invention; FIGS. 11 to 14 are cross-sectional views respectively illustrating use of pack sealing devices having different structures in accordance with various embodiments of the present invention; FIG. 15 is a perspective view illustrating use of the pack sealing device in accordance with another embodiment of the present invention; FIGS. 16 and 17 are front views illustrating use of the pack sealing device in accordance with another embodiment of the present invention, respectively; FIG. 18 (a) to (d) are cross-sectional views respectively illustrating different structures of a shape retaining means in accordance with various embodiments of the present invention; FIG. 19 is a bottom perspective view illustrating a pack sealing device according to another embodiment of the present invention; FIG. 20 is a front view illustrating a pack sealing device according to another embodiment of the present invention; FIG. 21 is a cross-sectional view taken along the line A-A′ of FIG. 20; FIG. 22 is a cross-sectional view illustrating a tip portion of the pack sealing device shown in FIG. 19; FIG. 23 is a cross-sectional view illustrating a pack sealing device modified from that of FIG. 22 in accordance with the present invention; FIG. 24 is a cross-sectional view illustrating an operation of the rod member shown in FIG. 23 in accordance with the present invention; FIG. 25 is a perspective view illustrating use of the pack sealing device shown in FIG. 19 in accordance with the present invention; FIGS. 26 and 27 are perspective views each illustrating a pack sealing device according to another embodiment of the present invention; FIG. 28 is an exploded cross-sectional view illustrating a pack sealing device according to another embodiment of the present invention; FIG. 29 is an exploded cross-sectional view illustrating a pack sealing device according to another embodiment of the present invention; FIG. 30 is a cross-sectional view illustrating a pack sealing device according to another embodiment of the present invention; FIG. 31 is a perspective view illustrating use of the pack sealing device shown in FIG. 28 in accordance with the present invention; FIG. 32 is a perspective view illustrating a procedure for coupling the pack sealing device of FIG. 31 to a pack in accordance with the present invention; FIG. 33 is a side view illustrating packs to which one or more rod members are attached at diverse positions, respectively, in accordance with the present invention; FIG. 34 is a cross-sectional view illustrating a state in which the opening portion of the pack are folded into several plies so that it is sealed by the pack sealing device in accordance with the present invention; FIG. 35 is a front view illustrating a rod member attached to a portion of the pack near one corner of the pack in accordance with another embodiment of the present invention; FIG. 36 is a front view illustrating a state in which the rod member is wrapped by the corner portion of the pack in the case of FIG. 35 in accordance with the present invention; FIG. 37 is a cross-sectional view illustrating a sealed state in the case of FIG. 35 in accordance with the present invention; FIG. 38 is a perspective view illustrating a rod member formed with grooves and bonded to the outer surface of the pack in accordance with another embodiment of the present invention; FIG. 39 is an enlarged cross-sectional view corresponding to a part of FIG. 38; FIG. 40 is an enlarged perspective view illustrating the rod member provided with the grooves; FIG. 41 is a perspective view illustrating the state in which the rod member of FIG. 40 is bent; FIG. 42 is a bottom view illustrating a tubular member according to another embodiment of the present invention; FIG. 43 illustrates a procedure for sealing a zipper pack by the tubular member in accordance with another embodiment of the present invention; FIG. 44 illustrate, in the form of front and cross-sectional views, the case in which the rod member is installed in the interior of the pack in accordance with another embodiment of the present invention; FIG. 45 is a front view illustrating an embodiment of the present invention modified from that of FIG. 44; FIG. 46 is a side view corresponding to FIG. 45; FIG. 47 is a perspective view illustrating the rod member of FIG. 44; FIG. 48 is a cross-sectional view illustrating the rod member of FIG. 44; FIG. 49 is a cross-sectional view illustrating a procedure for venting air from the pack in accordance with the present invention; FIG. 50 is a perspective view illustrating the procedure for venting air from the pack in accordance with the present invention; and FIG. 51 is a front view illustrating a procedure for taking out the contents of the pack in accordance with the present invention. BEST MODE FOR CARRYING OUT THE INVENTION In the annexed drawings, the same or similar elements are designated by the same reference numerals even though they are depicted in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. Now, preferred embodiments of the present invention will be described in detail with reference to the annexed drawings. Although diverse liquid, gaseous, and solid materials may be packed in a sealed or vacuum state in accordance with the present invention, the following description will be described in conjunction with food commonly encountered in the course of daily life, for convenience of description. Referring to FIG. 1, a pack sealing device 2 according to the present invention is illustrated which is adapted to seal a pack 8. The pack sealing device 2 includes a rod member 14, a tubular member 16 adapted to be slidably fitted around the rod member 14, a squeeze gap 18 defined between the rod member 14 and the tubular member 16 to squeeze a desired portion of the pack 8 in a state in which the tubular member 16 is fitted around the rod member 14, and a slit 20 formed at the tubular member 16 to extend in a longitudinal direction of the tubular member 16. The rod member 14 has an outer diameter different from the inner diameter of the tubular member 16 so that the squeeze gap 18 is defined therearound. That is, the outer diameter of the rod member 14 is smaller than the inner diameter of the tubular member 16. The tubular member 16 is open at one end (a front end) or both ends (front and rear ends) thereof so that it can be slidably fitted around the rod member 14. In accordance with such a structure of the tubular member 16, each of the squeeze gap 18 and slit 20 is open at one end thereof, so that it receives a desired portion of the pack 8 through one open end thereof, thereby allowing the pack portion to be slidably fitted between the rod member 14 and the tubular member 16. In order to achieve easy insertion of a desired portion of the pack 8 into the pack sealing device 2, each of the rod member 14 and tubular member 16 is formed with an inclined surface or inclined guide at one end thereof. Similarly, each of the squeeze gap 18 and slit 20 has an inclined surface or inclined guide at one end thereof. The rod member 14 may have a diverse cross-sectional shape. For example, the rod member 14 may have a circular, semicircular, oval, semi-oval, triangular, or rectangular cross-sectional shape. In addition, the rod member 14 may have a polygonal cross-sectional shape such as a diamond, trapezoidal, pentagonal, hexagonal, or octagonal cross-sectional shape, or a modified cross-sectional shape therefrom. That is, the rod member 14 may have an optional cross-sectional shape in so far as it is possible to achieve an easy squeezing of the pack 8 while securing a reliable sealing effect. In the pack sealing device 1 according to the embodiment of the present invention illustrated in FIGS. 1 and 2, the tubular member 14 is open at one end thereof so as to allow the opening portion of the pack 8 to be inserted therein, while being closed at the other end thereof by means of a thermal fusing or bonding method or a male/female fitting method. In accordance with such a structure of the tubular member 16, each of the squeeze gap 18 and slit 20 is open at one end thereof while being closed at the other end thereof. When it is desired to seal the pack 8, the opening portion of the pack 8 is first wrapped around one end of the rod member 14, and then inserted into the squeeze gap 18 while passing through the slit 20. Thus, the opening portion of the pack 8 is squeezed in the squeeze gap 18 in accordance with the cooperation of the rod member 14 and tubular member 16, so that it is maintained in a sealed state, as shown in FIGS. 11 to 14. That is, the opening portion of the pack 8 including the opening 4 is in contact with the rod member 14 and tubular member 16 at a wide area while being squeezed between the rod member 14 and the tubular member 16, so that it is maintained in a tightly sealed state. The rod member 14 is coupled at its rear end to the rear end of the tubular member 16. Due to such a structure, the slit 20 does not extend to the rear end of the tubular member 16, as shown in FIGS. 2, 3 and 5. A connector 32 is formed at the rear end of the tubular member 16 where the slit 20 is not formed, so as to firmly couple the rod member 14 to the tubular member 16. The rod member 14 has a constant outer diameter throughout the length thereof, except for its front end. At the front end thereof with which the pack 8 initially come into contact when it is to be coupled to the pack sealing device 2, the rod member 14 has a guide 14a having a tapered structure with a cross-sectional area gradually reduced as it extends toward its tip. In accordance with such a structure, the initial insertion of the opening portion of the pack 8 into the squeeze gap 18 can be easily carried out. The slit 20 is formed at its front end portion with facing inclined surfaces 16b gradually spaced away from each other as they extend to the front end of the slit 20. In accordance with such a structure of the slit 20, the initial insertion of the pack 8 into the pack sealing device 2 can be easily carried out. In order to easily carry out the insertion of the opening portion of the pack 8 including the opening 4, the front end of the rod member 14 is slightly protruded beyond the front end of the tubular member 16. When it is desired to seal the pack 8 using the pack sealing device 2, it is desirable to wrap, around the front end of the rod member 14, the opening portion of the pack 8 in a state in which the opening 4 is closed, and then insert the opening portion of the pack 8 into the squeeze gap 18 and slit 20. The squeeze gap 18 has a width corresponding to 2 to 10 times the thickness of the pack 8, so as to allow an easy insertion of the pack 8. Where the slit 20 has an excessively large width, it cannot seal the pack 8. Accordingly, the slit 20 preferably has a width slightly larger than that of the squeeze gap 18 so that the pack 8 is allowed to easily access the slit 20 in a folded state. Where the pack 8 has a small thickness, it may be folded to have a multi-ply structure for its sealing. In accordance with the present invention, the tubular member 16 and/or the rod member 14 are made of a reinforced synthetic resin material which is not opaque, but transparent or semitransparent, so as to allow the user to identify, with the naked eye, the fitted state of the pack 8 or whether or not foreign matter is present in the squeeze gap 18. The slit 20 has a length longer than the width W of the pack 8 or the width of the opening 4, as shown in FIG. 1, so as to completely seal the opening 4 of the pack 8. The rod member 14 and tubular member 16 can be coupled to each other, using a diverse coupling structure. For example, the coupling of the rod member 14 and tubular member 16 may be firmly achieved by means of a coupling structure using engagement protrusions and engagement holes, as shown in FIGS. 3 to 7. In this case, the rod member 14 is provided at its rear end with an enlarged extension. A horizontal slit 24 is centrally formed at the enlarged extension to extend in a longitudinal direction of the enlarged portion, so as to divide the enlarged extension into two portions 22. For convenience of description, the enlarged extension of the rod member 14 will be designated by the reference numeral 22 used to designate its divided portions. In accordance with this structure, the enlarged extension 22 has an elasticity in vertical and lateral directions. Small engagement protrusions 26 are centrally formed at the upper and lower portions of the outer surface of the enlarged extension 22, respectively. The tubular member 16 is provided at its rear end with a hollow enlarged extension 30 having a cross-sectional area increasing gradually as it is spaced away from the rear end of the tubular member 16, as shown in FIGS. 5 and 7. Engagement holes 28 are formed at portions of the enlarged extension 30 corresponding to portions of the enlarged extension 22 where the engagement protrusions 26 are formed, respectively. Each engagement protrusion 26 of the enlarged extension 22 has an inclined surface 26a adapted to come into contact with the rear end edge of the enlarged extension 30 when the enlarged extension 22 is inserted into the enlarged extension 30, thereby causing the enlarged extension 22 to have a reduced cross-sectional area. In accordance with this structure, the engagement of the engagement protrusions 26 with the engagement holes 28 can be easily achieved. In this case, the coupling of the rod member 14 to the tubular member 16 can be achieved by fitting the front end of the rod member 14 in the enlarged extension 30 of the tubular member 16, and pushing the rod member 14 into the tubular member 16 until the engagement protrusions 26 are engaged with the engagement holes 30. In the coupled state, the squeeze gap 18 is defined between the rod member 14 and the tubular member 16. Thus, the pack sealing device 12 is completed. FIGS. 8 and 9 illustrate another coupling structure for the rod member 14 and tubular member 16 to complete the pack sealing device 12. In the case of FIG. 8, the rod member 14 is provided at its rear end with an enlarged extension 14d. The rod member 14 also has a knob 14e connected to the enlarged extension 14d while having a diameter larger than the enlarged extension 14d. In this case, the rod member 14 may be forcibly fitted in the rear end of the tubular member 16 at its rear end, bonded to the rear end of the tubular member 16 by use of an adhesive, or thermally fused to the rear end of the tubular member 16, so as to complete the pack sealing device 12. By virtue of the knob 14e, it is possible to prevent the rod member 14 from being excessively inserted into the tubular member 16. The knob 14e also allows the user to conveniently use the pack sealing device 12. Where it is unnecessary to use the knob 14e, the rear end of the rod member 14 may be formed to have an outer diameter equal to the inner diameter of the tubular member 16. Alternatively, the portion of the rod member 14 corresponding to the knob 14e may be dispensed with. As shown in FIG. 9, the enlarged extension 14d may be provided with an annular groove 14f. An annular protrusion 16d is also provided at the inner surface portion of the tubular member 16 such that it is engagable with the annular groove 14f. When the rod member 14 is forcibly fitted in the tubular member 16, the annular groove 14f and annular protrusion 16d are firmly engaged with each other. The annular groove 14f has an inclined portion and a vertical portion. The vertical portion of the annular groove 14f faces toward the rear end of the associated rod member 14. Similarly, the annular protrusion 16d has an inclined portion and a vertical portion. The vertical portion of the annular protrusion 16d faces toward the front end of the associated tubular member 16. Since the knob 14e has an outer diameter larger than the outer diameter of the tubular member 16, it is possible to prevent the rod member 14 from being excessively inserted into the tubular member 16 to cause a state in which the engagement between the annular groove 14 and annular protrusion 16d is released. FIG. 11 illustrates the case in which the cross-sectional shape of the rod member 14 is circular, semicircular, oval or semi-oval. In this case, the pack 8 is wrapped around the outer surface of the rod member 14, so that the squeezed or sealed area of the pack 8 is increased. In this case, the tubular member 16 preferably has a circular inner cross-sectional shape. However, the tubular member 16 may have an inner cross-sectional shape corresponding to the cross-sectional shape of the rod member 14. That is, the tubular member 16 may have a circular, semicircular, oval or semi-oval inner cross-sectional shape. FIG. 12 illustrates the case in which a rod member 14c having a triangular cross-sectional shape is used. In this cases the rod member 14c is engaged with the slit 20 at its one corner 14c′, so that a more tight sealing effect is obtained. In this case, the tubular member 16 may have a circular, semicircular or triangular cross-sectional shape in order to allow the rod member 14c to be inserted therein. In the case of the rod member 14c having a triangular cross-sectional shape, a more tight sealing effect is obtained because the pack 8 is sharply bent at the corners 14c′ of the rod member 14c, as compared to the case of FIG. 11 in which the rod member has a circular cross-sectional shape. That is, when the pressure applied to the pack 8 increases, the tension of the pack 8 increases in accordance with the function of the corner 14c′ of the rod member 14c engaged with the slit 20, as shown in FIG. 12, so that the pack 8 is squeezed at the remaining corners 14c′ of the rod member 14c under an increased pressure. In this state, the engagement between the slit 14 and the rod member 14c is more firmly achieved. In this case, accordingly, the effect for sealing the pack 8 is not lost even when an expansive pressure is applied to the pack 8 in accordance with the fermentation or aging of the food 3 received in the pack 8, or a high external pressure is applied to the pack 8. Since the rod member 14 is engaged with the tubular member 16 at one corner thereof, it does not rotate even when the pack 8 expands by virtue of an internal or external pressure applied thereto, so that it does not lose its sealing effect. The inner surface of the tubular member 16 and the outer surface of the rod member 14, between which the pack 8 is fitted, are made of a material having a certain lubricity, such as Teflon, so as to allow the opening portion of the pack 8 including the opening 4 to be easily slidably fitted therebetween. FIG. 13 illustrates the case in which a rod member 14b having a square cross-sectional shape is used. In this case, the rod member 14b is engaged with the slit 20 at its one corner 14b′, so that a more tight sealing effect is obtained. In this case, the tubular member 16 may have a circular or square cross-sectional shape. In the case of the rod member 14b having a square cross-sectional shape, a more tight sealing effect is obtained because the pack 8 is sharply bent at the corners 14b′ of the rod member 14b, as compared to the case of FIG. 11 in which the rod member has a circular cross-sectional shape. FIGS. 15 to 17 are perspective and front views illustrating the state in which the opening 4 of the pack 8 is sealed by the pack sealing device 12. In FIGS. 15 to 17, the pack 8 is shown in a state in which its contents are omitted. The pack 8 shown in FIG. 15 has a pack structure which is mainly used in our daily life. The pack 3 can pack a food 3 in a sealed state. That is, the user can seal the pack 8 in a vacuum state by use of the pack sealing device 12 after opening the opening 4 of the pack 8, and putting a food 3 into the pack 8 through the opened opening 4. Where the contents of the pack 8 contain a large part of solid ingredients (solids), as in Kimchi, it is possible to store the contents of the pack 8 in a completely sealed state without causing gas from being introduced into the pack 8 or from being leaked from the pack 8. Thus, it is possible to maintain the freshness, smell and taste of Kimchi for a prolonged period of time. FIG. 16 illustrates the case in which a material such as a food 3 is packed in the pack 8 at a factory (manufacturing place), and the opening 4 of the pack 8 is then sealed by the pack sealing device 12, so that the pack containing the material can be sold. FIG. 17 illustrates the case in which a material such as a food 3 is packed in the pack 8 at a factory or restaurant, and the opening 4 is sealed by means of a thermal fusing method or thermal pressing method, so that the pack containing the material can be sold. In this case, the pack 8 may be sold in a state in which the pack sealing device is coupled to the opening portion 4 of the pack 8 including the bonded or fused opening 4. Where a consumer desires to take out the contents of this pack 8, he may open the opening 4 of the pack 8 by means of a cutting or tearing method, as in conventional cases. Once the opening 4 of the pack 8 is opened, as described above, the vacuum state or sealed state of the pack 8 is lost. In accordance with the present invention, however, the remaining contents of the pack 8 can be stored in a sealed or vacuum state by use of the pack sealing device 12 additionally provided in a state of being coupled to the pack 8. In this case, there is an advantage in that the contents of the pack 8 can be repeatedly taken out and stored in a vacuum or sealed state. In accordance with the present invention, the pack 8 is preferably made of a vinyl film product for vacuum package formed by bonding, by use of a lamination method, a vinyl film having a dense structure, but having a low thermal fusibility, and a polyethylene (PE) film or polypropylene (PP) film having a less dense structure than that of the vinyl film, but being thermally fusible in accordance with a thermal fusing method. By virtue of such a film structure, it is possible to prevent gas or smell molecules from moving through the film structure of the pack 8. That is, the pack 8 is manufactured to have a laminated structure, taking into consideration the fact that a vacuum pressure is applied to the pack 8, or an expansive pressure is applied to the pack 8 in accordance with the fermentation or aging of the food 3 received in the pack 8. For example, the pack 8 has a double-layer structure consisting of an outer film and an inner film, as shown in FIG. 18 (a) to (d). Preferably, the outer film comprises a vinyl film having a dense structure to exhibit a low permeability of gas molecules, whereas the inner film comprises a polyethylene (PE) film or polypropylene (PP) film which is harmless to the human body while being easily thermally fusible, so that the inner and outer films can be bonded to each other. Thus, the pack 8 may be made of a general vinyl product for vacuum package. Of course, the pack 8 may be made of other materials. The food 3 stored in the pack 8 may have a liquid phase, a solid phase, a gaseous phase, or a mixed phase thereof. Accordingly, the pack 8 is preferably made of a hygienic synthetic resin material (vinyl product or vinyl film) having a flexibility so that it is adaptable to the phase of the food 3. Also, the synthetic resin material preferably has a high toughness so that it sufficiently withstands a shrinkage pressure caused by vacuum or an expansion pressure. In addition, it is preferred that the pack 8 have diverse standard shapes and sizes, taking into consideration the volume for containing the food 3. In accordance with the present invention, the pack 8 may be provided with a shape retaining means 10, as shown in FIG. 1. When the opening 4 of the pack 8 is widened to put a material into the pack 8 therethrough, the shape retaining means 10 retains the opening 4 in the widened state. Also, when the user pulls the opposite lateral ends of the opening 4 while grasping those lateral ends by the hands such that the lateral ends are moved away from each other, the opening 4 is closed. At this time, the shape retaining means 10 retains the opening 4 in the closed state. By virtue of the shape retaining means 10, it is unnecessary for the user to continuously grasp desired portions of the opening 4 by the hands in order to retain the opening 4 in the opened state. The shape retaining means 10 is arranged in the vicinity of the opening 4 to extend along the opening 4. Preferably, the shape retaining means 10 extends in parallel to the opening 4. Of course, the shape retaining means 10 may extend inclinedly with respect to the opening 4. Also, the shape retaining means 10 may be formed to be integral with the pack 8. Where the shape retaining means 10 is integral with the pack 8, it may be formed by forming a portion of the pack near the opening 4 to have an outwardly protruded structure having a thickness corresponding to 2 to 10 times the thickness of the pack 8 at other portions of the pack 8. Alternatively, a separate outer protrusion may be formed on the pack portion near the opening 4. As shown in FIG. 1 and FIG. 18 (a) to (d), the shape retaining means 10 may comprise a flexible wire 10a or flexible plate member 10b, which is easily bent when an external force is applied thereto, and retained at the bent state unless another external force is applied thereto. In order to protect or reinforce the wire 10a or plate member lob, a separate synthetic resin sheath 83 or 84 may be bonded to the outer surface of the pack 8 such that it covers the wire 10a or plate member 10b. The wire 10a is made of a soft metal wire or a synthetic resin wire, whereas the plate member 10b is made of a soft metal plate or a synthetic resin plate. Of course, the wire 10 and plate member 10b may be made of any other materials in so far as they can retain the opened state of the opening 4 established by an external force applied thereto. The size of the wire 10a and plate member 10b may be determined in accordance with the size of the pack 8 or the length of the opening 4, so as to retain the opened state of the opening 4. Meanwhile, where the wire 10a or plate member 10b is partially or completely made of a metal or conductive material, there is a problem in that it is impossible to put the pack 8 into a microwave oven for cooking the contents of the pack 8. In this case, the wire 10a or plate member 10b may be heated by induction heat generated in the microwave oven, thereby causing the pack 8 to melt or fuse. In severe cases, the pack 8 may be burnt. Therefore, in the case of a pack adapted to be used in a microwave oven, it is desirable that the wire 10a and plate member 10b are made of a material not influenced by induction heat, such as a synthetic resin. Referring to FIG. 18 (a) to (d), diverse structures of the shape retaining means 10 are illustrated. As shown in FIG. 18 (a) and (d), wires 10a or plate members 10b made of an aluminum thin plate are attached to respective outer surfaces of the front and rear vinyl films 81 and 82 of the pack 8 by means of an adhesive or a thermal fusing or pressing method, so that they are integral with the pack 8. Also, sheaths 84, in which wires 10a or plate members lob made of an aluminum thin plate are embedded, may be attached to respective outer surfaces of the front and rear vinyl films 81 and 82 of the pack 8 by means of an adhesive or a thermal fusing or pressing method, so that they are integral with the pack 8, as shown in FIG. 18 (b). Alternatively, as shown in FIG. 18 (c), plate members 10b may be attached to respective outer surfaces of the front and rear vinyl films 81 and 82 of the pack 8 by means of an adhesive or a thermal fusing or pressing method, so that they are integral with the pack 8. Thus, the shape retaining means 10 is completed. The pack sealing device 12, which is adapted to seal the opening 4 of the pack 8, operates to bring the front and rear vinyl films 81 and 82 to come into tight contact with each other, thereby causing the pack 8 to be maintained in an airtight or watertight state. The pack sealing device 12 is configured such that it is easily coupled to and separated from the pack 8. Accordingly, it is possible to easily achieve the vacuum or sealed state of the pack 8 or the vacuum or seal-released state of the pack 8. Also, the pack 8 can be repeatedly used. Where the plate members lob are made of a synthetic resin material, they may have a plate structure having a thickness and elasticity similar to those of a pad adapted to be inserted under a notebook. As the plate members lob having such a structure are attached to the pack 8, it is possible to achieve a desired shape retention of the opening 4. In the above described cases, the elasticity, thickness, width and flexibility of the plate members lob are appropriately adjusted, based on the volume (capacity) of the pack 8 or the length of the opening 4, so as to retain an optimum opening shape. In the case of the wires 10a, their design conditions are determined in the same manner as described above. Where the shape retaining means 10 is to be integral with the pack 8, it may be formed by forming a portion of the pack near the opening 4 to have an outwardly protruded structure having a thickness corresponding to 2 to 10 times the thickness of the pack 8 at other portions of the pack 8. Alternatively, a separate outer protrusion may be formed on the pack portion near the opening 4. FIGS. 19 to 27 illustrate the case in which a bent portion 14k is formed at the front end of the rod member 14 included in the pack sealing device 2 in accordance with the present invention, so as to more easily achieve the coupling of the pack 8 to the pack sealing device 2. Where the rod member 14 of the pack sealing device 2 does not have such a bent portion, and the pack 8 has a vertical seam 23 at its central portion, as shown in FIG. 25, the vertical seam 23 may be caught by the front end of the rod member 14 during an insertion of the pack 8 into the pack sealing device 2. In order to solve such a problem, the bent portion 14k is formed at the front end of the rod member 14. A horizontal extension 14h is also provided at a front end of the bent portion 14k. Also, a round or semicircular protrusion 15 is formed at a front end of the horizontal extension 14h. In accordance with such a structure, it is possible to prevent the seam 23 from being caught by the front end of the rod member 14 when the pack 8 is inserted into the pack sealing device 2. Thus, the operation for sealing the pack 8 can be easily achieved. The round or semicircular protrusion 15 formed at the front end of the horizontal extension 14h not only guides an easy insertion of the pack 8 into the pack sealing device 2 for sealing thereof, but also prevents the user or persons positioned around the pack sealing device 2 from being injured by the rod member 14 while preventing articles positioned around the pack sealing device 2 from being damaged by the rod member 14. Meanwhile, the pack 8 coupled to the pack sealing device 2 may slide along the rod member 14 during a movement thereof from one location to another location or by an external force intentionally or unintentionally applied to the pack 8 or pack sealing device 2, so that it may be separated from the pack sealing device 2. In order to prevent such a problem, a stopper 13 may be formed at a portion of the rod member 14 arranged slightly beyond the tubular member 16 such that it extends upwardly from the rod member 14, as shown in FIG. 23. When the pack 8 is coupled to the pack sealing device 2 in a sealed state, its edge arranged toward the front end of the rod member 14 is caught by the stopper 13. Thus, the above described problem is eliminated. The stopper 13 has, at one side thereof, a vertical surface 13a facing toward the squeeze gap 18 so as to restrain a separation of the pack from the pack sealing device 2. The stopper 13 also has, at the other side thereof opposite to the vertical surface 13a, an inclined surface 13b adapted to make the pack 8 be easily inserted into the pack sealing device 2. As shown in FIG. 23, the upper end of the stopper 13 is normally arranged at a level, indicated by the line P1, slightly higher than the level of the squeeze gap 18 indicated by the line P2, so as to allow the stopper 13 to be sufficiently engaged with the facing edge of the pack 8. Where it is desired to separate pack 8 from the pack sealing device 2, the user depresses the front end of the rod member 14, as indicated by an arrow in FIG. 24, such that the upper end of the stopper 13 is positioned at a level lower than the level of the squeeze gap 18 indicated by the line P2. In this state, the stopper 13 is disengaged from the facing edge of the pack 8. Accordingly, it is possible to easily separate the pack 8 from the pack sealing device 2. As shown in FIG. 20, one or more rings 9 may be attached to the upper portion of an outer surface of the tubular member 16, in order to connect a string or necklace 7 to the tubular member 16. Under the condition in which the string or necklace 7 is connected to the rings 9 of the tubular member 16, it is possible to stably carry or store the contents of the pack. For instance, as shown in FIG. 26 or 27, after the user receives, in the pack 8 through the opening 4, cash or valuables 11a, or an electronic appliance, which may be easily damaged by moisture and dust while being liable to be lost, for example, a mobile phone 11, and then seals the pack 8 by use of the pack sealing device 2, he may wear the pack 8 on the neck via the string or necklace 7 to carry the pack 8 or hang the pack 8 on a wall to store the pack 8. In this case, it is possible to prevent an electronic appliance such as the mobile phone 11, or cash or valuables 11a from being wet, lost, damaged in a watering place or swimming beach. Also, a handle 31 may be provided at a central portion of the tubular member 16, as shown in FIG. 20, so as to allow the user to carry the pack 8 by the hand. Of course, both the rings 9 and the handle 31 may be provided at the tubular member 16. The handle 31 may have a detachable structure. In place of the rings 9, a separate clip 7a, to which, the string or necklace 7 is connected, may be detachably mounted to the central portion of the tubular member 16, as shown in FIG. 27. In this case, the same effect as in the case of FIG. 26 is obtained. FIGS. 28 to 30 illustrate the case in which the rod member 14 and tubular member 16 of the pack sealing device 2 are separable from each other. In this case, the rear end of the tubular member 19 may have an open structure as shown in FIG. 28, or a closed structure as shown in FIG. 29. In the latter case, an end member 18a is provided at the rear end of the tubular member 16. By virtue of the end member 18a, it is possible to prevent the rod member 14 from extend excessively beyond the rear end of the tubular member 16 upon sealing the pack 8. In the case of FIG. 30, the rings 9 are attached to the upper portion of the outer surface of the tubular member 16, in order to connect a string or necklace 7 to the tubular member 16. In this case, it is possible to stably carry or store cash or valuables 11a, or an electronic appliance, for example, a mobile phone 11, as described above. FIGS. 31 and 32 illustrate the case in which the rod member 14 is formed to be integral with the pack 8, or bonded or fused to the pack 8. That is, the rod member 14, which has the same length as that of the opening 4 of the pack 8, is fixedly attached to a desired portion of the outer surface of the pack 8 in the vicinity of the opening 4. In this case, the tubular member 16 is also detachably attached to a desired portion of the outer surface of the pack 8 in the vicinity of the opening 4. When the user desires to take out the contents of the pack 8, he opens the opening 4 of the pack 8. After taking out a desired amount of the contents from the pack 8, the user detaches the tubular member 16 from the pack 8, wraps the rod member 14 by the opening portion of the pack 8, and then slidably fits the tubular member 16 around the rod member 14 wrapped by the opening portion of the pack 8. Thus, the pack 8 is sealed by the pack sealing device 2. As the above described procedure is repeatedly carried out, the contents of the pack 8 can be repeatedly taken out and stored in a sealed state. As shown in FIG. 33, one or more rod members 14 may be attached to one outer surface or each outer surface of the pack 8. Where two or more rod members 14 are attached to one outer surface or each outer surface of the pack 8, they may be arranged at the same level to face each other, or at different levels in a zig-zag fashion. In this case, it is possible to vary the position where the pack 8 is sealed by the pack sealing device, in accordance with the level of the contents in the pack 8. Where the opening portion of the pack 8 including the opening 4 has a small thickness, it may be wrapped around the rod member 14 in a state of being folded into two, three, or four plies, as shown in FIG. 34, so as to achieve a tight seal. Typically, the rod member 14 is attached to the pack 8 such that it extends in parallel to the opening 4. However, the rod member 14 may be attached to one corner portion 25 of the pack 8 near one end of the opening 4 such that it extends inclinedly with respect to the opening 4, as shown in FIG. 35, in order to provide an effective sealing effect in the case in which the opening portion of the pack 8 is inclinedly cut or tore to open the opening 4 at one end thereof so that the user can conveniently take out the contents of the pack 8. As the rod member 14 is fixedly attached to the pack 8 at one side of the opening 4, and the tubular member is separably fitted around the rod member 14, it is possible to seal the pack 8. In this case, the sealing of the pack 8 is achieved by wrapping the corner portion 25 of the pack 8 around the rod member 14, as shown in FIG. 36 and then slidably fitting the tubular member 16 around the rod member 14 wrapped by the pack portion, as shown in FIG. 37. Since the opening 4 is opened at the corner portion 25 of the pack 8, it is possible to conveniently take out the contents of the pack 8. Of course, the contents of the pack 8 can be repeatedly taken out and stored in a sealed state. In accordance with the present invention, the rod member 14, which is adapted to be attached to the outer surface of the pack 8, may have a diverse cross-sectional shape. For example, the rod member 14 may have a circular, semicircular, triangular, rectangular, or polygonal cross-sectional shape, an oval cross-sectional shape having a stopper structure, or a modified cross-sectional shape thereof. Since the rod member 14 is adapted to be bonded or fused to the outer surface of the pack 8, it is preferred that the surface of the rod member 14 contacting the opening 4 or corner portion 25 of the pack 8 be planar so that it provides a wide contact area. Although the rod member 14 and tubular member 16 are preferably made of a flexible or soft material so as to allow the pack 8 to be easily opened, they should be made of a hard material where the pack 8 has a large size or volume. Where the rod member 14 formed integrally with the opening 4 of the pack 8 or bonded to the opening 4 of the pack 8 is made of a hard material, as in the above described case, it is desirable to form a plurality of uniformly spaced grooves 27 at the rod member 14, as shown in FIGS. 38 to 41, so as to allow the rod member 14 to be easily bent, as shown in FIGS. 39 and 41. In accordance with this structure, the opening 4 of the pack 8 can be easily opened. The space between adjacent ones of the grooves 27 may be appropriately determined in accordance with the size or length of the rod member 14. Also, a plurality of annular grooves 29 uniformly spaced from one another by a small distance may be formed at the outer surface of the tubular member 14 in the pack sealing device 2 in accordance with the present invention so that the tubular member 14 has a desired flexibility, as shown in FIG. 42. Meanwhile, the pack sealing device 2 may also be applied to a zipper pack 8k provided, at the pack opening 4, with a zipper 21 consisting of female and male zipper members, as shown in FIG. 43. In this case, the zipper 21 is wrapped by the opening portion of the zipper pack 8k under the condition in which its female and male zipper members are coupled. Thereafter, the tubular member 16 is slidably fitted around the zipper 21 wrapped by the opening portion of the zipper pack 8k, so as to seal the zipper pack 8k. FIG. 44 illustrates, in the form of front and cross-sectional views, another embodiment of the present invention in which the rod member 14 is fixed to the inner surface of the pack 8. In this case, the pack 8 is wrapped around the rod member 14, and the tubular member 16 is then slidably fitted around the rod member 14 wrapped by the pack 8, so as to seal the pack 8. For example, where the rod member 14 has a triangular cross-sectional shape, it is bonded at both ends thereof to respective opposite lateral seams 8a of the pack 8 while being bonded at one flat portion 14g thereof to the inner surface of the pack 8, upon manufacturing the pack 8. In this case, it is important to prevent the seal of the pack 8 from being destroyed by the rod member 14. In the case of FIG. 44, the seams 8a of the pack 8 may be excessively protruded due to the cross-sectional shape of the rod member 14. Furthermore, the seal at the seams 8a may be destroyed when the rod member 14 is unstably bonded to the seams 8a. To this end, the rod member 14 has a triangular cross-sectional shape at a middle portion 14m thereof while having flat portions 14n of a reduced thickness at both ends thereof to be bonded to respective lateral seams 8a of the pack 8, respectively. Since the rod member 14 has the flat portions 14n having a reduced thickness, it can be firmly bonded to the seams 8a of the pack 8. Preferably, each flat portion 14n is centrally aligned with the rod member 14. FIGS. 49 and 50 illustrate an example of a procedure for sealing the pack 8 after putting contents, such as a food 3, into the pack 8. When it is desired to put a food 3 of a liquid phase containing liquid ingredients, such as soup, into the pack 8, the user widens the opening 4 by the hands to open the opening 4. At this time, the opening 4 is retained in a widened state by the shape retaining means 10. In this state, the user puts a desired amount of the food 3 into the pack 8 through the widened opening 4, wraps the rod member 14 by the opening portion of the pack 8 including the opening 4, and then slidably fits the tubular member 16 around the rod member 14 by pushing the tubular member 16 along the rod member 14. Thus, the pack sealing device 12 is coupled to the pack 8. Prior to such a coupling of the pack sealing device 12, the opening 4 of the pack 8 is temporarily maintained in an incompletely sealed state by incompletely pushing the tubular member 16 along the rod member 14, as shown in FIG. 50, in order to vent air from the pack 8. In this state, the user depresses the pack 8 at opposite sides while holding the front and rear vinyl films 81 and 82 of the pack by the hands H1 and H2, as shown in FIG. 49. As the pack 8 is depressed, it is contracted, thereby causing the food 3 to rise in the pack 8. As a result, air O present above the food 3 is vent from the pack 8. After completely vent the air O present in the pack 8 by continuously depresses the pack 8 by the hands H1 and H2, the user completely pushes the tubular member 16 along the rod member 14, so as to completely fit the tubular member 16 around the rod member 14. Thus, the pack 8 is completely sealed. Where it is difficult to completely vent the air O, the user pushes the tubular member 16 along the rod member 14 under the condition in which he depresses the pack 8 by the hands H1 and H2 until a small amount of the food 3 is slightly leaked from the pack 8. Accordingly, it is possible to completely seal the pack 8 in a state in which the air O has been completely vented. Since the interior of the pack 8 is maintained in a vacuum state in accordance with a completely ventilation of air therefrom, it is possible to prevent the food 3 from being oxidized and rotting, while maintaining the freshness and intrinsic smell of the food. Accordingly, the food 3 can be stored for a prolonged period of time. Generally, a considerable amount of gas (oxygen, etc.) is present, in a dissolved state, in water such as city water. In the case of a food cooked using such water, gas contained in the food is escaped from the water during a procedure of cooling the food because it is evaporated. Accordingly, where such a cooked food is packed in a pack, it can have a state approximate to a vacuum state when air visible to the naked eye is removed from the pack. Since the pack 8 of the present invention can prevent gas or smell molecules of the food 3 from escaping therefrom by virtue of its vinyl film having a dense structure, it is possible to maintain the freshness and intrinsic smell and taste of the food 3 for a prolonged period of time. Also, the pack 8 is hygienic because its inner film contacting the food 3 is made of a polyethylene (PE) film or polypropylene (PP) film. For example, even when a highly smelly food, such as fish, beef, or Kimchi, is packed in the pack 8 in a sealed state, and then it is stored in a refrigerator, there is no occasion that the smell of the fish, beef, or Kimchi permeates the refrigerator, because the smell molecules of the fish, beef, or Kimchi cannot escape from the pack 8. In the case in which such a food is stored in a frozen state in a pack made of a general vinyl, for several months, however, the smell of the refrigerator may permeate the food. In accordance with the present invention, it is also possible to prevent the freshness and intrinsic smell and taste of the fish, beef, or Kimchi from being degraded, because the smell of the refrigerator cannot permeate the pack 8. Meanwhile, the pack 8 and pack sealing device 12 of the present invention can be reused after being washed. Accordingly, there is an advantage in terms of use of resources. Also, the present invention is applicable to temporary storage of garbage rotting easily and severely while smelling highly. That is, such garbage may be accumulatively put into the pack of the present invention to be temporarily stored prior to disposal thereof. In particular, it is wasteful to dump the pack 8 once used to store Kimchi or other food. In this regard, where such a pack is reused to store food garbage or other garbage in a sealed state, there is an advantage in that it is unnecessary to daily dump such garbage because the smell of the garbage can be perfectly confined in the pack in accordance with the present invention. Even in the summer season in which garbage may rot easily and severely, there is no problem caused by such rotting of garbage. Also, where the pack and pack sealing device of the present invention are used to store food of a liquid phase such as sweet drink made from fermented rice, beef soup, anchovy soup, loach soup, or soup of chopped beef with various condiments, or side dishes, such food or side dishes may be cooked in a large amount, and stored in the freezing or refrigerating compartment of a refrigerator in a state of being packed in the pack 8 so that they may be subsequently taken out from the pack 8 in a desired amount. The food may be packed in dosage in a plurality of packs, respectively. In this case, the packs may be stored in a frozen state in the freezing compartment of the refrigerator so that the food can be taken in dosage after being thawed every time it is to be taken. A desired number of the frozen packs stored in the freezing compartment of the refrigerator may be periodically transferred to the refrigerating compartment of the refrigerator so that they are stored in a refrigerated state. In this case, it is possible to eliminate the time taken to thaw the frozen food before the user takes the food. Also, the pack and pack sealing device of the present invention may be used to store boiled rice. For example, boiled rice may be put in a rice bowl which is, in turn, packed in the pack 8 of the present invention. In this case, the taste of the boiled rice can be maintained for a prolonged period of time. Where food is stored in the pack 8 of the present invention in a state of being put in a port, it is possible to maintain the freshness and intrinsic smell and taste of the food for a prolonged period of time because the smell of the food is perfectly confined in the pack 8, and external smell cannot permeate the pack 8. In addition, the pack and pack sealing device of the present invention may be used to store food to be taken in a picnic party or other events for leisure. Cooked food or food prepared to be simply cooked may be packed in the pack 8 in a sealed state, and then transported to an event place. In this case, there is convenience in that it is unnecessary to perform a complicated cooking process in the event place. It is also possible to prevent the smell of the food 3 from permeating the vehicle transporting the food 3 because the pack 8 prevents diffusion of the food smell. Thus, it is possible to prevent the interior of the vehicle from being contaminated. Where the food packed in the pack is soup or pot-stew, there is convenience in that the user can take the food after simply heating or boiling the food in the event place without requiring any cooking process. Since the pack sealing device 12 of the present invention provides a strong seal effect, it is possible to prevent gas from being introduced into the pack or outwardly leaked from the pack. Also, the pack 8 can sufficiently withstand an excessive expansion pressure generated therein because it is made of a vinyl film having a high toughness. That is, the pack 8 exhibits a superior seal effect for fermentable food. After an experiment, it could be seen that there is no occasion that gas generated in accordance with a fermentation of the food stored in the pack is leaked through the front and rear vinyl films 81 and 82 of the pack 8 or through the pack sealing device 12, or causes the pack 8 to be exploded. Since the vinyl film of the pack 8 has a surface having a certain smoothness, and the elements of the packing sealing device 12 are machined to have a certain smoothness, it is possible to easily achieve the coupling of the pack sealing device 12 to the pack 8. When the user widens the opening 4 of the pack 8 to put the food 3 into the pack 8, the shape retaining means 10 retains the opening 4 in the widened state. Accordingly, the user can easily put the food 3 into the pack 8. It is also possible to prevent the food 3 from being smeared on the outer surface of the pack 8 around the opening 4 or flowing along the outer surface of the pack 8 during the process of putting the food 3 into the pack 8. Thus, the pack 8 can be maintained in a clean state. Also, it is possible to reduce the phenomenon that the pack 8 is folded or otherwise varied in shape at its middle portion during the process of putting the food 3 into the pack 8, as compared to conventional cases. Accordingly, there are advantages in that it is possible to conveniently use the pack 8 while reducing the time taken to put the food 3 into the pack 8. When it is desired to take out the food 3 packed in a vacuum state in the pack 8, the user first laterally pulls the pack sealing device 12 such that the opening 4 of the pack 8 is slightly opened, and then inclines the pack 8 to take out a desired amount of the food 3 through the opened opening 4, as shown in FIG. 50. Thereafter, the user depresses the pack 8 at opposite sides while holding the front and rear vinyl films 81 and 82 of the pack 8 by the hands, as described above, in order to substantially completely vent air O present in the pack 8. Finally, the user laterally pushes the pack sealing device 12 to seal the opening 4 of the pack 8. Thus, the remaining food 3 can again be packed in a vacuum state in the pack 8. Although the preferred embodiments of the invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. INDUSTRIAL APPLICABILITY In accordance with the present invention, it is possible to pack diverse liquid, gaseous, and solid materials or objects in a sealed or vacuum state after putting such a material or object into the pack of the present invention through the opening of the pack, and then sealing the opening of the pack by the pack sealing-device of the present invention. The pack and pack sealing device of the present invention can be simply and conveniently used by young and old, men and women. Since each of the pack and pack sealing device of the present invention has a simple structure, it can provide a reliable sealing or vacuum effect without any failure. When it is desired to store food in a sealed or vacuum state, this storage can be simply and conveniently achieved using the pack and pack sealing device of the present invention. When the food packed in the pack is to be taken out for its cooking or consumption by the user, the sealed or vacuum state of the pack can be simply released as the user laterally pulls or pushes the pack sealing devices. In such a manner, the food packed in the pack can be repeatedly taken out and stored in a vacuum or sealed state. Since each of the pack and pack sealing device of the present invention has a simple structure, it can be easily used by people, young and old, men and women all alike, without involving any failure thereof. In some applications, the pack and pack sealing device of the present invention make our daily life more convenient. Thus, the present invention is useful in the pursuit of a happy daily life.
<SOH> BACKGROUND ART <EOH>Generally, where food and drink, in particular, food, is stored or packed in a sealed or vacuum state so that it cannot come into contact with air or oxygen, it is possible to prevent the food from being oxidized or rotting, to considerably lengthen the storage period of the food, and to maintain the freshness and intrinsic smell of the food for a prolonged period of time. For such a purpose, a zipper pack has been proposed in which a zipper consisting of female and male zipper members is provided at an opening of the pack, so as to conveniently seal the opening. However, this zipper pack has a problem in that the seal may be easily collapsed by external pressure. Also, there are problems of a difficulty in manufacture and an increase in manufacturing cost. Also, a hinged sealing device has been proposed which has two members hingably connected to each other, and adapted to clamp the opening portion of a pack therebetween. However, this hinged sealing device cannot provide a reliable seal. Furthermore, it is inconvenient to use this sealing device. In particular, there is a problem caused by the structure of the sealing device in that the seal at the middle portion of the sealing device is weak. Meanwhile, general vinyl packs made of a polyethylene (PE) film or polypropylene (PP) film can be inexpensively and easily manufactured. However, such a vinyl pack does not have a dense structure, so that smell molecules of the contents in the vinyl pack may pass through the vinyl pack, thereby emitting foul odors. When the opening of such a vinyl pack is widened to put a material into the vinyl pack, it may not be maintained in the widened state. For this reason, where a soup containing solids is to be put into the vinyl pack, there is a problem in that the liquid or solids of the soup may be smeared on the outer surface of the vinyl pack around the opening or flow along the outer surface of the vinyl pack, thereby staining the vinyl pack. Such a problem is mainly caused by the fact that both the general vinyl pack and the vacuum vinyl pack have an insufficient rigidity to maintain the opened state of their openings, or they have no means for maintaining the opened state of their openings.
<SOH> BRIEF DESCRIPTION OF THE DRAWINGS <EOH>FIG. 1 is a perspective view illustrating a pack and a pack sealing device according to an embodiment of the present invention; FIG. 2 is a perspective view illustrating the appearance of the pack sealing device according to the embodiment of the present invention; FIG. 3 is a perspective view illustrating a tubular member included in the pack sealing device according to the embodiment of the present invention; FIG. 4 is a perspective view illustrating a rod member included in the pack sealing device according to the embodiment of the present invention; FIG. 5 illustrates, in the form of front and side views, the tubular member of the pack sealing device according to the embodiment of the present invention; FIG. 6 illustrates, in the form of front and side views, the rod member of the pack sealing device according to the embodiment of the present invention; FIG. 7 is a cross-sectional view illustrating the pack sealing device according to the embodiment of the present invention; FIGS. 8 and 9 are cross-sectional views illustrating a pack sealing device according to another embodiment of the present invention; FIG. 10 is a cross-sectional view illustrating a procedure for sealing a pack by use of the pack sealing device according to the embodiment of the present invention; FIGS. 11 to 14 are cross-sectional views respectively illustrating use of pack sealing devices having different structures in accordance with various embodiments of the present invention; FIG. 15 is a perspective view illustrating use of the pack sealing device in accordance with another embodiment of the present invention; FIGS. 16 and 17 are front views illustrating use of the pack sealing device in accordance with another embodiment of the present invention, respectively; FIG. 18 ( a ) to ( d ) are cross-sectional views respectively illustrating different structures of a shape retaining means in accordance with various embodiments of the present invention; FIG. 19 is a bottom perspective view illustrating a pack sealing device according to another embodiment of the present invention; FIG. 20 is a front view illustrating a pack sealing device according to another embodiment of the present invention; FIG. 21 is a cross-sectional view taken along the line A-A′ of FIG. 20 ; FIG. 22 is a cross-sectional view illustrating a tip portion of the pack sealing device shown in FIG. 19 ; FIG. 23 is a cross-sectional view illustrating a pack sealing device modified from that of FIG. 22 in accordance with the present invention; FIG. 24 is a cross-sectional view illustrating an operation of the rod member shown in FIG. 23 in accordance with the present invention; FIG. 25 is a perspective view illustrating use of the pack sealing device shown in FIG. 19 in accordance with the present invention; FIGS. 26 and 27 are perspective views each illustrating a pack sealing device according to another embodiment of the present invention; FIG. 28 is an exploded cross-sectional view illustrating a pack sealing device according to another embodiment of the present invention; FIG. 29 is an exploded cross-sectional view illustrating a pack sealing device according to another embodiment of the present invention; FIG. 30 is a cross-sectional view illustrating a pack sealing device according to another embodiment of the present invention; FIG. 31 is a perspective view illustrating use of the pack sealing device shown in FIG. 28 in accordance with the present invention; FIG. 32 is a perspective view illustrating a procedure for coupling the pack sealing device of FIG. 31 to a pack in accordance with the present invention; FIG. 33 is a side view illustrating packs to which one or more rod members are attached at diverse positions, respectively, in accordance with the present invention; FIG. 34 is a cross-sectional view illustrating a state in which the opening portion of the pack are folded into several plies so that it is sealed by the pack sealing device in accordance with the present invention; FIG. 35 is a front view illustrating a rod member attached to a portion of the pack near one corner of the pack in accordance with another embodiment of the present invention; FIG. 36 is a front view illustrating a state in which the rod member is wrapped by the corner portion of the pack in the case of FIG. 35 in accordance with the present invention; FIG. 37 is a cross-sectional view illustrating a sealed state in the case of FIG. 35 in accordance with the present invention; FIG. 38 is a perspective view illustrating a rod member formed with grooves and bonded to the outer surface of the pack in accordance with another embodiment of the present invention; FIG. 39 is an enlarged cross-sectional view corresponding to a part of FIG. 38 ; FIG. 40 is an enlarged perspective view illustrating the rod member provided with the grooves; FIG. 41 is a perspective view illustrating the state in which the rod member of FIG. 40 is bent; FIG. 42 is a bottom view illustrating a tubular member according to another embodiment of the present invention; FIG. 43 illustrates a procedure for sealing a zipper pack by the tubular member in accordance with another embodiment of the present invention; FIG. 44 illustrate, in the form of front and cross-sectional views, the case in which the rod member is installed in the interior of the pack in accordance with another embodiment of the present invention; FIG. 45 is a front view illustrating an embodiment of the present invention modified from that of FIG. 44 ; FIG. 46 is a side view corresponding to FIG. 45 ; FIG. 47 is a perspective view illustrating the rod member of FIG. 44 ; FIG. 48 is a cross-sectional view illustrating the rod member of FIG. 44 ; FIG. 49 is a cross-sectional view illustrating a procedure for venting air from the pack in accordance with the present invention; FIG. 50 is a perspective view illustrating the procedure for venting air from the pack in accordance with the present invention; and FIG. 51 is a front view illustrating a procedure for taking out the contents of the pack in accordance with the present invention. detailed-description description="Detailed Description" end="lead"?
20050427
20090317
20060316
90391.0
B65B708
7
PASCUA, JES F
PACK SEALING METHOD AND DEVICE
SMALL
0
ACCEPTED
B65B
2,005
10,532,760
ACCEPTED
Process and apparatus to cool harvest grapes
The invention relates to a process and apparatus to cool harvest grapes, the grapes being transported from a harvest reception vessel (1) to a press (5) or to a maceration vessel (23), characterized in that the grapes are charged with carbon dioxide during transport to the press (5) and/or during transport to the maceration vessel (23). As a result a flavour improvement of the wine is achieved.
1. A process to cool harvest grapes comprising the steps of transporting the grapes to a press or to a maceration vessel, and charging the grapes with carbon dioxide during transport to the press or during transport to the maceration vessel. 2. A process according to claim 1, wherein gaseous carbon dioxide is brought into contact with the grapes. 3. A process according to claim 1, wherein liquid carbon dioxide is brought into contact with the grapes. 4. A process according to claim 1, wherein solid carbon dioxide is brought into contact with the grapes. 5. A process according to claim 1 wherein carbon dioxide is fed in the gaseous state to the grapes and is at least in part taken from a reservoir which contains liquid carbon dioxide. 6. An apparatus for producing wine comprising a harvest reception vessel, a press, a maceration vessel, a connection line to the harvest reception vessel, a connection line to the press and a connection line to the maceration vessel, each of said connection lines being configured for transporting the grapes wherein at least one feed line is provided to at least one of the connection lines, through which carbon dioxide is fed into the at least one of the connection lines. 7. An apparatus for producing wine comprising a harvest reception vessel, a press, a connection line for transporting the grapes from the harvest reception vessel to the press, and a feed line for feeding carbon dioxide into the connection line. 8. An apparatus according to claim 6, wherein at least one of the feed lines for carbon dioxide is connected to a reservoir for carbon dioxide which contains liquid and gaseous carbon dioxide. 9. The process of claim 1, wherein the grapes are transported from a harvest reception vessel. 10. The process of claim 1, further comprising the step of directing the movement of the grapes with one or more valves. 11. The process of claim 1, further comprising the step of detecting the temperature of the grapes. 12. The process of claim 1, further comprising the steps of measuring the temperature of the grapes and controlling the temperature of the grapes by providing carbon dioxide in a manner responsive to the measured temperature. 13. The process of claim 1, wherein the temperature of the grapes is controlled with a programmable logic controller. 14. The process of claim 1, further comprising the step of directing the movement of the carbon dioxide to the grapes with one or more valves. 15. The apparatus of claim 6, further comprising one or more valves configured to direct the movement of the grapes. 16. The apparatus of claim 6, further comprising one or more temperature measuring devices. 17. The apparatus of claim 6, further comprising a programmable logic controller configured to control the amount of carbon dioxide provided. 18. The apparatus of claim 6, further comprising one or more valves to control the movement of carbon dioxide.
The invention relates to a process for producing wine, the grapes being transported from a harvest reception vessel to a press or fed to a maceration vessel. In addition, the invention relates to an apparatus for cooling grapes between a harvest reception vessel and a press or a maceration vessel. In wine production, the conventional sequence is known in which the grapes after harvest pass into a vessel (harvest reception vessel), from which they are transported to the press. To produce a better wine the grapes are subject to a maceration process for a few hours before the fermentation process. The grapes are put to a maceration vessel to extract flavours from the grape skins. The grapes remain in the maceration vessel for a few hours before the fermentation process begins. There are also wine producing installations that do not comprise a maceration vessel. In this case the maceration takes place in the press. The formation of flavour is particularly effected by the conditions (for example temperature, residence time) in the above-described production steps. The object underlying the present invention is to provide an improved process and an apparatus suitable for improvement in wine flavour. On the processing side, the object set is achieved by the fact that the grapes are charged with carbon dioxide during transport to the press and/or maceration vessel. If the grapes are charged with carbon dioxide during transport to the press and carbon dioxide is introduced into the maceration vessel for cooling the grapes during maceration, an outstanding improvement of the wine taste is achievable. Expediently, carbon dioxide is brought into contact with the grapes. It has proved to be particularly favorable to add carbon dioxide until the grape temperature is somewhat more than 7° C. The carbon dioxide is fed to the grapes with great advantage as gaseous carbon dioxide, as liquid carbon dioxide and as solid carbon dioxide or dry ice. The input of gaseous carbon dioxide creates an inert atmosphere for the grapes. The input of liquid carbon dioxide causes a significant drop in grape temperature that helps to improve the taste. A drop of temperature is also achievable by introducing cold carbon dioxide gas, preferably cold carbon dioxide gas gained from a liquid carbon dioxide source. With the injection of liquid carbon dioxide dry ice and gaseous carbon dioxide may be generated depending on the design of the injector. The injection of dry ice is favorable fpr a smooth cooling down of grape temperature due to the sublimation taking place. Preferably, the carbon dioxide fed in the liquid state to the grapes is at least in part taken from a reservoir which contains liquid carbon dioxide. Such a reservoir has an advantageously high storage density. On the apparatus side, the object set is firstly achieved by means of the fact that a feeder is provided for carbon dioxide, via which the carbon dioxide is added to the connection line upstream of the press. Secondly, the object set is also achieved by means of the fact that a feeder for carbon dioxide is provided in the connection line to the maceration vessel. According to a particularly preferred embodiment of the invention, both solutions are combined, so that a feeder for carbon dioxide is provided via which the carbon dioxide is added to the connection line upstream of the press and a feeder for carbon dioxide is provided into the connection line to the maceration vessel. The two embodiments solve the object set of improving the wine flavour not only in each case individually, but also in combination with one another, a particularly outstanding flavour being able to be achieved in the combination. Expediently, the feeder for carbon dioxide is connected to a reservoir for carbon dioxide which contains liquid and gaseous carbon dioxide. The invention and other details of the invention will be described in more detail below with reference to an exemplary embodiment shown diagrammatically in the FIGURE. The FIGURE shows a diagram for wine production: the grapes, after harvest, are introduced into the harvest reception vessel 1, from which they are transported to a vessel 2 from which they are fed using a pump 3 via a connection line 4 to the press 5 or to a maceration vessel 23. The way of the grapes is determined by the position of the valves 20, 21 and 22. A plurality of temperature measuring points are installed on the transport path of the grapes and used to determine the respective grape temperature. The inlet temperature is measured by the measuring device 6 and sent to a programmable logic controller (PLC). This temperature is compared to a set point (desired temperature) and the amount of carbon dioxide to be fed through valve 12 is calculated by the PLC. The valve 12 is a regulation valve, its opening degree is driven by the PLC. The valves 18 and 19 are used to choose the line along which the grapes are transported, e.g. to the press 5 or to the maceration vessel 23. The temperature measuring devices 8 and 9 control the temperature after the injection of carbon dioxide. In case of a drop in temperature exceeding a pretermined intervall, the injection of carbon dioxide is shut down by the PLC. This control function is very important to avoid freezing of the transport pipes and lines, in case the grape flow is not at correct speed. Carbon dioxide is fed from at least one reservoir for carbon dioxide (not shown) via a line 10 which bears liquid carbon dioxide and has a pneumatic regulation valve 12, and a line 11 which bears gaseous carbon dioxide and has an electrically operated valve 13. If only one reservoir is present, the line 11 is thus connected to the head space of the reservoir where the carbon dioxide is present in the gaseous state, and the line 10 is disposed further down, so that via the line 10 liquid carbon dioxide can be taken from the reservoir. The two lines 10 and 11 are combined into one line 14. The line 14 has a safety valve 15. The carbon dioxide is apportioned between the lines 16 and 17 each of which has an electrically operated valve 18, 19. Opening the electrically operated valve 18 enables carbon dioxide to be introduced into the connection grapes transport line 24. Opening the electrically operated valve 19 enables carbon dioxide to be introduced into the connection line 25 bearing grapes. The valves 20, 21 and 22 represent diagrammatically the possibilities of feeding grapes into the press, the maceration vessel 23 and for further processing. The possibilities result from the potential combinations of the two valve settings (open or closed) for the valves 20, 21 and 22. In the exemplary embodiment, the use of the programmable logic controller PLC will also be described in more detail. Control points for this controller are the harvest temperature (measured at the temperature measuring point 6), the grape sensor 7 which determines whether grapes are present in the vessel 2, the valve position of the valves 20, 21 and 22 and the temperature at the temperature measuring points 8 and 9. The controller (PLC) first compares the temperature value determined at the temperature measuring point 6 with a pre-set value. If grapes are present in the vessel 2, the pump 3 is started. At least one valve 21, 22 must be open, then the feed of carbon dioxide is also started. The injection line is choosen by opening the valve 18 or 19. First the valve 13 (gaseous state) is open for a few seconds to rise the pressure and clean the injector inside the connection to the grapes transport pipe. Second the valve 12 (liquid state) is open gradually, the valve 13 is closed. There are two main operating possibilities: If the users choice is only to protect the grapes by an inert gas during transport, only the valves 18 or 19 and the valve 13 is openend, in case all conditions controlled by the PLC are fulfilled. Carbon dioxide gas is injected during all transport time. The valve 12 stays in closed position. For lowering the temperature of the grapes significantly the valve 12 has to be opened. In contrary to the first possibility, where the valve 12 stays closed and there is only gaseous input, there is a significant drop in temperature with the second possibility of injecting liquid carbon dioxide. As described before, the injection of liquid carbon dioxide can generate dry ice which is very favorable for cooling the grapes smoothly. The grapes are at least inertized. Depending on the amount of carbon dioxide fed and its temperature, the grapes are additionally cooled, preferably to a temperature of 7° C. The temperature of the carbon dioxide can be varied by the valve position of the valves 12 and 13. When valve 12 is open and valve 13 is closed, the coldest temperature is achieved, whereas with valve 12 closed and valve 13 open the highest temperature can be reached. The degree of opening valve 12 is controlled as a function of the difference in temperature at each temperature measuring point, e.g. temperature measuring point 6, and the pre-set values of grape temperature. The controller is set in such a manner that the feed of carbon dioxide is stopped as soon as pump 3 is stopped or the valves 21/22 are closed or the temperature measured at 8 or 9 is too low. When the feed of carbon dioxide is started, advantageously, at first for approximately 5 seconds only valve 13 is open (gaseous feed) while valve 12 remains closed. This prevents liquid carbon dioxide being injected at high pressure via a nozzle 26 into the connection line 24 and/or 25. After expiry of the 5 seconds, valve 12 is slowly opened up to the degree of opening pre-set by the controller (PLC). The cooling effect is monitored via temperature measurements at the temperature measuring points 6, 8 and 9. If the temperature measured there falls below 7° C., the PLC interrupts the feed of carbon dioxide. This reliably prevents freezing of the grapes or moisture freezing onto the connection lines.
20051116
20100907
20060713
59658.0
F25D2500
0
ALI, MOHAMMAD M
PROCESS AND APPARATUS TO COOL HARVEST GRAPES
UNDISCOUNTED
0
ACCEPTED
F25D
2,005
10,533,598
ACCEPTED
Energy filter image generator for electrically charged particles and the use thereof
The invention relates to an energy filter image generator for filtering electrically charged particles. The inventive energy filter comprises at least two toroidal energy analysers (30, 40) arranged one inside the other. A transfer lens device (20) is disposed between the plane of emergence (5) of the first energy analyser (30) and the plane of incidence of the second energy analyser (40), thereby making it possible to obtain the perfect energy filtered reproduction of the surface (1′) of a sample on a detector (10).
1. Image-generating energy filter for electrically charged particles such as electrons and ions with at least two toroidal energy analyzers arranged in a row, where at least one energy analyzer has a diaphragm at its entrance plane and another diaphragm at its exit plane, characterized in that: a transfer lens device (20, 20′) is located between the exit plate (5) of the first energy analyzer (30, 30′, 30″) and the entrance plane (6) of the second energy analyzer (40, 40′, 40″), which device has negative lateral magnification VL, negative angular magnification VW, image rotation around the angle γ=μ−180°, and a telescopic beam path, where its respective deflection angles φ are equal and its energy-dispersive planes (33, 43) are rotated around the angle β with respect to each other. 2. Energy filter according to claim 1, characterized in that the transfer lens device (20, 20′) is designed so that, in the energy-dispersive plane (33), it projects the intermediate image ZB1 (23) present at the exit plane (5) of the first energy analyzer (30, 30′, 30″) with a linear magnification of V L = ZB 2 ZB 1 < 0 and with an angular magnification of V W = - α 2 α 1 < 0 ⁢ ⁢ where ⁢ ⁢ V W ⁢ V L ⁢ E 2 E 1 = 1 , rotated around the angle γ, onto the entrance plane (6) of the second energy analyzer (40, 40′, 40″) as intermediate image ZB2 (24), where α1 is the exit angle of the charged particles from the exit plane (5) of the first energy analyzer (30, 30′, 30″); α2 is the entrance angle to the entrance plane (6) of the second energy analyzer (40, 40′, 40″); E1 is the kinetic energy of the charged particles in the exit plane of the first energy analyzer (30, 30′, 30″); and E2 is the kinetic energy of the charged particles in the entrance plane of the second energy analyzer (40, 40′, 40″), and where the charged particles in the transfer lens device (20, 20′) pass through a telescopic beam path. 3. Energy filter according to claim 1, characterized in that the energy analyzers (30, 30′, 30″; 40, 40′, 40″) and the transfer lens device (20) are arranged with radial symmetry around the center of the transfer lens device. 4. Energy filter according to claim 1, characterized in that the energy analyzers (30, 30′, 30″; 40, 40′, 40″) are built with different dimensions. 5. Energy filter according to claim 1 characterized in that the energy analyzers are spherical sectors (30′, 40′), hemispherical analyzers (30, 40), or cylindrical analyzers (30″, 40″). 6. Energy filter according to claim 5, characterized in that the energy-dispersive planes (33, 43) of the hemispherical analyzers (30, 40) are rotated around the axis (200) of the transfer lens device (20) by the angle β=180°, so that the beam path has a the shape of an “S”. 7. Energy filter according to claim 1, characterized in that the transfer lens device (20) comprises at least one electrostatic tube lens (21, 22). 8. Energy filter according to claim 1, characterized in that the transfer lens device (20′) comprises at least one magnetic lens. 9. Energy filter according to claim 1, characterized in that the transfer lens device (20) comprises at least one multipole lens (121, 122). 10. Energy filter according to claim 1, characterized in that the transfer lens device (20) has at least two lenses (21, 21′) and (22, 22′), and in that the exit plane (5) of the first energy analyzer (30, 30′, 30″) is located at the focal point of the first lens (21, 21′) and the entrance plane (6) of the second energy analyzer (40, 40′, 40″) is located at the focal point of the second lens (22, 22′), where the distance between the two lenses is 2F, where F stands for the focal distance of the lenses (21, 22, 21′, 22′). 11. Use of an energy filter according to claim 1 for electron microscopes. 12. Use of an energy filter according to claim 1 for time-resolved measuring instruments. 13. Energy filter according to claim 2, characterized in that the energy analyzers (30, 30′, 30″; 40, 40′, 40″) and the transfer lens device (20) are arranged with radial symmetry around the center of the transfer lens device. 14. Energy filter according to claim 2, characterized in that the energy analyzers (30, 30′, 30″; 40, 40′, 40″) are built with different dimensions. 15. Energy filter according to claim 2, characterized in that the energy analyzers are spherical sectors (30′, 40′), hemispherical analyzers (30, 40), or cylindrical analyzers (30″, 40″). 16. Energy filter according to claim 2, characterized in that the energy-dispersive planes (33, 43) of the hemispherical analyzers (30, 40) are rotated around the axis (200) of the transfer lens device (20) by the angle β=180°, so that the beam path has a the shape of an “S”. 17. Energy filter according to claim 2, characterized in that the transfer lens device (20) comprises at least one electrostatic tube lens (21, 22). 18. Energy filter according to claim 2, characterized in that the transfer lens device (20′) comprises at least one magnetic lens. 19. Energy filter according claim 2, characterized in that the transfer lens device (20) comprises at least one multipole lens (121, 122). 20. Energy filter according to claim 2, characterized in that the transfer lens device (20) has at least two lenses (21, 21′) and (22, 22′), and in that the exit plane (5) of the first energy analyzer (30, 30′, 30″) is located at the focal point of the first lens (21, 21′) and the entrance plane (6) of the second energy analyzer (40, 40′, 40″) is located at the focal point of the second lens (22, 22′), where the distance between the two lenses is 2F, where F stands for the focal distance of the lenses (21, 22, 21′, 22′).
The invention pertains to an image-generating energy filter for electrically charged particles such as electrons and ions with at least two toroidal energy analyzers arranged in a row, where at least one energy analyzer has a diaphragm in its entrance plane and another diaphragm in its exit plane. The invention also pertains to the use of these image-generating energy filters. The diaphragms in the entrance and exit planes can be slit diaphragms or circular diaphragms perpendicular to the associated energy-dispersive plane. The term “energy filter” is understood to mean preferably an imaging or image-generating energy filter. The use of imaging filters is especially advantageous when the image fields being processed in parallel contain more than 100×100 pixels. The recording times are then much shorter than those of a spectrometer, which scans the sample sequentially. Energy filters are used in, for example, photoelectron spectroscopy, which is one of the most important methods of the quantitative elementary analysis of surfaces. Measuring the energy distribution of photoelectrons with high local resolution is called spectromicroscopy. There are essentially two different methods which can be used to achieve a high degree of local resolution. In the first variant, the sample is scanned by a focused photon beam, and the energies of the photoelectrons coming from the individual emission spots thus defined are analyzed. In the second variant, the photon beam is focused just long enough to illuminate the visual range of the objective lens. Electron-optical means are then used to produce a magnified image of the intensity distribution of the generated photoelectrons. To derive a map of the distribution of the elements or of the chemical bonds, the kinetic energies of the photoelectrons must be analyzed. Various techniques have been developed to accomplish this in transmission-electron microscopy. Here, too, there are essentially two different principles: There are microscopes which use all of the electrons to generate an image. A small percentage of the electrons pass through an energy analyzer to generate a spectrum of a portion of the image. In another part of the microscope, only a narrow energy band is processed, but a complete image is transported through the energy analyzer. The electrons are filtered by electrostatic or magnetic devices, which allow only the electrons with a certain energy to pass through. The intensity of the resulting beam reflects the concentration of a chemical component present on the surface of the sample. In this method, it is important for the local resolution not to deteriorate as the beam passes through the monochromator. Several different energy analyzers have been developed to perform this imaging function. Because of its good transmission and energy resolution, the hemispherical analyzer has become widely accepted in commercial devices for energy analysis not requiring image quality. The possible imaging properties of electrostatic energy analyzers were studied many years ago on the basis of analyzers with general toroidal fields (B. Wannberg, G. Engdahl, A Skollermo: Imaging properties of electrostatic energy analyzers with toroidal fields, J. Electron Spectr. Rel. Phenomen. 9 (1976), pp. 111-127). For a toroidal potential, the radius of curvature in a first direction is different from that in a second direction perpendicular to the first. A spherical capacitor with a ratio of 1 between the radii is included as a special case in this general description. A cylindrical capacitor is curved in only one direction, and the ratio between its radii is zero. Some spectrometers make it possible to adjust the transition between the field forms in a continuously variable manner, as described, for example, in K. Jost: Novel Design of a spherical electron spectrometer, J. Phys. E.: Sci. Instr., 12, 1979, pp. 1006-1012. An electron microscope with an energy filter comprising a spherical analyzer of hemispherical design is known from EP 0,293,924 B1. To improve the imaging quality of the energy filter, a complicated lens system is set up in front of the entrance slit so that the arriving electron beams are as close to perpendicular as possible. For electrons which start at the mean path radius r0=x0, it should be true that α0=−α1, where α0 stands for the angle at the entrance to the energy filter and α1 for the angle at the exit. It is claimed that the entrance angles of these electrons are transferred exactly to the exit angles regardless of their energy. To take advantage of this property, a magnified image of the sample is placed not at the entrance slit of the analyzer but rather at the focal point of a lens, which is set up in front of the slit diaphragm of the analyzer. Thus the position of the image is transformed into angles. The entrance slit diaphragm is placed on the image side of the lens at the focal point. The exit slit of the analyzer selects the desired energy range. Another lens behind the analyzer reconstructs a now energy-filtered local image from the transmitted angle image. This can be magnified further and made visible on a screen with the help of an intensity amplifier, such as a microchannel plate. An electron spectrometer with a similar arrangement is described in EP 0,246,841 B1. A local resolution of down to 2.5 μm is obtained with this energy analyzer of the toroidal capacitor type, which has a lens system in front and another behind. It was overlooked, however, that the equation α1=−α0 is usually only a rough approximation. In Nucl. Instr. Methods A291 (1990), pp. 60-66, it is shown that the entrance and exit angles also depend on the entrance and exit locations. The entrance and exit angles will differ significantly from each other when the entrance and exit positions are different. It is then true that (tan α0):x0=−(tan α1):x1. The aberrations increase with the size of the magnified image field, that is, with the possible difference between x1 and x0. The following example can illustrate the magnitude of these defects: In the case of a visual field with a diameter of 4 mm, where, for example, x0=122 mm and x1=126 mm, and for an acceptance angle of α0=5°, we can calculate an exit angle of α1 of 5.16°. This is a 3% deviation from the incidence angle. In the case of a visual field with a radius of 100 μm, this results in an imaging error of 3 μm at the edge of the image field. Electrons with the same entrance position but different entrance angles also have different exit positions and different exit angles according to: tan ⁢ ⁢ α 1 = tan ⁢ ⁢ α 0 ⁡ ( 1 - 2 cos 2 ⁢ α 0 ) - 1 . This is described in, for example, T. Sagara et al., Resolution Improvements for hemispherical energy analyzers, Rev. Sci. Instr. 71, 2000, pp. 4201-4207. In another example, a hemispherical analyzer is used in a different operating mode. Here the potentials are selected so that the electrons travel along a hyperbolic path in a field which rises with the square of the-radius. U.S. Pat. No. 5,185,524 describes an electrostatic analyzer with spherical mirrors. The electrons pass into the inner sphere through slits and are brought back out through the inner sphere to a focal point by an opposing field. Both the object and the image are located inside the inner sphere. The disadvantages of this arrangement are described in Nucl. Instr. Methods 42, 1966, pp. 71-76. Large slits are present in the inner sphere at locations where the cross section of the beam is not small. Pieces of netting are attached at these points to ensure the required spherical potential. Only a portion of the field passes through the mesh, which limits the local resolving power. Each mesh opening represents a small diverging lens. Another disadvantage of using netting in the path of the beam is the production of secondary electrons, which leads to an increase in background noise and thus reduces the displayable contrast. The energy-selecting slit is located in the electrical field between the hemispheres and is therefore difficult to reach and adjust. The voltages which must be applied to the outer sphere are much higher than those required for the conventional hemispherical analyzer. In this design, as also in the preceding one, there are inherent aberrations, which can be attributed to the merely two-fold symmetry of the instrument's construction. DE 196 33 496 A1 describes a monochromator for electron microscopy with mirror symmetry. The design in the form of a Ω avoids second-order aberrations, and even some of the third-order aberrations disappear. One of the essential criteria for the selected design was the avoidance of an intermediate focus. The goal here is to make it possible to monochromatize a primary electron beam of small diameter and high current density. This requirement leads to a complicated mechanical solution. The design consists of eight toroidal sectors, which must be adjusted very precisely with respect to each other. The device is therefore very costly to make and very time-consuming to adjust. A similar mirror-symmetric arrangement of monochromators is selected in EP 0,470,299 A1. This arrangement also lacks an intermediate lens, but it does have a straight connecting tube. The energy-selecting slit is located in the plane of symmetry. No provisions are made for generating images in this case, either. An energy filter consisting of a complementary opposing pair of 90° sectors, which are arranged with respect to each other in such a way that they form an “S”, is known from U.S. Pat. No. 5,466,933. An aperture diaphragm is set up between the two sectors. With this energy filter, an image of the incoming parallel electron beam is produced at the exit from the sector arrangement. Although this arrangement using parallel electron beams does make it possible to obtain a high-contrast image at the exit of the energy filter, the intensity present at the exit is extremely low. The intensity can be increased by allowing electrons with an entrance angle ao not equal to zero to enter as well, but then the pixels are smeared and the contrast is reduced. WO 01/61,725 A1 describes an emission electron microscope, which contains an image-generating beam path consisting of an electron-optic imaging system, which subjects the electron beam to a parallel shift and analyzes its energy. It consists of two spherical energy analyzers with a lens inserted between them. This lens is located at the focal point of the two analyzers. An intermediate image of the sample or the angle image of the sample is placed at the center of this lens. Because the magnification of field lenses is positive, aberrations which arise on passage through the first deflector are not corrected. This document does not mention or discuss the correction of aberrations. DE 3,014,785 A1 describes a double monochromator for charged particles, which contains a delay lens in the form of slit diaphragms between the two monochromator subunits. The monochromator operates without loss of energy resolution at higher intensities than was possible in the past. No lens which might improve the imaging properties of the system is mentioned. Slit diaphragms are also described in U.S. Pat. No. 4,742,223. The imaging properties of the system are not discussed. U.S. Pat. No. 5,448,063 describes an image-generating, mirror-symmetric energy filter, which compensates only for 2nd and 3rd-order aberrations. This defect correction is achieved only by the use of complicated equipment, which includes additional hexapole fields. The task of the invention is therefore to create an image-generating energy filter with minimal aberration, which guarantees both a high-contrast image with high local resolution and high intensity at the exit. This task is accomplished by an energy filter which is characterized in that a transfer lens device with negative lateral magnification VL, negative angle magnification VW, image rotation by the angle γ=β−180°, and a telescopic beam path is placed between the exit plane of the first energy analyzer and the entrance plane of the second energy analyzer, where all the deflection angles φ of the transfer lens are the same, and where its energy-dispersive planes (33, 43) are rotated around the angle β with respect to each other. The energy analyzers are rotated around the axis of the transfer lens device. A “telescopic beam path” is understood to be a beam path in which the various clusters of parallel beams are converted to a single parallel beam cluster regardless of their angles of incidence. The angle γ stands for the degree to which the image is rotated from its inverse position. This inverse position is achieved by the use of, for example, electrostatic lenses. The advantage of the energy filter is that it is not mandatory to work with particle beams arriving in perpendicular fashion at the entrance plane of the first energy analyzer; that is, the entrance angle α0 can be allowed to be unequal to zero, which means that a high-contrast image of high intensity can be produced at the exit of the energy filter. The aberrations present at the exit from the first energy analyzer, especially the second-order aberrations, are transformed by the transfer lens device and projected onto the entrance plane of the second energy analyzer in such a way that that these aberrations are completely eliminated when the charged particles travel through the second energy analyzer. The image quality of the energy filter is limited essentially only by the quality of the transfer lens device. The transfer lens device is preferably designed so that, in the energy-dispersive plane, it projects the intermediate image ZB1 present at the exit plane of the first energy analyzer with a linear magnification of V L = ZB 2 ZB 1 < 0 and with an angular magnification of V W = α 2 α 1 < 0 , where ⁢ ⁢ V W ⁢ V L ⁢ E 2 E 1 = 1 , rotated around the angle γ=β−180°, onto the entrance plane of the second energy analyzer as an intermediate image of the size ZB2, where α1 is the exit angle of the charged particles from the exit plane of the first energy analyzer; α2 is the entrance angle to the entrance plane of the second energy analyzer; E1 is the kinetic energy of the charged particles in the exit plane of the first energy analyzer; E2 is the kinetic energy of the charged particles in the entrance plane of the second energy analyzer, and where the charged particles travel through a telescopic beam path in the transfer lens device. For an electrostatic transfer lens device, β=180° and VL and VW are negative. For a magnetic transfer lens device, VL and VW are also negative, but the image can be subject to rotation, which means that it is necessary to select β≅180°. The energy analyzers and the transfer lens device are preferably set up with point symmetric around the center Z of the transfer lens device. This means that the energy analyzers have the same construction dimensions and that VL=−1 and VW=−1. The energy analyzers can also have different construction dimensions, as a result of which an arrangement with quasi-radial symmetry is created, in which VW and VL are less than 0. VW=VL=−1 can be obtained by adjusting the radii and the pass energies appropriately to each other. Within the scope of the invention, the choice of the type of deflection fields used for the analyzers is essentially free. Magnetic fields, either permanent or generated by electrical current, can be used, but electrostatic fields are especially preferred. The toroidal energy analyzers are preferably sectors of a sphere or cylindrical analyzers, especially with a deflection angle of more than 90°. Hemispherical analyzers with deflection angles of φ=180° are especially preferred, because these have an especially high energy dispersion at their exit. In a spherical field, in which the potential energy of the particle is ˜1/r, the charged particles move along closed elliptical paths. All of the particles which start at one point, even though of different energies and even of different angles, reach their exact original position again after a circuit of 360°. As a result, there are no aberrations at the exit. In a closed spherical analyzer of this type, the two energy-dispersive planes of the two hemispheres would by definition enclose the angle β=0. After traveling 180°, the particles with different energies reach their maximum distance from each other. If an aperture which does not disturb the radial field is placed here, only the particles of the desired energy are allowed to pass through. Nevertheless, in a closed spherical analyzer of this type, there is no room to put an entrance lens and a detector, for example, or a transfer lens. In the case of two hemispherical analyzers which are arranged with respect to each other in such a way that their energy-dispersive planes are rotated around the angle β, the imaging properties of the transfer lens device makes it possible to retain the properties of a complete spherical analyzer, so that defect-free images will be obtained at the exit of the energy filter. The transfer lens device ensures that the paths are exact images of each other, the only difference being that the entrance point to the first hemispherical analyzer is separated in space from the exit point of the second hemispherical analyzer. The effect thus obtained is that of a spherical capacitor. It is known that non-relativistic particles travel along closed, periodic elliptical paths. The angles and positions are the same after a complete circuit. This is independent of the starting position, of the entrance angle, and of the energy of the charged particles. The energy-dispersive plane of the hemispherical analyzers is preferably rotated by an angle of β=180° around the axis of the transfer lens device, so that the beam path has the shape of an “S”. This arrangement offers the advantage that an especially simple transfer lens device can be used. For practical reasons, the angle β between the dispersion planes is preferably within the range between 5° and 355°, especially between 15° and 340°. The energy analyzers can be of different designs; if so, the design of the transfer lens device must be modified accordingly. In the case of different energy analyzers, e.g., different pass energies E1 and E2, the lateral magnification and the angular magnification must be adjusted to produce the desired intermediate image on the entrance plane of the second energy analyzer. In the design of the transfer lens arrangement, therefore, it is necessary to take in the account the Lagrange-Helmholtz equation ZB1*α*√{square root over (E1)}=const.=ZB2*α2*√{square root over (E2)}. From a cost standpoint, however, it is advantageous to use identical energy analyzers and to work with the same pass energies. In this case, the lateral magnification of the transfer lens device is VL=−1, and the angular magnification of the transfer lens device is VW=−1. The transfer lens device preferably comprises at least one electrostatic lens, especially an electrostatic tube lens, which is used especially in conjunction with two hemispherical analyzers with energy-dispersive planes which are preferably rotated with respect to each other by the angle of β=180°. The transfer lens device can comprise at least one magnetic lens. Magnetic lenses offer the advantage that they produce smaller aberrations than electrostatic lenses. They are therefore preferred in cases where, because the energy analyzers are rotated by the angle β from each other, the intermediate image ZB1 must also be projected with a rotation around the angle γ=β−180°. The transfer lens device preferably has at least two lenses. It is advantageous to locate the exit plane of the first energy analyzer at the focal point of the first lens and to locate the entrance plane of the second energy analyzer at the focal point of the second lens, where 2F stands for the distance between the two lenses and F stands for the focal distance of the two lenses. The transfer lens device can also have at least one electrostatic or magnetic multipole lens. Multipole lenses offer the advantage that they can provide an image without any spherical aberrations. A multipole lens is set up between the two energy analyzers in such a way that a radially symmetric arrangement is obtained. According to one possible use of the energy filter, the filter is placed in the imaging beam path of an image-generating electron-optic system. The task of the energy filter is to select electrons of certain energies from the beam path through appropriate adjustment of the diaphragms of the energy filter. It is irrelevant whether an intermediate image of the sample to be studied, the Fourier-transformed intermediate image, or some other intensity distribution of the imaging beam path is sent to the entrance slit of the energy analyzer. The energies of these charged particles and energy bandwidth of the detected beam path can be determined and varied by changing the energy window. One of the preferred uses of the energy filter is in electron microscopy. Here the energy filter is used to produce an image of the electrons emitted and back-scattered by an object. These electrons have by nature a wide energy spectrum. The contrast can be improved by using electrons from a narrow energy band. By selectively setting the energy window, a succession of specific signals can be selected out and amplified, while the others can be attenuated. It is therefore possible to emphasize a certain set of data. Another preferred use of the energy filter is in time-resolved measuring instruments. The advantage of the energy filter is that even differences in the times of flight which occur in the first energy analyzer are eliminated by the transfer lens device and passage through the second energy analyzer. Exemplary embodiments of the invention are explained in greater detail below on the basis of the drawings: FIG. 1 shows a schematic diagram of an energy filter with two hemispherical analyzers; FIG. 2 shows a schematic diagram of a transfer lens device; FIG. 3 shows an embodiment of the arrangement shown in FIG. 1; FIG. 4 shows a perspective view of the embodiment according to FIG. 3; FIG. 5 shows another embodiment, which differs from that shown in FIG. 4 by a different angle of rotation; FIG. 6 shows a schematic diagram of another embodiment in which spherical sectors are used as energy analyzers; FIG. 7 shows another embodiment with a total of four toroidal sectors; FIG. 8 shows an energy filter with cylindrical analyzers; FIG. 9 shows a transfer lens device with multipole lenses; and FIG. 10 shows a transfer lens device with magnetic lenses. FIG. 1 shows a schematic cross-sectional diagram of an energy filter, which has two hemispherical analyzers 30 and 40, between which a transfer lens device 20 is located. The two energy analyzers 30, 40 together with the transfer lens device 20 are set up in such a way that the beam path lies in a plane and has the shape of an “S”. The overall arrangement has radial symmetry with respect to the center Z of the transfer lens device 20; the radial symmetry is two-fold. The electrons curve to the left in the first energy analyzer 30, and after they have passed through the transfer lens device 20, they curve to right in the second energy analyzer 40. This means that the two energy-dispersive planes 33, 43 of the two energy analyzers are rotated by the angle β=−180° with respect to each other (see FIG. 4). FIG. 1 shows only the center beam paths 4 and 7 of the electrons in the first and second energy analyzers. The energy filter has image-generating properties while avoiding aberrations of the second and higher orders. The surface 1′ of the sample 1 is a certain distance g from the first lens system 2, which forms an image of the electrons emerging from the surface 1′ on the entrance plane 3 of the first hemispherical analyzer 30. The object distance g can be the same as the focal distance of the lens system 2, so that the image distance b is approximately equal to infinity. In this case, the entrance plane 3 of the first energy analyzer 30 is preferably located in the image-side focal plane of the lens system 2. In the entrance plane 3 there is a first energy-defining slit diaphragm 25, which is perpendicular to the plane of the drawing and has the width B1 (see also FIG. 3). The hemispherical analyzer 30 forms an image of the electrons entering through the slit diaphragm 25 with aberrations in the exit plane 5, where a second slit diaphragm 26 with the width B2 is located. Because the electrons enter the slit diaphragm 25 in the entrance plane 3 at various angles α0, they also exit at different exit angles α1 upon leaving the deflection field of the first energy analyzer. The second slit diaphragm 26 is perpendicular to the plane of the drawing in which the linear focus of the astigmatic intermediate image ZB1 23 lies. The energy dispersion occurs in the plane of the drawing. This dispersion is defined as the deviation from the central beam path 4 by a value which is proportional to the energy deviation. By changing the width B2 of the slit (see also FIG. 3), it is possible to adjust or to change selectively the energy bandwidth of the electrons let through by the slit diaphragm 26. As a result, the only electrons which reach the intermediate image ZB1 23 are those which lie within this energy bandwidth. The electron beam is monochromatic as a result. A transfer lens device 20 is set up behind this exit plane 5. This device consists of two identical converging lenses 21 and 22 and forms an image of the first intermediate image 23 produced in the exit plane 5 as an inverted second intermediate image ZB2 24, that is, VL=−1, at the entrance plane 6 of the second energy analyzer 40. The transfer lens device 20 not only inverts the intermediate image ZB1 23 on the entrance plane 6 but also inverts the angles, so that the entrance angles α2 in the entrance plane 6 of the second energy analyzer 40 are described by α2=−σ1. The aberrations are eliminated in the second energy analyzer 40 as a result of the inversion of the astigmatism of the intermediate image ZB1 23 in conjunction with the inversion of the path curvature present in the first energy analyzer 30. An energy-filtered, stigmatic image 29, which can be projected by the lens system 9 onto a detector 10, is thus created in the exit plane 8. In this embodiment, the second energy analyzer 40 also has a slit diaphragm 27 of width B3 in the entrance plane 6 and a slit diaphragm 28 of with B4 in the exit plane 8. If the distance of the surface 1′ of the sample 1 or of a magnified or reduced image is equal to the focal distance of the lens system 2, the distance of the lens system 9 from the exit plane 8 will also be equal to the focal distance, and the distance to the detector 10 will be equal to the focal distance of the lens system 9. Diffraction images instead of real images are then present at the entrance and exit planes of the two energy analyzers 30, 40. If the lens systems 2 and 9 are operated asymmetrically, it is possible to use the energy filter to obtain a diffraction image of sample 1 without any aberrations of the second and higher orders. It is said that the lens systems are operated “asymmetrically” when either the lens system 2 projects the surface of the sample onto the entrance plane 3 and the lens system 9 is adjusted in such a way that the intermediate image 29 is situated at the focal distance of the lens system 9, or conversely the lens system 2 is adjusted in such a way that the sample surface (or its intermediate image) lies in the focal plane of the lens and simultaneously the lens system 9 projects the plane 8 sharply onto the detector 10. The diffraction image of the sample is then projected by the lens system 2 onto the entrance plane 3. This diffraction image is energy-filtered and ultimately arrives at the exit plane 8. From there it is projected by the lens system 9 onto the detector 10. FIG. 2 shows a schematic diagram of the beam path in the transfer lens device 20. The two identical electrostatic converging lenses 21, 22 have an F-2F-F arrangement, where F is the focal distance of the lenses 21, 22. On the basis of this lens arrangement, the first intermediate image ZB1 23 in the exit plane 5 with the lateral magnification VL=−1 and the beams with the angular magnification VW=−1 are projected onto the entrance plane 6 as a second intermediate image ZB2 24. The beam path is radially symmetric and telescopic. When other types of lenses are used, e.g., electron-optic cylindrical lenses, the angular and lateral magnifications can also be +1 in the non-dispersive plane. FIG. 3 shows a possible embodiment of the arrangement illustrated schematically FIG. 1 with three possible electron paths E0, E1, and E2. A cross section through the energy-dispersive planes is shown. The electrons start from the surface 1′ of the sample 1, pass through the slit diaphragm 25 of width B1, and enter the first hemispherical analyzer 30, in which an electrostatic deflecting field is applied between the inner shell 31 and the outer shell 32. When the electrons enter the slit diaphragm 25 at a right angle, as they do at point X0, they describe a path E0, which describes a semicircle in each of the first and second hemispherical analyzers. Because the path E0 meets the axis 200 of the transfer lens device 20, the electrons are also projected onto point X0 of the slit diaphragm 27 of the second hemispherical analyzer 40, and the path along which they travel in the second hemispherical analyzer is radially symmetric to point Z. The electrons on path E1 start at point X1 of the slit diaphragm 25 of the first hemispherical analyzer 30 with a different energy and a different entrance angle α0,1, whereas the electrons of path E2 start at point X1 with the entrance angle −α0,2. The electrons are deflected to point X2 in the second slit diaphragm 26, describing elliptical paths in both cases. The exit angles are α1,1 and α1,2, where |α1,1|=|α1,2| was selected in this example. The pixel X0 of the first intermediate image ZB1 in the slit diaphragm 26 is projected with the lateral magnification −1 and with the angular magnification −1 onto the plane 6 at point X3 as a pixel of the second intermediate image ZB2. For the angles we therefore have α1,2=−α2,2 and α1,1=−α2,1. In the second energy analyzer 40, an equally intense electrostatic deflecting field is applied between the inner shell 41 and the outer shell 42, so that the electron paths E1 and E2 have elliptical courses which correspond to the elliptical paths in the first energy analyzer 30. The electrons exit at point X4 at the angles α3.1 and α3.2, which correspond in turn to the angles α0.1 and α0.2. The deviations of the angles are α1.1 and α1.2 are compensated by the second pass, i.e., by the pass through the energy analyzer 40. It is also true with respect to the point X4 that X4=X1. An energy-filtered image of the sample 1 is thus obtained without aberration in the plane of the slit diaphragm 28. FIG. 4 shows a perspective view of the embodiment shown in FIG. 3. The energy-dispersive planes 33 and 43 and the slit diaphragms 25, 26, 27, and 28 in the hemispherical analyzers 30, 40 are illustrated. The second hemispherical analyzer 40 is rotated by the angle β=180° around the axis 200 of the transfer lens device 20, which axis passes through the slit diaphragm 27. FIG. 5 shows another embodiment, in which the second hemispherical analyzer 40 is rotated by the angle of only β=90° around the axis 200 passing through the slit diaphragm 27. FIG. 6 shows an embodiment corresponding to that of FIG. 3, where, instead of the hemispherical analyzers 20, 30 [Sic; →30, 40—Tra], spherical sectors 20′, 30′ [Sic; →30′, 40′—Tra] are used, which have inner shells 31′, 41′ and outer shells 32′, 42′ with deflection angles of φ≦180°. The arrangement of the diaphragms 25, 26, 27 differs from the arrangement according to FIG. 3 in that they are not located in the entrance and exit planes of the spherical sectors. This embodiment also shows two-fold radial symmetry with respect to point Z. FIG. 7 shows the arrangement according to FIG. 6 supplemented by two additional toroid sectors 50a, 50b. The toroid sector 50a is placed in front of the first spherical sector 30′, and the toroid sector 50b is placed behind the second spherical sector 40′. These additional toroid sectors 50a, 50b serve to correct higher-order aberrations. FIG. 8 shows an energy filter consisting of two cylindrical analyzers 30′, 40′ [Sic; →30″, 40″—Tra] with inner shells 31″, 41″ and outer shells 32″, 42″ and a transfer lens device 20. The axis 200 of the transfer lens system 20 is not collinear to the cylinder axes 34, 44 but extends instead in the direction of the central paths 4′, 7′ through the cylindrical analyzers, which form an angle of 42.3° with the cylinder axes 34, 44. FIGS. 9a and 9b show a transfer lens device 20 which avoids both spherical aberration and the coma error. This can be achieved by combining electrical or magnetic round lenses (21, 22) with two sextupole lenses 121, 122. The axis 200 of the transfer lens device extends in direction z. FIG. 9a shows a cross section through a sextupole segment perpendicular to its axis. The force F on a particle changes its direction between two adjacent electrodes, the voltages U and −U relative to the axis potential being applied to alternate electrodes. FIG. 9b shows schematically the course of two electrons a certain distance away from the axis. At the point of entrance, the axes of these electrons are parallel in the xy cross section. The broken lines show the paths observed when the sextupoles 121 and 122 are turned off, and the solid lines show the path observed when they are turned on. The path near the axis is affected to only a slight extent by the sextupoles. The sextupoles lie in the exit and entrance planes 5, 6 of the energy analyzers. FIG. 10 shows a schematic diagram of a magnetic transfer lens device 20 [Sic →20′—Tra] analogous to the electrostatic lenses of FIG. 2. The magnetic fields of the lenses 22′ and 21′ are generated by coils. The essential difference between this and an electrostatic transfer lens device is an additional rotation of the image by the angle γ, where γ is based on the position of the image at V L = - ZB 2 ZB 1 . List of Reference Symbols 1 sample 1′ surface of sample 2 first lens system 3 entrance plane 4, 4′ central beam bath in the first energy analyzer 5 exit plane 6 entrance plane 7, 7′ central beam path in the second energy analyzer 8 exit plane 9 lens system 10 detector 20, 20′ transfer lens device 21, 21′ first transfer lens 22, 22′ second transfer lens 23 first intermediate image 24 second intermediate image 25 first slit diaphragm 26 second slit diaphragm 27 third slit diaphragm 28 fourth slit diaphragm 29 image 30, 30′, 30″ first toroidal energy analyzer 31, 31′, 32″ inner shell 32, 32′, 32″ outer shell 33 energy-dispersive plane 34 axis 40, 40′, 40″ second toroidal energy analyzer 41, 41′, 41″ outer shell 43 energy-dispersive plane 44 axis 50a, 50b toroid sector 121 sextupole lens 122 sextupole lens 200 axis of the transfer lens device
20050503
20070731
20060126
68745.0
H01J4900
0
WELLS, NIKITA
ENERGY FILTER IMAGE GENERATOR FOR ELECTRICALLY CHARGED PARTICLES AND THE USE THEREOF
SMALL
0
ACCEPTED
H01J
2,005
10,533,675
ACCEPTED
Visualizing system, visualizing method, and visualizing program
A vector field (70) including its local three-dimensional attribute is substantially visualized on a two-dimensional field of view in an intuitionally visible way (p5, p8). For the visualization, the vector field (70) is mapped onto a three-dimensional coordinate space (80) to produce corresponding coordinate point sequences (p1), the degree of elevation (A) in a local area of a plane in which the coordinate point sequences are connected (p2) is determined, the degree of depression (C) in the local area is determined (p3), the degree of elevation/depression (B) in the local area is determined by weight-combining the degree of elevation (A) and the degree of depression (C) (p4), the coordinate space (80) is mapped onto a two-dimensional plane (90), and gray-scale display (F) corresponding to the degree of elevation/depression is conducted on the area of the two-dimensional plane (90) corresponding to the local area (p5).
1. A visualization processing system (VPS1; VPS2) characterized by a first operator (61) for mapping a vector field (70) in a three-dimensional coordinate space (80) to obtain a corresponding sequence of coordinate points, a second operator (62) for determining an elevation degree (A) in a local region of a plane connecting the sequence of coordinate points, a third operator (63) for determining a depression degree (C) in the local region of the plane connecting the sequence of coordinate points, a fourth operator (64) for synthesizing the elevation degree (A) and the depression degree (C) in a weighting manner to determine an elevation-depression degree (B) in the local region of the plane connecting the sequence of coordinate points, and a fifth operator (65) for mapping the coordinate space (80) on a two-dimensional plane (90), providing a tone indication (F) commensurate with the elevation-depression degree to a region on the two-dimensional plane corresponding to the local region of the plane connecting the sequence of coordinate points. 2. The visualization processing system (VPS1; VPS2) as claimed in claim 1, characterized in that the elevation degree (B) is defined in terms of a solid angle at one side in the local region of the plane connecting the sequence of coordinate points. 3. The visualization processing system (VPS1; VPS2) as claimed in claim 2, characterized in that the depression degree (C) is defined in terms of a solid angle at the other side in the local region of the plane connecting the sequence of coordinate points. 4. The visualization processing system (VPS1; VPS2) as claimed in claim 1, further characterized by a sixth operator (66) for determining an inclination distribution (D) of the plane connecting the sequence of coordinate points, and the fifth operator (65) provideing on the two-dimensional plane a color-toned indication (F) of the inclination distribution (D), and for a brightness thereof, give the tone indication (F). 5. The visualization processing system (VPS1; VPS2) as claimed in claim 4, characterized in that the fifth operator (65) provides the color-toned indication (F) of the inclination distribution (D) in reddish colors. 6. The visualization processing system (VPS1; VPS2) as claimed in claim 1, further characterized by a seventh operator (67) for connecting, among the sequence of coordinate points, those coordinate points equivalent of an attribute in the vector field (70) to obtain an attribute isopleth line (I), and an eighth operator (68) for mapping the attribute isopleth line (I) on the two-dimensional plane (90) given the tone indication (F). 7. A visualization processing system (VPS1; VPS2) characterized by a first means (61) for mapping a vector field (70) in a three-dimensional coordinate space (80) to obtain a corresponding sequence of coordinate points, a second means (62) for determining an elevation degree (A) in a local region of a plane connecting the sequence of coordinate points, a third means (63) for determining a depression degree (C) in the local region of the plane connecting the sequence of coordinate points, a fourth means (64) for synthesizing the elevation degree (A) and the depression degree (C) in a weighting manner to determine an elevation-depression degree (B) in the local region of the plane connecting the sequence of coordinate points, and a fifth means (65) for mapping the coordinate space (80) on a two-dimensional plane (90), providing a tone indication (F) commensurate with the elevation-depression degree (B) to a region on the two-dimensional plane (90) corresponding to the local region of the plane connecting the sequence of coordinate points. 8. A visualization processing method characterized by a first step (P1) of mapping a vector field (70) in a three-dimensional coordinate space (80) to obtain a corresponding sequence of coordinate points, a second step (P2) of determining an elevation degree (A) in a local region of a plane connecting the sequence of coordinate points, a third step (P3) of determining a depression degree (C) in the local region of the plane connecting the sequence of coordinate points, a fourth step (P4) of synthesizing the elevation degree (A) and the depression degree (C) in a weighting manner to determine an elevation-depression degree (B) in the local region of the plane connecting the sequence of coordinate points, and a fifth step (P5) of mapping the coordinate space (80) on a two-dimensional plane (90), providing a tone indication (F) of the elevation-depression degree (B) to a region on the two-dimensional plane (90) corresponding to the local region of the plane connecting the sequence of coordinate points. 9. A visualization processing program characterized in that the program is functionable to have a computer execute a first process (P1) for mapping a vector field (70) in a three-dimensional coordinate space (80) to obtain a corresponding sequence of coordinate points, a second process (P2) for determining an elevation degree (A) in a local region of a plane connecting the sequence of coordinate points, a third process (P3) for determining a depression degree (C) in the local region of the plane connecting the sequence of coordinate points, a fourth process (P4) for synthesizing the elevation degree (A) and the depression degree (C) in a weighting manner to determine an elevation-depression degree (B) in the local region of the plane connecting the sequence of coordinate points, and a fifth process (P5) for mapping the coordinate space (80) on a two-dimensional plane (90), providing a tone indication (F) of the elevation-depression degree (B) to a region on the two-dimensional plane (90) corresponding to the local region of the plane connecting the sequence of coordinate points. 10. A visualization processing system (VPS1) for generating a gradient reddening stereoscopic image, characterized by a database having stored therein a multiplicity of digital data provided with three-dimensional coordinates, and a computer comprising a means for generating a stereoscopic contour image having contour lines connecting three-dimensional coordinates of digital data having identical Z values, a means for meshing intervals between contour lines, a means for allocating focused points to meshes, determining an average of differences in Z value between a respective mesh given a focused point and neighboring meshes, a means for generating a gradient reddening image having assigned to the mesh given the focused point a red tone commensurate with a degree in magnitude of a difference of the average, a means for generating a gray scale image having a varied brightness depending on a ridge-valley shaping tendency of the mesh given the focused point, and a means for performing a multiplying synthesis of the gradient reddening image and the gray scale image, to display on a screen a gradient reddening stereoscopic image representing degrees of gradient and degrees of height in color. 11. A visualization processing method for generating a gradient reddening stereoscopic image, characterized by a step of generating a stereoscopic contour image having contour lines connecting three-dimensional coordinates of digital data having identical Z values, a step of meshing intervals between contour lines, a step of allocating focused points to meshes, determining an average of differences in Z value between a respective mesh given a focused point and neighboring meshes, a step of generating a gradient reddening image having assigned to the mesh given the focused point a red tone commensurate with a degree in magnitude of a difference of the average, a step of generating a gray scale image having a varied brightness depending on a ridge-valley shaping tendency of the mesh given the focused point, and a step of performing a multiplying synthesis of the gradient reddening image and the gray scale image, to display on a screen a gradient reddening stereoscopic image representing degrees of gradient and degrees of height in color. 12. A visualization processing program for generating a gradient reddening stereoscopic image, characterized in that the program is adapted to have a computer function as a means for reading a multiplicity of digital data provided with three-dimensional coordinates, a means for generating a stereoscopic contour image having contour lines connecting three-dimensional coordinates of digital data having identical Z values, a means for meshing intervals between contour lines, a means for allocating focused points to meshes, determining an average of differences in Z value between a respective mesh given a focused point and neighboring meshes, a means for generating a gradient reddening image having assigned to the mesh given the focused point a red tone commensurate with a degree in magnitude of a difference of the average, a means for generating a gray scale image having a varied brightness depending on a ridge-valley shaping tendency of the mesh given the focused point, and a means for performing a multiplying synthesis of the gradient reddening image and the gray scale image, to display on a screen a gradient reddening stereoscopic image representing degrees of gradient and degrees of height in color.
FIELD OF ART The present invention relates to a visualization processing system, a visualization processing method, and a visualization processing program, and particularly, to a visualization processing system, a visualization processing method, and a visualization processing program which are adapted for visualization, in a manner that allows an intuitive visual perception (e.g. a manner that gives a visually solid appearance), on a substantially two-dimensional field of view (e.g. a flat or curved plane), of a vector field (e.g. a set of topographic data representing an earth's surface) including a distribution of three-dimensional vectors (e.g. stereoscopic topographic data) that have substantially three components indicated together, or three-dimensional vectors of specified three components of multi-dimensional vectors (e.g. such data that have stereoscopic topographic data and geologic data together). The present invention further relates to a visualization processing system, a visualization processing method, and a visualization processing program which are adapted for an expression using a color tone, in place of contour lines, of altitude and inclination of concavo-convex part of terrain based on a great amount of digital image data represented by three-dimensional coordinates, to thereby generate a gradient-reddening stereoscopic image that can provide a visually solid appearance. BACKGROUND ART For a visualization of three-dimensional vector field on a two-dimensional plane, many attempts have been made since ancient times. Most typically, there has been known a method of converting two components into coordinate values, and plotting an intersection thereof on a two-dimensional plane, providing each intersection with a note of attribute of the remaining third component (e.g. a town guide map), which however is unable to afford an easy grasp of a difference of the third component. In this respect, there has been made also a graphic expression of an attributive feature of the third component (e.g. a town street guide map), which is still bound to the localization of information, and has covered successive changes in the attribute. To this point, there has been generally employed a method of entering a continuous feature of two components (e.g. an outline such as of a coast, river, lake, or marsh) and attribute isopleth lines of the third component (e.g. contour lines), which is yet difficult of the intuitive visible perception of an attribute variation. A topographic map is now supposed for more specific discussion. In a mesh measurement by an analyzing mapper, the terrain is lattice-like divided, having altitude values given thereto, to provide a DEM (Digital Elevation Model) data. This is processed in a computer for calculation of parameters concerning, e.g, the terrain's heights, inclination angles, slope azimuths, laplacians, valley divisions, water systems, etc., allowing for a distribution of calculation results over a plane to be converted into a corresponding image. In an airborne laser measurement, available data contain more detail information. All the data is not involved in a topographic map. For example, information on the height and inclilnation is extracted, to be entered as contour lines in the map. It however is uneasy to imagine a stereoscopic terrin therefrom. There is also an image provided with a stereoscopic appearance, as a hill shade lighted from a diagonal upside, which has an emphasized inclination in a particular direction. In this concern, there is a gray scale (tone of brightness) or a rainbow color (tone of hue) indicated in a terrin image, which allows an intuitive visual perception of termin's geometrical features and their distribution, and is useful, but unable to give an effective visually solid appearance. Reference-1: “Japanese Patent Application Laying-Open Publication 146902” There is also an image processed by using either an avobeground opening or an underground opening as a mega filter, which allows a capture of terrain's features in a relatively large district, but feels something missing in visually solid appearance, particularly in local appearances to be visually solid. Reference-2: “Iwate University thesis: Indication of terrain features by an opening, the photogrammetry and remote sensing, by Ryuuzou Yokoyama, Michio Shirasawa, and Yutaka Kikuchi (1999), vo. 38, no. 4, 2&34”. Description is now made of conventional methods of providing a topographic map with a visually solid appearance. (Stereo-Matching Image, Three-Dimensional Image) Basically, an image that makes use of a parallax, employing two photographs. There are varieties of methods, such as cases by a red/blue filter, a polarizing filter, a diffraction grating, or a lenticurar lenz, any of which however has to be seen in a particular direction, and needs a glass. Moreover, expansion as well as scaling down is difficult. The three-dimensional image is an image looked down in a particular direction, which is inadequate to read, as having a portion unseen if in shadow, looking small if distant, and lacking resolution if close. Moreover, time is necessary for image creation. (Indication by Contour Lines) The contour line is suitable to the indication of terrain in mountainous districts, but for steep inclinations (e.g. a sudden cliff part) or gentle slopes or flat lands (a plain part), the reading of topographic features takes a time due to an extreme convergence or divergence of contour lines having stepwise allotted heights. The angle of inclination as well as the orientation is to be guessed from the variation of spacing between contour lines. Hence, being unfit in a simple expansion or scaling, it needs a remake in some case. Crowded contour lines have their gaps lost, and are substituted by a legend of cliff. This task is complex, and constitutes an impediment to vectorization. Small irregularity cannot be read unless a height is given to each contour line. (Set of Image Data having Two-Dimensional Altitude Values) In a mapping work by aerial photographic measurement, the acquisition of information is directly made of contour lines as connected particular altitudes, having no altitudes given between contour lines. In the case of mesh measurement by an analyzing mapper or airborne laser measurement, the DEM data is acquired, and based thereon a two-dimensional distribution of contour lines is determined, whereby, although contour lines are smoothed as necessary, information else than finally contained in contour lines, e.g. information of a three-dimensional geometry between contour lines, is left unused. This invention was made in view of the foregoing points. It therefore is an object of the invention to provide a visualization processing system, a visualization processing method, and a visualization processing program, which are adapted to visualize a vector field, with local solid attributes thereof inclusive, on a substantially two-dimensional field of view, in a manner that allows an intuitive visible perception. It also is an object of the invention to provide a visualization processing system, a visualization processing method, and a visualization processing program, which are adapted to generate a gradient reddening stereoscopic image that allows at a glance a stereoscopic grasp of terrain's heights and inclination degrees. SUMMARY OF INVENTION To achieve the object, a visualization processing system according to the invention is characterized by a first operator for mapping a vector field in a three-dimensional coordinate space to obtain a corresponding sequence of coordinate points, a second operator for determining an elevation degree in a local region of a plane connecting the sequence of coordinate points, a third operator for determining a depression degree in the local region of the plane connecting the sequence of coordinate points, a fourth operator for synthesizing the elevation degree and the depression degree in a weighting manner to determine an elevation-depression degree in the local region of the plane connecting the sequence of coordinate points, and a fifth operator for mapping the coordinate space on a two-dimensional plane, providing a tone indication commensurate with the elevation-depression degree to a region on the two-dimensional plane corresponding to a divided region of the plane connecting the sequence of coordinate points. According to the invention, a vector field is mapped in a three-dimensional coordinate space, obtaining a corresponding sequence of coordinate points, and there are determined in a local region of a plane connecting the sequence of coordinate points an elevation degree, that is a rising tendency (e.g. a ridge shaping tendency in a topographic map), and a depression degree, that is a sinking tendency (e.g. a valley shaping tendency in a topographic map), which are synthesized in an end-fit weighting manner (in a broad sense inclusive of the difference), determining in the local region an elevation-depression degree, that is a rising and sinking tendency (e.g. a ridge-valley shaping tendency in a topographic map), which is tone-indicated in a corresponding region on a two-dimensional plane, so that the vector field can be visualized, with its local solid attributes inclusive, on a substantially two-dimensional plane in a manner that allows an intuitive visible perception. The elevation degree may preferably be defined in terms of a solid angle at one side in the local region of the plane connecting the sequence of coordinate points. The depression degree may preferably be defined in terms of a solid angle at the other side in the local region of the plane connecting the sequence of coordinate points. The visualization processing system may preferably further comprise a sixth operator for determining an inclination distribution of the plane connecting the sequence of coordinate points, and the fifth operator may preferably provide on the two-dimensional plane a color-toned indication, i.e. chroma saturation indication, of the inclination distribution (more preferably, in reddish colors), and for a brightness thereof, give the tone indication. The visualization processing system may preferably further comprise a seventh operator for connecting, among the sequence of coordinate points, those coordinate points equivalent of an attribute in the vector field to obtain an attribute isopleth line, and an eighth operator for mapping the attribute isopleth line on the two-dimensional plane given the tone indication. A visualization processing method according to the invention is characterized by a first step of mapping a vector field in a three-dimensional coordinate space to obtain a corresponding sequence of coordinate points, a second step of determining an elevation degree in a local region of a plane connecting the sequence of coordinate points, a third step of determining a depression degree in the local region of the plane connecting the sequence of coordinate points, a fourth step of synthesizing the elevation degree and the depression degree in a weighting manner to determine an elevation-depression degree in the local region of the plane connecting the sequence of coordinate points, and a fifth step of mapping the coordinate space on a two-dimensional plane, providing a tone indication of the elevation-depression degree to a region on the two-dimensional plane corresponding to a divided region of the plane connecting the sequence of coordinate points. A visualization processing program according to the invention is characterized in that the program is functionable to have a computer execute a first process for mapping a vector field in a three-dimensional coordinate space to obtain a corresponding sequence of coordinate points, a second process for determining an elevation degree in a local region of a plane connecting the sequence of coordinate points, a third process for determining a depression degree in the local region of the plane connecting the sequence of coordinate points, a fourth process for synthesizing the elevation degree and the depression degree in a weighting manner to determine an elevation-depression degree in the local region of the plane connecting the sequence of coordinate points, and a fifth process for mapping the coordinate space on a two-dimensional plane, providing a tone indication of the elevation-depression degree to a region on the two-dimensional plane corresponding to a divided region of the plane connecting the sequence of coordinate points. According to the invention, a visualization processing system for generating a gradient reddening stereoscopic image is characterized by a database having stored therein a multiplicity of digital data provided with three-dimensional coordinates, and a computer which comprises a means for generating a stereoscopic contour image having contour lines connecting three-dimensional coordinates of digital data having identical Z values, a means for meshing intervals between contour lines, a means for allocating focused points to meshes, determining an average of differences in Z value between a respective mesh given a focused point and neighboring meshes, a means for generating a gradient reddening image having assigned to the mesh given the focused point a red tone commensurate with a degree in magnitude of a difference of the average, a means for generating a gray scale image having a varied brightness depending on a ridge-valley shaping tendency of the mesh given the focused point, and a means for performing a multiplying synthesis of the gradient reddening image and the gray scale image, to display on a screen a gradient reddening stereoscopic image representing degrees of gradient and degrees of height in color. According to the invention, a visualization processing method for generating a gradient reddening stereoscopic image is characterized by a step of generating a stereoscopic contour image having contour lines connecting three-dimensional coordinates of digital data having identical Z values, a step of meshing intervals between contour lines, a step of allocating focused points to meshes, determining an average of differences in Z value between a respective mesh given a focused point and neighboring meshes, a step of generating a gradient reddening image having assigned to the mesh given the focused point a red tone commensurate with a degree in magnitude of a difference of the average, a step of generating a gray scale image having a varied brightness depending on a ridge-valley shaping tendency of the mesh given the focused point, and a step of performing a multiplying synthesis of the gradient reddening image and the gray scale image, to display on a screen a gradient reddening stereoscopic image representing degrees of gradient and degrees of height in color. According to the invention, a visualization processing program for generating a gradient reddening stereoscopic image is characterized in that the program is adapted to have a computer function as a means for reading a multiplicity of digital data provided with three-dimensional coordinates, a means for generating a stereoscopic contour image having contour lines connecting three-dimensional coordinates of digital data having identical Z values, a means for meshing intervals between contour lines, a means for allocating focused points to meshes, determining an average of differences in Z value between a respective mesh given a focused point and neighboring meshes, a means for generating a gradient reddening image having assigned to the mesh given the focused point a red tone commensurate with a degree in magnitude of a difference of the average, a means for generating a gray scale image having a varied brightness depending on a ridge-valley shaping tendency of the mesh given the focused point, and a means for performing a multiplying synthesis of the gradient reddening image and the gray scale image, to display on a screen a gradient reddening stereoscopic image representing degrees of gradient and degrees of height in color. BRIEF DESCRIPTION OF THE DRAWINGS The above and further features, functions, and effects of the invention become more apparent from the following description of best modes for carrying out the invention, when the same is read in conjunction with the accompanying drawings, in which: FIG. 1 is a block diagram of a visualization processing system according to a first mode of embodiment of the invention; FIG. 2 is a flowchart showing a processing procedure and process results of the visualization processing system of FIG. 1; FIG. 3 is a detail of part A of the flowchart of FIG. 2; FIG. 4 is a detail of part B of the flowchart of FIG. 2; FIG. 5 is a detail of part C of the flowchart of FIG. 2; FIG. 6 is a detail of part D of the flowchart of FIG. 2; FIG. 7 is a detail of part E of the flowchart of FIG. 2; FIG. 8 is a detail of part F of the flowchart of FIG. 2; FIG. 9 is a detail of part G of the flowchart of FIG. 2; FIG. 10 is a detail of part H of the flowchart of FIG. 2; FIG. 11 is a block diagram of a visualization processing system for generating a gradient reddening stereoscopic image according to a second mode of embodiment of the invention; FIG. 12 is an illustration of a laser measurement in the visualization processing system of FIG. 11; FIG. 13 is an illustration of an eight-directional array in the visualization processing system of FIG. 11; FIG. 14 is an illustration of principles of an aboveground opening and an underground opening in the visualization processing system of FIG. 11; FIG. 15 is a diagram illustrating principal patterns of aboveground opening and underground opening in the visualization processing system of FIG. 11; FIG. 16 is a stereoscopic illustration of an aboveground opening and an underground opening in the visualization processing system of FIG. 11; FIG. 17 is a diagram illustrating a sample point and a distance of aboveground opening and underground opening in the visualization processing system of FIG. 11; FIG. 18 is a diagram illustrating gray scale allocation in the visualization processing system of FIG. 11; FIG. 19 is a block diagram of an convexity-emphasized image creator, a concavity-emphasized image creator, and a first synthesizer of the visualization processing system of FIG. 11; FIG. 20 is a block diagram of an inclination-emphasized image creator, and a second synthesizer of the visualization processing system of FIG. 11; FIG. 21 is an illustration of a generation step of a synthetic image of an aboveground opening image and an underground opening image in the visualization processing system of FIG. 11; FIG. 22 is an illustration of steps for generation of a gradient reddening stereoscopic image in the visualization processing system of FIG. 11; FIG. 23 is a view of a stereoscopically visualized image of Aokigahara, Mt. Fuji, obtained by the visualization processing system of FIG. 11; FIG. 24 is a contour-lined topographic map based on an aerial mapping measurement of a southern region of a Tenjinyama ski area, Aokigahara, Mt. Fuji; FIG. 25 is a contour-lined topographic map based on laser measurement data of the same region; FIG. 26 is a magnified view of a stereoscopically visualized image of the same region; FIG. 27 is a magnified view of a stereoscopically visualized image of another region; FIG. 28 is a magnified view of a stereoscopically visualized image of another region; FIG. 29 is an X-ray fluoroscopic view of a human body; FIG. 30 is a graduation-tinted slice image of the fluoroscopic view of FIG. 29; FIG. 31 is a red-toned elevation-depression degree distribution image obtained by processing the fluoroscopic view of FIG. 29 by the visualization processing system of FIG. 1; and FIG. 32 is a synthetic image of the image of FIG. 30 and the image of FIG. 31 superposed thereon. BEST MODES FOR CARRYING OUT THE INVENTION There will be described below best modes for carrying out the invention. FIRST MODE OF EMBODIMENT First, description is made of a first mode of embodiment of the invention, with reference to FIG. 1 to FIG. 10. FIG. 1 is a block diagram of a visualization processing system VPS1 according to this mode of embodiment, FIG. 2, a flowchart showing process procedures P1 to P8 and process results A to I of the system VPS1, and FIG. 3 to FIG. 10, details of principal process results A to H, respectively. As shown in FIG. 1, the visualization processing system VPS1 has a central information processing unit (CPU) 51 composed as an adequate combination of a workstation, a processor, or a microcomputer, and logics, registers, etc., an information input section 54 including a keyboard (KB), a mouse, interactive software switches, external communication channels, etc., for inputting necessary control and/or operational information to the central information processing unit 51, an information output section 55 including a display, a printer, external communication channels, etc., for performing indication and/or transmission, in a wide sense, of information output from the central information processing unit 51, a first memory 52 such as a read-only memory (ROM) having stored therein an operating system, application programs, and the like to be read to the central information processing unit 51, and a second memory 53 such as a random access memory (RAM) for storing information to be occasionally processed in the central information processing unit 51 as well as information occasionally written from the central information processing unit 51. The first and second memories 52, 53 may preferably be integrated or subdivided in a suitable manner. The first memory 52 has stored therein a visualization processing program 60 operable on a prescribed application. In this mode of embodiment, the visualization processing program 60 is composed of a first to an eighth processing file 61 to 68 including program groups to be read in the central information processing unit 51, where they are adapted to execute eight visualization processes P1 to P8 shown in FIG. 2, respectively, while the classification and allocation of those program groups can be set in a voluntary manner. In the second memory 53 is stored a vector field 70 constituting an object of process of the visual processing program 60. The vector field 70 may be a finite set of (a total number of N) information vectors having one or more components allowing extraction of substantially three or more kinds of information. In this mode of embodiment, each vector is given as a two-component vector that contains, for a focused point representing a minute finite-division region of a ground surface of Mt. Fuji, an identification (Id) number allowing confirmation to be made of information on the latitude and information on the longitude by a reference table, and a height difference relative to a neighboring focused point or reference point of triangulation. The first processing file 61 is adapted to calculate, from an identification number Idn and a height difference of a two-component vector Vn processed as an n-th (n=1 to N), the longitude xn, latitude yn, and sea level altitude zn, and associate their values with a corresponding coordinate point Qn={Xn=xn, Yn=yn, Zn=zn} in a virtual three-dimensional (3D) X-Y-Z orthogonal coordinate space 80 stored in the second memory 53, i.e., store the identification number Id of the vector Vn in a storage region in the memory 53 correspondent to the coordinate point Qn, to thereby map the vector Vn into the coordinate space 80. This is made for the total number of N vectors, whereby the vector field 70 is mapped in the coordinate space 80 (FIG. 2, process P1). The first processing file 61 is further adapted to determine by the method of least squares or the like a curved plane S connecting with a necessary smoothness a sequence of a total number of N or an adequate smaller number of Id-numbered coordinate points {Qn: n≦N} within the coordinate space 80, divide it into a total number of M {M≦N} minute plane regions{Sm: m≦M}, defining their focused points Qm, and store relevant information in the memory 53. A second processing file 62 is adapted to verify, for a respective plane region Sm, a local region Im+ at an obverse side (Z+ side) of the curved plane S residing within a prescribed radius from a focused point Qm thereof, and determine a degree of openness defined thereby (i.e. a see-through solid angle to the heaven end or a second-order differential value equivalent thereto) Ψm+ about the focused point Qm (FIG. 2, process P2), storing it as an elevation degree of the plane region Sm. FIG. 3 shows, as a process result A, an image in which the elevation degree Ψm+ is tone-indicated over an entirety of the curved plane S. This image A clearly indicates a ridge side of terrain, i.e., a convexity (of the curved plane S) like an evident convexity. A third processing file 63 is adapted to verify, for the plane region Sm, a local region Lm− at a reverse side (Z− side) of the curved plane S residing within the prescribed radius from the focused point Qm, and determine a degree of openness defined thereby (i.e. a see-through solid angle to the earth end or a second-order differential value equivalent thereto) Ψm− about the focused point Qm (FIG. 2, process P3), storing it as a depression degree of the plane region Sm. FIG. 5 shows, as a process result C, an image in which the depression degree Ψm− is tone-indicated over an entirety of the curved plane S. This image C clearly indicates a valley side of terrain, i.e., a concavity (of the curved plane S) like an evident concavity. It should be noted that this image C does not constitute a simple reverse of the image A. A fourth processing file 64 is adapted to synthesize, for the plane region Sm, the elevation degree Ψm+ and the depression degree Ψm− in a weighting manner (w+Ψm++w−Ψm−) with a sharing proportion w+:w−(w++w−=0) determined in an end-fit manner (that is, depending on which of ridge and valley is to be put above), thereby determining a stereoscopic effect to be brought about the focused point Qm by a local region Lm (Lm+, Lm−) at obverse and reverse of the curved plane S residing within the prescribed radius (FIG. 2, process P4), storing it as an elevation-depression degree Ψm of the plane region Sm. FIG. 4 shows, as a process result B, an image in which the elevation-depression degree Ψm is tone-indicated over an entirety of the curved plane S. This image B clearly indicates a convexity (of the curved plane S) like an evident convexity, and a concavity like an evident concavity, thereby defining ridge and valley of terrain, with an intensified visually solid feeling. It is noted, for the image B, the weighting in synthesis is w+=−w−=1. Description is now made of a sixth processing file 66. This file 66 is adapted to determine, for the plane region Sm, a maximum degree of inclination Gm thereof (or a first-order differential value equivalent thereto) directly or indirectly via the method of least squares (FIG. 2, process P6), storing it as an inclination Gm of the plane region Sm. FIG. 6 shows, as a process result D, (an achromatic indication image of) an image in which the inclination Gm is color-toned to be indicated in a red-spectral color R over an entirety of the curved plane S. This image D also has the effect of visually projecting a stereoscopic appearance of terrain (that is the curved plane S). A fifth processing file 65 is adapted for mapping (FIG. 2, process P5) the three-dimensional coordinate space 80, together with relevant information thereof (Tm, Gm, R), onto a two-dimensional plane 90 in the information output section 55, to thereby provide, to a region 90m on the two-dimensional plane 90 corresponding to the region Sm as a division of the plane S connecting a sequence of coordinate points Qm, an R color-toned indication of the inclination Gm, and for a brightness of the R color tone, a tone indication commensurate with the elevation-depression degree Ψm. FIG. 8 shows, as a process result F. (an achromatic indication image of) this image. In this image F. terrain (that is the curved plane S) has a visually solid appearance. An image E of FIG. 7 shows a result of a mapping (process P5), by the processing file 65 onto the two-dimensional plane 90, of information on the image D (i.e. R color tone indication of inclination Gm) and information on elevation-depression degrees (i.e. elevation degrees Tm+) corresponding to the image A, where ridge part is emphasized. An image G of FIG. 9 shows a result of a mapping (process P5), by the processing file 65 onto the two-dimensional plane 90, of information on the image D (i.e. R color tone indication of inclination Gm) and information on elevation-depression degrees (i.e. depression degrees Ψm−) corresponding to the image C, where valley part is emphasized. A seventh processing file 67 is adapted to determine attribute isopleth lines (in this mode of embodiment, terrain's isometric contour lines and shape contour lines) Ea connecting, among the sequence of coordinate points Qn, those coordinate points Qn equivalent of an attribute (in this mode of embodiment, sea level altitude zn) extracted from components of vectors Vn of the vector 70 field, storing them, and to output or indicate, as necessary (FIG. 2, process P7). FIG. 2 shows an indication process result I of the same. This result I also contributes to the grasp of a stereoscopic configuration of terrain (that is the curved plane S). The eighth processing file 68 is adapted to map or output for display the three-dimensional space 80, together with relevant information (Ψm, Gm, R) hereof, onto the two-dimensional plane 90, mapping or outputting for display the attribute isopleth lines Ea (FIG. 2, process P8). FIG. 10 shows, as a process result H, (an achromatic indication image of) a display image of the same. In this image H also, terrain (that is the curved plane S) has a visually solid appearance. Therefore, the visualization processing system VPS1 according to this mode of embodiment comprises a first operator (61) for mapping a vector field 70 in a three-dimensional coordinate space 80 to obtain a corresponding sequence of coordinate points Qm, a second operator (62) for determining an elevation degree Ψm+ in a local region Lm+ of a plane S connecting the sequence of coordinate points, a third operator (63) for determining a depression degree Ψm− in a local region Lm− of the plane S connecting the sequence of coordinate points, a fourth operator (64) for synthesizing the elevation degree and the depression degree in a weighting manner to determine an elevation-depression degree Ψm in a local region Lm of the plane S connecting the sequence of coordinate points, and a fifth operator (65) for mapping the coordinate space 80 on a two-dimensional plane 90, providing a tone indication commensurate with the elevation-depression degree to a region 90m on the two-dimensional plane 90 corresponding to a divided region Sm of the plane S connecting the sequence of coordinate points. The operator means herein an element, a set thereof, or a means for executing an operation process command or operation process function programmed or set in advance. The visualization processing system VPS1 further comprises a sixth operator (66) for determining an inclination Gm distribution of the plane S connecting the sequence of coordinate points, and the fifth operator (65) is adapted to provide on the two-dimensional plane 90 a color-toned indication of the inclination distribution, in a red spectral color R, and for a brightness thereof, give the tone indication. The visualization processing system VPS1 further comprises a seventh operator (67) for connecting, among the sequence of coordinate points, those coordinate points equivalent of an attribute in the vector 70 field to obtain attribute isopleth lines Ea, and an eighth operator (68) for mapping the attribute isopleth lines Ea on the two-dimensional plane 90 given the tone indication. According to this mode of embodiment, a vector field 70 can be visualized on a substantially two-dimensional plane 90 in a manner that allows an intuitive visual perception, with a local stereoscopic attribute thereof inclusive. A visualization processing method according to this mode of embodiment comprises a first step P1 of mapping a vector field in a three-dimensional coordinate space to obtain a corresponding sequence of coordinate points, a second step P2 of determining an elevation degree in a local region of a plane connecting the sequence of coordinate points, a third step P3 of determining a depression degree in the local region of the plane connecting the sequence of coordinate points, a fourth step P4 of synthesizing the elevation degree and the depression degree in a weighting manner to determine an elevation-depression degree in the local region of the plane connecting the sequence of coordinate points, and a fifth step P5 of mapping the coordinate space on a two-dimensional plane, providing a tone indication of the elevation-depression degree to a region on the two-dimensional plane corresponding to a divided region of the plane connecting the sequence of coordinate points. A visualization processing program 60 according to this mode of embodiment is functionable to have a central information processing unit 51 execute a first process P1 for mapping a vector field in a three-dimensional coordinate space to obtain a corresponding sequence of coordinate points, a second process P2 for determining an elevation degree in a local region of a plane connecting the sequence of coordinate points, a third process P3 for determining a depression degree in the local region of the plane connecting the sequence of coordinate points, a fourth process P4 for synthesizing the elevation degree and the depression degree in a weighting manner to determine an elevation-depression degree in the local region of the plane connecting the sequence of coordinate points, and a fifth process P5 for mapping the coordinate space on a two-dimensional plane, providing a tone indication of the elevation-depression degree to a region on the two-dimensional plane corresponding to a divided region of the plane connecting the sequence of coordinate points. SECOND MODE OF EMBODIMENT Next, description is made of a second mode of embodiment of the invention, with reference to FIG. 11 to FIG. 28. FIG. 11 is a block diagram of a visualization processing system VPS2 including a gradient reddening stereoscopic image generator 4 according to this mode of embodiment, FIG. 12, an illustration of a laser measurement in the system VPS2, FIG. 13, an illustration of an eight-directional array, FIG. 14, an illustration of principles of an aboveground opening and an underground opening, FIG. 15, a diagram illustrating principal patterns of aboveground opening and underground opening, FIG. 16, a stereoscopic illustration of an aboveground opening and an underground opening, FIG. 17, a diagram illustrating a sample point and a distance of aboveground opening and underground opening, FIG. 18, a diagram illustrating gray scale allocation, FIG. 19, a block diagram of an convexity-emphasized image creator, a concavity-emphasized image creator, and a first synthesizer, FIG. 20, a block diagram of an inclination-emphasized image creator, and a second synthesizer, FIG. 21, an illustration of a generation step of a synthetic image of an aboveground opening image and an underground opening image, and FIG. 22, an illustration of steps for generation of a gradient reddening stereoscopic image. Further, FIG. 23 is a view of a stereoscopically visualized image of Aokigahara, Mt. Fuji, obtained by the visualization processing system VPS2, FIG. 24, a contour-lined topographic map based on an aerial mapping measurement of a southern region of a Tenjinyama ski area, Aokigahara, Mt. Fuji, FIG. 25, a contour-lined topographic map based on laser measurement data of the same region, FIG. 26, a magnified view of a stereoscopically visualized image of the same region, FIG. 27, a magnified view of a stereoscopically visualized image of another region, and FIG. 28, a magnified view of a stereoscopically visualized image of another region. This mode of embodiment is configured to determine an inclination corresponding to the inclination Gm in the first mode of embodiment, an aboveground opening corresponding to the elevation degree Ψm+ in the first mode of embodiment, and an underground opening corresponding to the depression degree Ψm− in the first mode of embodiment, as three parameters based on DEM (Digital Elevation Model) data, and store their flat plane distribution as a gray scale image. A difference image between aboveground and underground is entered in a gray, and the inclination, in a red channel, for creation of a pseudo-color image, to thereby effect indication to be whitish at a ridge or crest part, and blackish in valley or howe, while it gets red as inclined part becomes steep. Such combination of indication allows creation of an image (hereafter sometimes called a stereoscopic reddened map) to be solid in appearance even on a single sheet. In other words, for a map to be solid, this mode of embodiment employs a stereoscopic indication method, in which intervals between contour lines are meshed, and for a respective mesh, a difference to a neighboring mesh, that is, an inclination is indicated by a red color tone, and whether high or low in comparison with periphery is indicated by a gray scale. This corresponds to the elevation-depression degree Ψm in the first mode of embodiment, which is referred to as a ridge-valley shaping tendency in this mode of embodiment, suggesting a brighter place to be (ridge-like) higher than periphery, and a darker place to be (valley-like) lower than periphery, of which brightness and darkness are multiplication-synthesized to thereby generate a solid appearance. FIG. 11 shows a schematic arrangement of the gradient reddening stereoscopic image generator 4 according to this mode of embodiment. As shown in FIG. 11, the gradient reddening stereoscopic image generator 4 of this mode of embodiment is provided with a computer function described below. The gradient reddening stereoscopic image generator 4 further has a variety of databases connected thereto. A database 1 has a laser data Ri stored therein. For the laser data (Rx, Ry, Rz: coordinates of laser data referred to by addition of R), as illustrated in FIG. 12, by an aircraft flying level in the sky above a target district (preferably, a digital camera pickup range), a laser beam is emitted downward, and from the time required to go and back, aircraft's location and posture, and angle of emission, ground surface's x, y, z are determined by (computer) calculation and stored. Employed for grasp of the aircraft's location is a GPS (not shown), and for grasp of the posture, an IMU. The laser emitter (unshown at Z) is adapted for 33,000 shots per second, allowing acquisition of altitude points (Rx, Ry, Rz) in a density of one point every 80 cm. In the case a plurality of reflected pulses are measured for one shot of laser emission, data of a final reflection is employed and stored. Further, by checking received laser data for a tendency of distribution, points spiked higher than periphery are removed as being laser data of trees having failed to be passed, in addition to removal of laser data else than tree, such as a house, automobiles, or bridge. Therefore, the database 1 simply stores a laser data Ri of ground surface. A database 2 has stored therein at least a contour map Hi ( 1/25,000: with numbered contour lines) of the digital camera pickup range. Further, the contour map is provided with characteristic point coordinates (Hx, Hy, Hz: contour map data). Further, a database 3 has stored therein a stereo-matching data Mi. The stereo-matching data Mi is created as a stereoscopic image from two air photos that have picked up an identical area. For example, a known building is extracted from the two photos, and a side of the building is given a Z value for solidization (Mx, My, Mz), which constitutes a reference for Z values to be given to others. A DEM data creator 6 reads laser data Ri of the database 1, generating a contour map in which respective altitudes identical in value are connected, and creates a TIN for the contour map, to restore a ground surface. It then determines heights of crossing points between the TIN and respective lattice points, to produce DEM (Digital Elevation Model) data. Further, the DEM data creator 6 reads a contour map Hi stored in the database 2, and generates the TIN mutually connecting contour lines, which is converted to the above-noted DEM data. Next, description is made of a DEM data to be employed in this mode of embodiment. For example, for a “numeric map 50-m mesh (altitude)”, from meshes of a 1/25,000 topographic map vertically and horizontally divided into 200 equal pails (by mesh pitches of 2.25 seconds in latitude-line direction and 1.50 seconds in longitude-line direction), their central altitudes are read at intervals of 1 m, to be arrayed two-dimensional. Further, in this mode of embodiment, the gradient reddening stereoscopic image creator 4 includes an aboveground opening data creator 9, an underground opening data creator 10, a gradient calculator 8, a convexity-emphasized image creator 11, a concavity-emphasized image creator 12, an inclination emphasizer 13, a first synthesizer 14, and a second synthesizer 15. In this mode of embodiment, the concept of an opening is used. The opening is a quantified degree by which a spot in concern is convex aboveground or concave underground in comparison with surroundings. In other words, as illustrated in FIG. 14, an aboveground opening is defined as an extent of the sky to be seen within a range of a distance L from a focused sample point, and an underground opening is defined as an extent under the ground, within a range of the distance L, when taking a survey in the soil in a handstand position. The openings depend on the distance L and a surrounding terrain. FIG. 15 illustrates, for 9 kinds of principal terrains, their aboveground opening and underground opening by graphs of octagons representing an aboveground angle and an underground angle in respective azimuths. Generally, the aboveground opening increases as the spot is projected higher from the surrounding, and has a value to be large at a crest or ridge, but small in a howe or at a valley bottom. To the contrary, the underground opening increases as the spot is cut underground lower, and has a value to be large in a howe or at a valley bottom, but small at a crest or ridge. Actually, even in the range of distance L, a variety of principal terrains are weaved, so that the octagonal graphs of aboveground angle and underground angle are frequently deformed, giving varieties of opening values. As will be described, D φL and D ψL have non-increasing characteristics to L, and Φ L and Ψ L have non-increasing characteristics to L, accordingly. Further, the opening diagram permits extraction of information to fit to the terrain scale, by specification of a calculated distance, allowing for an indication free from dependency on directional and local noises. That is, excellent extraction of ridge line and valley line allows abundant geographical and geological information to be read: as illustrated in FIG. 16, on a DEM data (ground surface: solid: FIG. 16(a)) within a fixed range, a spot A in concern is set, which is connected with a point B to be a greatest peak when viewed in any one of eight directions therefrom, by a straight line L1 that defines, to a horizontal line, an angular vector θi to be determined. In this way, over the eight directions, angular vectors are determined, of which an average is called an aboveground opening θi; and on an invert DEM data (FIG. 16(c)), which is a reverse of a solid (FIG. 16(b)) having an air layer pushed on the DEM data of the fixed range (ground surface: solid), the spot A in concern is connected with a point C (corresponding to a deepest place) to be a greatest peak when viewed in any one of eight directions therefrom, by a straight line L2 that defines, to the horizontal line, an angle to be determined. This angle is determined over the eight angles, and averaged, which is called an underground opening ψi. That is, the aboveground opening data creator 9 produces, on a DEM data included within a range of a fixed distance from a focused point, a terrain section in each of eight directions, and determines a maximum value (in view of a plumb direction) among inclinations of connection lines (L1 of FIG. 16(a)) between the focused point and respective terrain points. A process like this is executed in the eight directions. The angle of inclination is an angle from the zenith (90 degrees on a flat, above 90 degrees at a ridge or crest, or below 90 degrees at a valley bottom or in a howe); and the underground opening data creator 10 produces, within a range of the fixed distance from the focused point on an invert DEM data, a terrain section in each of eight directions, and determines a maximum value among inclinations of connection lines between the focused point and respective terrain points (to be a minimum value when looking L2 in the plumb direction in a three-dimensional figure of a ground surface of FIG. 16(a)). A process like this is executed in the eight directions. When looking L2 in the plumb direction in the three-dimensional figure of the ground surface of FIG. 16(a), the angle ψi has 90 degrees on a flat, under 90 degrees at a ridge or crest, or above 90 degrees at a valley bottom or in a howe. In other words, for the aboveground opening and underground opening, as illustrated in FIG. 17, two base points A (iA, jA, HA) and B (iB, jB, HB) are supposed. As the sample spacing is 1 m, the distance between A and B is given, such that P={(iA−iB)2+(jA−jB)2}1/2 (1). FIG. 17(a) illustrates a relationship between sample points A and B, relative to an altitude 0 m as a reference. An elevation angle θ the sample point A has to the sample point B is given, such that θ=tan−1{(HB−HA)/P. The sign of θ is positive for {circle around (1)} HA<HB, or negative for {circle around (2)} HA>HB. A set of sample points residing in an azimuth D within a range of a distance L from a focused sample point is denoted DSL, which will be called “a D-L set of a focused sample point”. Letting now D β L: a maximum value among elevation angles for respective elements of DSL of a focused sample point, and D δ L: a minimum value among elevation angles for respective elements of DSL of a focused sample point (refer to FIG. 17(b)), the following definitions are given. Definition 1: an aboveground angle and an underground angle of a D-L set of a focused sample point shall mean respectively such that DφL=90−DβL, and DψL=90+DδL. D φ L means a maximum value of a zenith angle in which the sky in an azimuth D can be seen within a distance L from a focused sample point. A generally called horizon angle corresponds to the aboveground angle as L is an infinity. And, D ψL means a maximum value of a nadir angle in which the soil in an azimuth D can be seen within a distance L from a focused sample point. As L is increased, the number of sample points belonging to DSL increases, whereto D β L has a non-decreasing characteristic, and on the contrary, D δ L has a non-increasing characteristic. Therefore, D φ L as well as D ψ 1 has a non-increasing characteristic to L. In the geodesy, the high angle is a concept defined to a horizontal plane as a reference passing a focused sample point, and strictly, not coincident with θ. Further, for a strict discussion of aboveground angle and underground angle, the curvature of the earth should also be considered, and the definition 1 is not always an exact description. The definition 1 is a concept defined for a geomorphic analysis assumed to be made by using DEM to the last. The aboveground angle and the underground angle have been concepts for a specified azimuth D, which will be expanded by introducing the following definition. Definition II: An aboveground opening and an underground opening of a distance L from a focused sample point shall mean respectively such that ΦL=(0φL+45φL+90φL+135φL+180φL +225φL+270φL+315φL)/8,and ΨL=(0ψL+45ψL+90ψL+135ψL+180ψL +225ψL+270ψL+315ψL)/8. The aboveground opening represents an extent of the sky to be seen within a range of the distance L from the focused sample point, and the underground opening represents an extent under the ground, within a range of the distance L, when taking a survey in the soil in a handstand position (refer to FIG. 14). The gradient calculator 8 is adapted to mesh a DEM data into squares, and determine an average gradient of surfaces of squares neighboring a focused point on the meshes. The neighboring squares are four in number, any one of which is chosen as a focused square. Then, an average inclination and heights at four comers of the focused square are determined. The average inclination is a gradient of surface approximated from four points by using the method of least squares. The convexity-emphasized image creator 11 has a first gray scale for indicating a ridge and a valley bottom by brightness, as illustrated in FIG. 18(a), and is adapted, every time when the aboveground opening data creator 9 determines an aboveground opening (as an average angle when a range of L is seen in eight directions from a focused point: an index for judgment of whether the residing place is high), to calculate a brightness (luminance) commensurate with the aboveground opening θi. For example, for values of aboveground opening falling within a range of about 40 degrees to 120 degrees, the first gray scale is associated with a range of 50 degrees to 110 degrees, which is allotted to 255 tones. That is, toward a ridge part (convex), the place has a greater value of aboveground opening, and becomes white in color. Then, as shown in FIG. 19, at the convexity-emphasized image creator 11, a convexity emphasizing color allotment process 20 reads an aboveground opening image data Da, and allots, to a mesh region having a focused point (coordinate) (in the case contour lines connecting identical Z values of DEM data are meshed (e.g. 1 m) into squares, and a focused point is set to a point at any of four comers of mesh) a color data based on the first gray scale, which is stored (as an aboveground opening image data Dpa) in an aboveground opening file 21. Then, a tone corrector 22 stores, in a file 23, the aboveground opening image data Dpa having color tones thereof inverted, as an aboveground opening layer Dp. That is, there is obtained an aboveground opening layer Dp adjusted for the ridge to be indicated white. A concavity extractor 12 has a second gray scale for indicating a valley bottom and a ridge by brightness, as illustrated in FIG. 18(b), and is adapted, every time when the underground opening data creator 10 determines an underground opening ψi (as an average in eight directions from a focused point), to calculate a brightness commensurate with the underground opening ψi. For example, for values of underground opening falling within a range of about 40 degrees to 120 degrees, the second gray scale is associated with a range of 50 degrees to 110 degrees, which is allotted to 255 tones. That is, toward a valley bottom part (concave), the place has a greater value of underground opening, and becomes black in color. Then, as shown in FIG. 19, at the concavity-emphasized image creator 12, a concavity emphasizing color allotment process 25 reads an underground opening image data Db, and allots, to a mesh region having a focused point (coordinate) (in the case contour lines connecting identical Z values of DEM data are meshed (e.g. 1 m) into squares, and a focused point is set to a point at any of four comers of mesh) a color data based on the second gray scale, which is stored in an underground opening file 26. Then, a tone correction process 27 makes a correction of color tones of the underground opening image data Db. If the color is toned excessively black, it is set to a tone of color according to a corrected tone curve. This is called an underground opening layer Dq, and stored in a file 28. The inclination-emphasized image creator 13 has a third gray scale for indicating a degree of inclination by brightness, as illustrated in FIG. 18(c), and is adapted, every time when the gradient calculator 8 determines an inclination degree (as an average in four directions from a focused point), to calculate a brightness (luminance) commensurate with the inclination degree. For example, for values of inclination αi falling within a range of about 0 degree to 70 degrees, the third gray scale is associated with a range of 0 degree to 50 degrees, which is allotted to 255 tones. That is, 0 degree to be white, and 50 degrees to be black. The color is blackened as the spot has a greater inclination α. Then, as shown in FIG. 20, at the inclination-emphasized image creator 13, an inclination emphasizing color allotment process 30 stores, in a file 31, a difference image between the underground opening image data Db and the aboveground opening image data Da, as a gradient image Dra. At this time, a color data based on the third gray scale is allotted to a mesh region having a focused point (coordinate) (in the case contour lines connecting identical Z values of DEM data are meshed (e.g. 1 m) into squares, and a focused point is set to a point at any of four comers of mesh). Then, a reddening process has an RGB color mode function for emphasizing R. That is, there is obtained in a file 33 a gradient-emphasized image Dr that has an emphasized red as the inclination is greater. The first synthesizer 14 is adapted for a multiplication of the aboveground opening layer Dp and the underground opening layer Dq to obtain a synthetic image Dh (Dh=Dp+D1) thereby synthesized. At this time, a balance of both is adjusted to avoid collapsing valley part. The above-noted “multiplication” is a term in a layer mode on a photoshop, that corresponds to an OR operation for numeric process. Brightness Gray scale i-1 i-2 i-3 Lighter as higher aboveground 36 52 45 Darker as higher underground 32 48 61 Total 68 100 106 In the balance adjustment, for allocation of value between aboveground and underground at a spot, the ground surface is cut out by a fixed radius (L/2) about the spot. Assuming an entirety of sky to be uniform in brightness, the extent of sky looked up from a surface of ground gives a brightness of the ground surface. That is, an aboveground opening constitutes the brightness. However, assuming light spiking around, a value of underground opening should be considered. Depending on how the ratio of both is settled, an arbitrary modification can be achieved, such as for an emphasis at a ridge part of terrain, for example. For a desirable emphasis of a terrain in a valley, the value of b may be increased. Index ⁢ ⁢ of ⁢ ⁢ brightness = a × aboveground ⁢ ⁢ opening - b × underground ⁢ ⁢ opening , where a+b=1. That is, as illustrated in FIG. 21, the aboveground opening layer Dp (with ridge emphasized white) and the underground opening layer Dq (with bottom emphasized black) are multiplication-synthesized to obtain a synthetic image gray-toned for indication (Dh=Dp+D1). On the other hand, the second synthesizer is adapted for synthesizing the gradient-emphasized image Dr in the file and the synthetic image Dh obtained by a synthesis at the first synthesizer, to have a stereoscopic reddening image Ki emphasized at the ridge in red color, for indication on the display. That is, as illustrated in FIG. 22, there is obtained the gradient-emphasized image Dr in which red is emphasized for greater gradients than the gradient image Dra, besides the synthetic image Dh of a gray tone indication by a multiplication-synthesis of the aboveground opening layer Dp (with ridge emphasized white) and the underground opening layer Dq (with bottom emphasized black). Then, the gradient-emphasized image Dr is synthesized with the synthetic image Dh. FIG. 23 is a stereoscopic map of a whole neighborhood of Aokigahara, whereto a process according to this mode of embodiment is employed. As seen from FIG. 23, just in the south of Tenjinnyama ski area, a glacial hole crater row extends, which has a crater that had outflown an Aokigahara lava flow. It is difficult to verify the location in an aerial photograph where the deep forest constitutes an obstacle. Further, the glacial hole crater row looks as it may be in a map by laser data (refer to FIG. 25), while an indication thereof is difficult in a contour map by aerial survey (refer to FIG. 24). Contrary thereto, in a stereoscopic picture according to this mode of embodiment, as seen from FIG. 6, the glacial hole crater row appears as it is clear defined, as well as a lava flow formed with undulations and routes of the climb. Further, in FIG. 27 and FIG. 28 as magnified views, there can be seen visually defined lava flows, road inclinations, and undulations, It is noted that the technique in this mode of embodiment is applicable to a terrain of Venus as well as a terrain of Mars. In addition, it is applicable for visualization of a ruggedness measured by an electron microscope. Further, if applied to a game machine, it allows a stereoscopic feeling to be given without putting glasses. As is above, in this mode of embodiment, based on a DEM (Digital Elevation Model) data, three parameters of inclination, aboveground opening, and underground opening are determined, and their distribution on a flat plane is stored as a gray scale image. A difference image between aboveground and underground is entered in a gray, and the inclination, in a red channel, for creation of a pseudo-color image, to thereby effect indication to be whitish at a ridge or crest pat, and blackish in valley or howe, while it gets red as inclined part becomes steep. By combination of such indication, an image can be generated with a stereoscopic appearance even on a single sheet. Therefore, it allows at a glance a grasp of degrees of concavo-convex heights as well as a degree of gradient. THIRD MODE OF EMBODIMENT Description is now made of a third mode of embodiment of the invention to which the visualization processing system VPS1 of FIG. 1 is aided, with reference to FIG. 29 to FIG. 32. FIG. 29 is an X-ray fluoroscopic view of a human body, FIG. 30, a graduation-tinted slice image of the fluoroscopic view of FIG. 29, FIG. 31, a red-toned elevation-depression degree distribution image obtained by processing the fluoroscopic view by the visualization processing system VPS1, and FIG. 32, a synthetic image of the image of FIG. 30 and the image of FIG. 31 superposed thereon. The graduation-tinted slice image of FIG. 30 is an image, as the X-ray fluoroscopic view of FIG. 29 having hue of pixels thereof sliced and graduation-tinted in dependence on their brightness, for which, in this mode of embodiment, a field of vectors having positional information and brightness of the pixels as their components is stored, in the memory 53, as the vector field 70 of the visualization processing system VPS1, and displayed, at the information output section 55, as a result of process P7 by the seventh processing file 67 of the visualization processing program 60. Further, the red-toned elevation-depression degree distribution image of FIG. 31 is displayed, at the information output section 55, as a result of process P5 by the fifth processing file 65 of the visualization processing program 60. Then, the synthetic image of FIG. 32 is displayed, at the information output section 55, as a result of process P8 by the eighth processing file 68 of the visualization processing program 60. INDUSTRIAL APPLICABILITY According to the invention, there can be provided a visualization processing system, a visualization processing method, and a visulialtion processing program, which are adapted to visualize a vector field, with local solid attributes thereof inclusive, on a substantially two-dimensional field of view, in a manner that allows an intuitive visible perception. Further, there can be provided a visualization processing system, a visualization processing method, and a visualization processing program, which are adapted to generate a gradient reddening stereoscopic image that allows at a glance a stereoscopic grasp of terrain's heights and inclination degrees
<SOH> BACKGROUND ART <EOH>For a visualization of three-dimensional vector field on a two-dimensional plane, many attempts have been made since ancient times. Most typically, there has been known a method of converting two components into coordinate values, and plotting an intersection thereof on a two-dimensional plane, providing each intersection with a note of attribute of the remaining third component (e.g. a town guide map), which however is unable to afford an easy grasp of a difference of the third component. In this respect, there has been made also a graphic expression of an attributive feature of the third component (e.g. a town street guide map), which is still bound to the localization of information, and has covered successive changes in the attribute. To this point, there has been generally employed a method of entering a continuous feature of two components (e.g. an outline such as of a coast, river, lake, or marsh) and attribute isopleth lines of the third component (e.g. contour lines), which is yet difficult of the intuitive visible perception of an attribute variation. A topographic map is now supposed for more specific discussion. In a mesh measurement by an analyzing mapper, the terrain is lattice-like divided, having altitude values given thereto, to provide a DEM (Digital Elevation Model) data. This is processed in a computer for calculation of parameters concerning, e.g, the terrain's heights, inclination angles, slope azimuths, laplacians, valley divisions, water systems, etc., allowing for a distribution of calculation results over a plane to be converted into a corresponding image. In an airborne laser measurement, available data contain more detail information. All the data is not involved in a topographic map. For example, information on the height and inclilnation is extracted, to be entered as contour lines in the map. It however is uneasy to imagine a stereoscopic terrin therefrom. There is also an image provided with a stereoscopic appearance, as a hill shade lighted from a diagonal upside, which has an emphasized inclination in a particular direction. In this concern, there is a gray scale (tone of brightness) or a rainbow color (tone of hue) indicated in a terrin image, which allows an intuitive visual perception of termin's geometrical features and their distribution, and is useful, but unable to give an effective visually solid appearance. Reference-1: “Japanese Patent Application Laying-Open Publication 146902” There is also an image processed by using either an avobeground opening or an underground opening as a mega filter, which allows a capture of terrain's features in a relatively large district, but feels something missing in visually solid appearance, particularly in local appearances to be visually solid. Reference-2: “Iwate University thesis: Indication of terrain features by an opening, the photogrammetry and remote sensing, by Ryuuzou Yokoyama, Michio Shirasawa, and Yutaka Kikuchi (1999), vo. 38, no. 4, 2&34”. Description is now made of conventional methods of providing a topographic map with a visually solid appearance. (Stereo-Matching Image, Three-Dimensional Image) Basically, an image that makes use of a parallax, employing two photographs. There are varieties of methods, such as cases by a red/blue filter, a polarizing filter, a diffraction grating, or a lenticurar lenz, any of which however has to be seen in a particular direction, and needs a glass. Moreover, expansion as well as scaling down is difficult. The three-dimensional image is an image looked down in a particular direction, which is inadequate to read, as having a portion unseen if in shadow, looking small if distant, and lacking resolution if close. Moreover, time is necessary for image creation. (Indication by Contour Lines) The contour line is suitable to the indication of terrain in mountainous districts, but for steep inclinations (e.g. a sudden cliff part) or gentle slopes or flat lands (a plain part), the reading of topographic features takes a time due to an extreme convergence or divergence of contour lines having stepwise allotted heights. The angle of inclination as well as the orientation is to be guessed from the variation of spacing between contour lines. Hence, being unfit in a simple expansion or scaling, it needs a remake in some case. Crowded contour lines have their gaps lost, and are substituted by a legend of cliff. This task is complex, and constitutes an impediment to vectorization. Small irregularity cannot be read unless a height is given to each contour line. (Set of Image Data having Two-Dimensional Altitude Values) In a mapping work by aerial photographic measurement, the acquisition of information is directly made of contour lines as connected particular altitudes, having no altitudes given between contour lines. In the case of mesh measurement by an analyzing mapper or airborne laser measurement, the DEM data is acquired, and based thereon a two-dimensional distribution of contour lines is determined, whereby, although contour lines are smoothed as necessary, information else than finally contained in contour lines, e.g. information of a three-dimensional geometry between contour lines, is left unused. This invention was made in view of the foregoing points. It therefore is an object of the invention to provide a visualization processing system, a visualization processing method, and a visualization processing program, which are adapted to visualize a vector field, with local solid attributes thereof inclusive, on a substantially two-dimensional field of view, in a manner that allows an intuitive visible perception. It also is an object of the invention to provide a visualization processing system, a visualization processing method, and a visualization processing program, which are adapted to generate a gradient reddening stereoscopic image that allows at a glance a stereoscopic grasp of terrain's heights and inclination degrees.
<SOH> SUMMARY OF INVENTION <EOH>To achieve the object, a visualization processing system according to the invention is characterized by a first operator for mapping a vector field in a three-dimensional coordinate space to obtain a corresponding sequence of coordinate points, a second operator for determining an elevation degree in a local region of a plane connecting the sequence of coordinate points, a third operator for determining a depression degree in the local region of the plane connecting the sequence of coordinate points, a fourth operator for synthesizing the elevation degree and the depression degree in a weighting manner to determine an elevation-depression degree in the local region of the plane connecting the sequence of coordinate points, and a fifth operator for mapping the coordinate space on a two-dimensional plane, providing a tone indication commensurate with the elevation-depression degree to a region on the two-dimensional plane corresponding to a divided region of the plane connecting the sequence of coordinate points. According to the invention, a vector field is mapped in a three-dimensional coordinate space, obtaining a corresponding sequence of coordinate points, and there are determined in a local region of a plane connecting the sequence of coordinate points an elevation degree, that is a rising tendency (e.g. a ridge shaping tendency in a topographic map), and a depression degree, that is a sinking tendency (e.g. a valley shaping tendency in a topographic map), which are synthesized in an end-fit weighting manner (in a broad sense inclusive of the difference), determining in the local region an elevation-depression degree, that is a rising and sinking tendency (e.g. a ridge-valley shaping tendency in a topographic map), which is tone-indicated in a corresponding region on a two-dimensional plane, so that the vector field can be visualized, with its local solid attributes inclusive, on a substantially two-dimensional plane in a manner that allows an intuitive visible perception. The elevation degree may preferably be defined in terms of a solid angle at one side in the local region of the plane connecting the sequence of coordinate points. The depression degree may preferably be defined in terms of a solid angle at the other side in the local region of the plane connecting the sequence of coordinate points. The visualization processing system may preferably further comprise a sixth operator for determining an inclination distribution of the plane connecting the sequence of coordinate points, and the fifth operator may preferably provide on the two-dimensional plane a color-toned indication, i.e. chroma saturation indication, of the inclination distribution (more preferably, in reddish colors), and for a brightness thereof, give the tone indication. The visualization processing system may preferably further comprise a seventh operator for connecting, among the sequence of coordinate points, those coordinate points equivalent of an attribute in the vector field to obtain an attribute isopleth line, and an eighth operator for mapping the attribute isopleth line on the two-dimensional plane given the tone indication. A visualization processing method according to the invention is characterized by a first step of mapping a vector field in a three-dimensional coordinate space to obtain a corresponding sequence of coordinate points, a second step of determining an elevation degree in a local region of a plane connecting the sequence of coordinate points, a third step of determining a depression degree in the local region of the plane connecting the sequence of coordinate points, a fourth step of synthesizing the elevation degree and the depression degree in a weighting manner to determine an elevation-depression degree in the local region of the plane connecting the sequence of coordinate points, and a fifth step of mapping the coordinate space on a two-dimensional plane, providing a tone indication of the elevation-depression degree to a region on the two-dimensional plane corresponding to a divided region of the plane connecting the sequence of coordinate points. A visualization processing program according to the invention is characterized in that the program is functionable to have a computer execute a first process for mapping a vector field in a three-dimensional coordinate space to obtain a corresponding sequence of coordinate points, a second process for determining an elevation degree in a local region of a plane connecting the sequence of coordinate points, a third process for determining a depression degree in the local region of the plane connecting the sequence of coordinate points, a fourth process for synthesizing the elevation degree and the depression degree in a weighting manner to determine an elevation-depression degree in the local region of the plane connecting the sequence of coordinate points, and a fifth process for mapping the coordinate space on a two-dimensional plane, providing a tone indication of the elevation-depression degree to a region on the two-dimensional plane corresponding to a divided region of the plane connecting the sequence of coordinate points. According to the invention, a visualization processing system for generating a gradient reddening stereoscopic image is characterized by a database having stored therein a multiplicity of digital data provided with three-dimensional coordinates, and a computer which comprises a means for generating a stereoscopic contour image having contour lines connecting three-dimensional coordinates of digital data having identical Z values, a means for meshing intervals between contour lines, a means for allocating focused points to meshes, determining an average of differences in Z value between a respective mesh given a focused point and neighboring meshes, a means for generating a gradient reddening image having assigned to the mesh given the focused point a red tone commensurate with a degree in magnitude of a difference of the average, a means for generating a gray scale image having a varied brightness depending on a ridge-valley shaping tendency of the mesh given the focused point, and a means for performing a multiplying synthesis of the gradient reddening image and the gray scale image, to display on a screen a gradient reddening stereoscopic image representing degrees of gradient and degrees of height in color. According to the invention, a visualization processing method for generating a gradient reddening stereoscopic image is characterized by a step of generating a stereoscopic contour image having contour lines connecting three-dimensional coordinates of digital data having identical Z values, a step of meshing intervals between contour lines, a step of allocating focused points to meshes, determining an average of differences in Z value between a respective mesh given a focused point and neighboring meshes, a step of generating a gradient reddening image having assigned to the mesh given the focused point a red tone commensurate with a degree in magnitude of a difference of the average, a step of generating a gray scale image having a varied brightness depending on a ridge-valley shaping tendency of the mesh given the focused point, and a step of performing a multiplying synthesis of the gradient reddening image and the gray scale image, to display on a screen a gradient reddening stereoscopic image representing degrees of gradient and degrees of height in color. According to the invention, a visualization processing program for generating a gradient reddening stereoscopic image is characterized in that the program is adapted to have a computer function as a means for reading a multiplicity of digital data provided with three-dimensional coordinates, a means for generating a stereoscopic contour image having contour lines connecting three-dimensional coordinates of digital data having identical Z values, a means for meshing intervals between contour lines, a means for allocating focused points to meshes, determining an average of differences in Z value between a respective mesh given a focused point and neighboring meshes, a means for generating a gradient reddening image having assigned to the mesh given the focused point a red tone commensurate with a degree in magnitude of a difference of the average, a means for generating a gray scale image having a varied brightness depending on a ridge-valley shaping tendency of the mesh given the focused point, and a means for performing a multiplying synthesis of the gradient reddening image and the gray scale image, to display on a screen a gradient reddening stereoscopic image representing degrees of gradient and degrees of height in color.
20051222
20100727
20061123
70611.0
G06T1120
0
PRENDERGAST, ROBERTA D
VISUALIZING SYSTEM, VISUALIZING METHOD, AND VISUALIZING PROGRAM
UNDISCOUNTED
0
ACCEPTED
G06T
2,005
10,533,788
ACCEPTED
Fluorine-containing vinylethers, their polymers, and resist compositions using such polymers
The invention relates to a fluorine-containing vinyl ether represented by the formula (1), wherein R represents an organic group containing at least one fluorine atom and a cyclic structure. The invention further relates to a fluorine-containing copolymer containing (a) a first unit derived from a first monomer that is a fluorine-containing vinyl ether represented by the formula (8) where R1 is —H or a C1-C8 alkyl group that optionally contains an oxygen atom; and (b) a second unit derived from a second monomer that is at least one selected from acrylic esters and methacrylic esters.
1. A fluorine-containing vinyl ether represented by the formula 1, wherein R represents an organic group comprising at least one fluorine atom and a cyclic structure. 2. A fluorine-containing vinyl ether according to claim 1, wherein the organic group comprises: (a) the cyclic structure that is selected from the group consisting of cyclopentane ring, cyclohexane ring, norbornene ring, aromatic rings, tricyclodecane ring; and (b) at least one substituent that is selected from the group consisting of (—OH)m, (—R1)n, and —COOR4 where R1 is at least one substituent selected from the group consisting of —F, —CF3, and —R2C(CF3)2OR3, where R2 is CH2 or C2H4, and R3 is H or an acid-labile protecting group, R4 is H, a C1-C15 alkyl group, or a C1-C15 substituent containing an ether bond, and m is 0 or 1, and n is an integer of 1-8. 3. A fluorine-containing vinyl ether according to claim 1, which is represented by the formula 2, where R1 is at least one substituent selected from the group consisting of —F, —CF3, and —R2C(CF3)2OR3, where R2 is CH2 or C2H4, and R3 is H or an acid-labile protecting group, and p is an integer of 1-5, and m is 0 or 1. 4. A fluorine-containing vinyl ether according to claim 1, which is represented by the formula 3, where R1 is at least one substituent selected from the group consisting of —F, —CF3, and —R2C(CF3)2OR3, where R2 is CH2 or C2H4, and R3 is H or an acid-labile protecting group, and q is an integer of 1-4, and m is 0 or 1. 5. A fluorine-containing vinyl ether according to claim 1, which is represented by the formula 4, where R1 is at least one substituent selected from the group consisting of —F, —CF3, and —R2C(CF3)2OR3, where R2 is CH2 or C2H4, and R3 is H or an acid-labile protecting group, and p is an integer of 1-5, and m is 0 or 1. 6. A fluorine-containing vinyl ether according to claim 1, which is represented by the formula 5, where n is an integer of 1-8. 7. A fluorine-containing vinyl ether according to claim 1, which is represented by the formula 6, where R5 is a C0-C5 alkyl group, and n is an integer of 1-8. 8. A fluorine-containing vinyl ether according to claim 1, which comprises a hexafluoroisopropanol unit represented by the formula 7, 9. A fluorine-containing vinyl ether according to claim 1, which is represented by one of the following formulas: where R3 is H or an acid-labile protecting group; R4 is H, a C1-C15 alkyl group, or a C1-C15 substituent having an ether bond; R5 is a C0-C5 alkyl group; R6 is H or F; and R7 is CF3, OH, CO2H, CO2R8, or OCOR8 where R8 is C1-C15 alkyl group. 10. A fluorine-containing polymer comprising a unit derived from a fluorine-containing vinyl ether according to claim 1. 11. A resist composition comprising a fluorine-containing polymer according to claim 10. 12. A fluorine-containing copolymer comprising: a first unit derived from a first monomer that is a fluorine-containing vinyl ether represented by the formula 8: where R1 is —H or a C1-C8 alkyl group that optionally contains an oxygen atom; and a second unit derived from a second monomer that is at least one selected from the group consisting of acrylic esters and methacrylic esters. 13. A fluorine-containing copolymer according to claim 12, wherein the second monomer contains an acid-labile protecting group. 14. A fluorine-containing copolymer according to claim 12, wherein the second monomer is a first methacrylic ester represented by the general formula 9: where R2 is —CH3 or —CH2CH3. 15. A fluorine-containing copolymer according to claim 12, wherein the second monomer is an acrylic or methacrylic ester comprising a lactone ring. 16. A fluorine-containing copolymer according to claim 12, wherein the second monomer is a second methacrylic ester represented by the formula 10: 17. A fluorine-containing copolymer according to claim 12, wherein the second monomer is a combination of first and second methacrylic esters represented by the formulas 9 and 10, and wherein the fluorine-containing vinyl ether is represented by the formula 11, where R2 is —CH3 or —CH2CH3. 18. A resist composition comprising a fluorine-containing copolymer according to claim 12.
BACKGROUND OF THE INVENTION The present invention relates to fluorine-containing vinyl ethers, their polymers and copolymers, and resist compositions using such polymers and copolymers. Hitherto, fluorine-containing polymers have been used in various fields, since they are superior in heat resistance and chemical resistance. In particular, amorphous fluorine-containing polymers are further superior in transparency, and therefore they have been used and studied in the fields of optical fiber and resist composition (see Japanese Patent Application Publication 2002-201231). In fact, the introduction of fluorine atoms lowers refractive index or improves transparency of the vacuum ultraviolet region light. In the development of resist compositions (see Y. Kamon et al., J. Photopolym. Sci. Technol., 15, 535 (2002)), now, a major resist type is a positive-type resist composition, in which an acid is generated by light irradiation and then solubility of a resin of the resist composition in alkali aqueous solution changes due to a chemical change of the resin by an action of the acid as a catalyst. In the trend toward shorter wavelength light source to manufacture smaller semiconductor devices, there are problems that resins (e.g., novolak resins and acrylic resins) used in current resists are insufficient in transparency. Thus, there are a demand for polymers that contain fluorine atoms, do not contain structures such as carbonyl, and are superior in heat resistance and solubility in various solvents, and a demand for monomers for synthesizing such polymers. Recent research and development have revealed that acrylic resins have a possibility to have relatively good resist characteristics (see Y. Kamon et al., J. Photopolym. Sci. Technol., 15, 535 (2002)). Acrylic resins, however, contain carbonyl structures that absorb vacuum ultraviolet light. Therefore, they are still not sufficient in transparency and are required to achieve further improvement. Since conventional fluorine-containing monomers are inferior in copolymerizability with acrylic or methacrylic esters, it has been difficult to copolymerize acrylic monomers with fluorine-containing monomers. Thus, there are a demand for fluorine-containing monomers that do not have carbonyl structures and are superior in copolymerizability with acrylic or methacrylic monomers and a demand for copolymers of such fluorine-containing monomers and acrylic or methacrylic monomers. SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide (a) monomers that can be a raw material for producing polymers, which are low in light scattering and absorption and high in transparency, (b) such polymers, and (c) resist compositions using such polymers. It is another object of the present invention to provide (a) fluorine-containing copolymers that are low in light scattering and absorption and high in transparency and (b) resist compositions using such copolymers. According to a first aspect of the present invention, there is provided a fluorine-containing vinyl ether represented by the formula 1, wherein R represents an organic group comprising at least one fluorine atom and a cyclic structure. The organic group (R) of the formula 1 may comprise: (a) the cyclic structure that is selected from the group consisting of cyclopentane ring, cyclohexane ring, norbornene ring, aromatic rings, tricyclodecane ring; and (b) at least one substituent that is selected from the group consisting of (—OH)m, (—R1)n, and —COOR4 where R1 is at least one substituent selected from the group consisting of —F, —CF3, and —R2C(CF3)2OR3, where R2 is CH2 or C2H4, and R3 is H or an acid-labile protecting group, R4 is H, a C1-C15 alkyl group, or a C1-C15 substituent containing an ether bond, and m is 0 or 1, and n is an integer of 1-8. The fluorine-containing vinyl ether of the formula 1 may be represented by the formula 2, where R1 is at least one substituent selected from the group consisting of —F, —CF3, and —R2C(CF3)2OR3, where R2 is CH2 or C2H4, and R3 is H or an acid-labile protecting group, and p is an integer of 1-5, and m is 0 or 1. The fluorine-containing vinyl ether of the formula 1 may be represented by the formula 3, where R1 is at least one substituent selected from the group consisting of —F, —CF3, and —R2C(CF3)2OR3, where R2 is CH2 or C2H4, and R3 is H or an acid-labile protecting group, and q is an integer of 1-4, and m is 0 or 1. The fluorine-containing vinyl ether of the formula 1 may be represented by the formula 4, where R1 is at least one substituent selected from the group consisting of —F, —CF3, and —R2C(CF3)2OR3, where R2 is CH2 or C2H4, and R3 is H or an acid-labile protecting group, and p is an integer of 1-5, and m is 0 or 1. The fluorine-containing vinyl ether of the formula 1 may be represented by the formula 5, where n is an integer of 1-8. The fluorine-containing vinyl ether of the formula 1 may be represented by the formula 6, where R5 is a C0-C5 alkyl group, and n is an integer of 1-8. The fluorine-containing vinyl ether of the formula 1 may comprise a hexafluoroisopropanol unit represented by the formula 7, According to the first aspect of the present invention, there are provided (a) a fluorine-containing polymer comprising a unit derived from the fluorine-containing vinyl ether of the formula 1, and (b) a resist composition comprising this fluorine-containing polymer. According to a second aspect of the present invention, there is provided a fluorine-containing copolymer comprising: a first unit derived from a first monomer that is a fluorine-containing vinyl ether represented by the formula 8: where R1 is —H or a C1-C8 alkyl group that optionally contains an oxygen atom; and a second unit derived from a second monomer that is at least one selected from the group consisting of acrylic esters and methacrylic esters. The second monomer may be a first methacrylic ester represented by the following formula 9. The second monomer may be an acrylic or methacrylic ester comprising a lactone ring. The second monomer may be a second methacrylic ester represented by the following formula 10. A fluorine-containing copolymer according to the second aspect of the present invention may comprise: a first unit derived from a first monomer that is a fluorine-containing vinyl ether represented by the formula 11; and a second unit derived from a second monomer that is a combination of first and second methacrylic esters represented by the formulas 9 and 10, where R2 is —CH3 or —CH2CH3. According to the present invention, there is provided a resist composition comprising a fluorine-containing copolymer of the second aspect of the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS The first aspect of the present invention is described in detail, as follows. The inventors unexpectedly found that a novel fluorine-containing vinyl ether according to the first aspect of the present invention is free from the above-mentioned conventional problems. Specifically, it was found that the fluorine-containing vinyl ether is capable of producing homopolymers and copolymerizing with various monomers, and that the resulting fluorine-containing polymers dissolve in various organic solvents and have high transparency. Therefore, they are useful as transparent resist compositions. Specific examples of the fluorine-containing vinyl ether include those represented by the following structural formulas: where R3 is H or an acid-labile protecting group; R4 is H, a C1-C15 alkyl group, or a C1-C15 substituent having an ether bond; R5 is a C0-C5 alkyl group; R6 is H or F; and R7 is CF3, OH, CO2H, CO2R8, or OCOR8 where R8 is C1-C15 alkyl group. Of the fluorine-containing vinyl ethers represented by the above structural formulas, those containing a hexafluoroisopropanol unit (—C(CF3)2—OH) or hexafluoroisopropanol derivative unit (—C(CF3)2—OR3, where R3 is a hydrogen or acid-labile protecting group optionally containing a hetero atom(s) such as oxygen) serve to improve adhesion of the resulting polymer to substrate. Examples of such acid-labile protecting group include t-butoxycarbonyl group, methoxymethyl group, 2-methyl-2-adamantyl ester group, and 2-ethyl-2-adamantyl ester group. Of fluorine-containing vinyl ethers, those containing structures, such as bicyclo[2.2.1]heptane and tricyclodecane, are preferable since polymers derived from those vinyl ethers are low in light absorption caused by double bond and are superior in heat resistance. It is possible to apply various known processes to produce the fluorine-containing vinyl ether of the present invention. For example, it is possible to treat a fluorine-containing alcohol with an alkali metal, followed by a reaction with acetylene or vinyl halide. As this alkali metal, it is possible to use various alkali metal compounds, such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, and potassium carbonate. It is known to synthesize vinyl ethers by vinyl exchange reaction using palladium as catalyst. This vinyl exchange reaction is conducted in the presence of a vinyl ether or alcohol to obtain the target vinyl ether. In particular, it is preferable to use a palladium catalyst, since reaction conditions become mild and since side reactions do not easily occur. It is possible to use a bivalent palladium such as palladium acetate Pd(OAc)2 as the palladium catalyst. It is also possible to use a ligand (to be bonded to palladium) for the purpose of controlling the reaction activity of palladium. The type of this ligand is not particularly limited. Preferable examples of this ligand include nitrogen-containing bidentate ones (e.g., 2,2′-bipyridyl and 1,10-phenanthroline) since the amount of by-products is small. It is possible to react palladium with ligand prior to the vinyl exchange reaction. Alternatively, it is possible to separately add palladium and ligand to the reaction system upon the vinyl exchange reaction to make ligand bonded to palladium.
<SOH> BACKGROUND OF THE INVENTION <EOH>The present invention relates to fluorine-containing vinyl ethers, their polymers and copolymers, and resist compositions using such polymers and copolymers. Hitherto, fluorine-containing polymers have been used in various fields, since they are superior in heat resistance and chemical resistance. In particular, amorphous fluorine-containing polymers are further superior in transparency, and therefore they have been used and studied in the fields of optical fiber and resist composition (see Japanese Patent Application Publication 2002-201231). In fact, the introduction of fluorine atoms lowers refractive index or improves transparency of the vacuum ultraviolet region light. In the development of resist compositions (see Y. Kamon et al., J. Photopolym. Sci. Technol., 15, 535 (2002)), now, a major resist type is a positive-type resist composition, in which an acid is generated by light irradiation and then solubility of a resin of the resist composition in alkali aqueous solution changes due to a chemical change of the resin by an action of the acid as a catalyst. In the trend toward shorter wavelength light source to manufacture smaller semiconductor devices, there are problems that resins (e.g., novolak resins and acrylic resins) used in current resists are insufficient in transparency. Thus, there are a demand for polymers that contain fluorine atoms, do not contain structures such as carbonyl, and are superior in heat resistance and solubility in various solvents, and a demand for monomers for synthesizing such polymers. Recent research and development have revealed that acrylic resins have a possibility to have relatively good resist characteristics (see Y. Kamon et al., J. Photopolym. Sci. Technol., 15, 535 (2002)). Acrylic resins, however, contain carbonyl structures that absorb vacuum ultraviolet light. Therefore, they are still not sufficient in transparency and are required to achieve further improvement. Since conventional fluorine-containing monomers are inferior in copolymerizability with acrylic or methacrylic esters, it has been difficult to copolymerize acrylic monomers with fluorine-containing monomers. Thus, there are a demand for fluorine-containing monomers that do not have carbonyl structures and are superior in copolymerizability with acrylic or methacrylic monomers and a demand for copolymers of such fluorine-containing monomers and acrylic or methacrylic monomers.
<SOH> SUMMARY OF THE INVENTION <EOH>It is therefore an object of the present invention to provide (a) monomers that can be a raw material for producing polymers, which are low in light scattering and absorption and high in transparency, (b) such polymers, and (c) resist compositions using such polymers. It is another object of the present invention to provide (a) fluorine-containing copolymers that are low in light scattering and absorption and high in transparency and (b) resist compositions using such copolymers. According to a first aspect of the present invention, there is provided a fluorine-containing vinyl ether represented by the formula 1, wherein R represents an organic group comprising at least one fluorine atom and a cyclic structure. The organic group (R) of the formula 1 may comprise: (a) the cyclic structure that is selected from the group consisting of cyclopentane ring, cyclohexane ring, norbornene ring, aromatic rings, tricyclodecane ring; and (b) at least one substituent that is selected from the group consisting of (—OH) m , (—R 1 ) n , and —COOR 4 where R 1 is at least one substituent selected from the group consisting of —F, —CF 3 , and —R 2 C(CF 3 ) 2 OR 3 , where R 2 is CH 2 or C 2 H 4 , and R 3 is H or an acid-labile protecting group, R 4 is H, a C 1 -C 15 alkyl group, or a C 1 -C 15 substituent containing an ether bond, and m is 0 or 1, and n is an integer of 1-8. The fluorine-containing vinyl ether of the formula 1 may be represented by the formula 2, where R 1 is at least one substituent selected from the group consisting of —F, —CF 3 , and —R 2 C(CF 3 ) 2 OR 3 , where R 2 is CH 2 or C 2 H 4 , and R 3 is H or an acid-labile protecting group, and p is an integer of 1-5, and m is 0 or 1. The fluorine-containing vinyl ether of the formula 1 may be represented by the formula 3, where R 1 is at least one substituent selected from the group consisting of —F, —CF 3 , and —R 2 C(CF 3 ) 2 OR 3 , where R 2 is CH 2 or C 2 H 4 , and R 3 is H or an acid-labile protecting group, and q is an integer of 1-4, and m is 0 or 1. The fluorine-containing vinyl ether of the formula 1 may be represented by the formula 4, where R 1 is at least one substituent selected from the group consisting of —F, —CF 3 , and —R 2 C(CF 3 ) 2 OR 3 , where R 2 is CH 2 or C 2 H 4 , and R 3 is H or an acid-labile protecting group, and p is an integer of 1-5, and m is 0 or 1. The fluorine-containing vinyl ether of the formula 1 may be represented by the formula 5, where n is an integer of 1-8. The fluorine-containing vinyl ether of the formula 1 may be represented by the formula 6, where R 5 is a C 0 -C 5 alkyl group, and n is an integer of 1-8. The fluorine-containing vinyl ether of the formula 1 may comprise a hexafluoroisopropanol unit represented by the formula 7, According to the first aspect of the present invention, there are provided (a) a fluorine-containing polymer comprising a unit derived from the fluorine-containing vinyl ether of the formula 1, and (b) a resist composition comprising this fluorine-containing polymer. According to a second aspect of the present invention, there is provided a fluorine-containing copolymer comprising: a first unit derived from a first monomer that is a fluorine-containing vinyl ether represented by the formula 8: where R 1 is —H or a C 1 -C 8 alkyl group that optionally contains an oxygen atom; and a second unit derived from a second monomer that is at least one selected from the group consisting of acrylic esters and methacrylic esters. The second monomer may be a first methacrylic ester represented by the following formula 9. The second monomer may be an acrylic or methacrylic ester comprising a lactone ring. The second monomer may be a second methacrylic ester represented by the following formula 10. A fluorine-containing copolymer according to the second aspect of the present invention may comprise: a first unit derived from a first monomer that is a fluorine-containing vinyl ether represented by the formula 11; and a second unit derived from a second monomer that is a combination of first and second methacrylic esters represented by the formulas 9 and 10, where R 2 is —CH 3 or —CH 2 CH 3 . According to the present invention, there is provided a resist composition comprising a fluorine-containing copolymer of the second aspect of the present invention. detailed-description description="Detailed Description" end="lead"?
20050504
20070814
20060406
68418.0
C07C4318
0
KEYS, ROSALYND ANN
FLUORINE-CONTAINING VINYL ETHERS, THEIR POLYMERS, AND RESIST COMPOSITIONS USING SUCH POLYMERS
UNDISCOUNTED
0
ACCEPTED
C07C
2,005
10,533,813
ACCEPTED
Operating method for a hydraulic injection valve comprising a piezoelectric actuator and a control unit
The invention relates to a method and a control unit for operating a hydraulic injection valve, which comprises at least one piezoelectric actuator (2), a displaceable component (3) and a hydraulic element (9) such as bearing or a transmission system. The use of a drive voltage (U) modifies the length of an actuator (2), which makes it possible to control the stroke of the displaceable component (a valve needle 3). The inventive control unit (10) produces a polarizing voltage (UB) which pre-stresses the actuator (2) and whose polarization direction is opposite to the polarization direction of said actuator (2). Said invention makes it possible to obtain the greater modification of the length when the actuator (2) operates in the polarization direction than the drive voltage starts at 0 volts, as it was in practice before. Said invention makes it possible to reduce energy consumption.
1-10. (canceled) 11. A method for operating an injection valve having at least one piezoelectric actuator, a displaceable component, a hydraulic element, and a common housing with said actuator, said component, and said element disposed therein, the method which comprises: reversibly controlling a stroke of the displaceable component by applying a drive voltage to the actuator; and biasing the actuator with a bias voltage having a bias opposing a polarization direction of the actuator. 12. The method according to claim 11, wherein the bias voltage is lower than a voltage causing a change in a polarity of the actuator. 13. The method according to claim 11, which comprises increasing the stroke of the displaceable component by applying the bias voltage. 14. The method according to claim 11, which comprises determining the bias voltage to effect a reduction in an energy consumption of the actuator. 15. The method according to claim 11, which comprises specifying the drive voltage together with bias voltage for setting a defined stroke of the displaceable component. 16. The method according to claim 15, which comprises determining a volume of material injected with the injection valve by way of the defined stroke of the displaceable component. 17. In a control unit for generating a drive voltage for an injection valve, the injection valve having at least one piezoelectric actuator, a displaceable component, and a hydraulic element commonly disposed in a common housing, and wherein a stroke of the displaceable component is reversibly controllable by application of a drive voltage to the actuator, the improvement which comprises: said control unit being configured to generate a bias voltage for biasing the actuator in opposition to a polarization direction of the actuator, and to set the drive voltage to increase the stroke of the displaceable component using the bias voltage. 18. The control unit according to claim 17, wherein the bias voltage is lower than a voltage that would result in a change in a polarity of the actuator. 19. In combination with a gasoline engine, the control unit according to claim 17 configured to drive an injection valve for injecting fuel into the gasoline engine. 20. In combination with a diesel engine, the control unit according to claim 17 configured to drive an injection valve for injecting fuel into the diesel engine.
The invention relates to a method for operating a hydraulic injection valve (injector) embodied having at least one piezoelectric actuator, a displaceable component and a hydraulic element, all of which are disposed in a common housing, wherein the stroke of said displaceable component can be reversibly controlled through the application of a drive voltage to the actuator, or relates, as the case may be, to a control unit of the kind cited in the independent claims 1 and 7. The use of a piezoelectric actuator operated by means of a drive voltage that corresponds to its polarization direction for controlling an injection valve, in particular for injecting fuel into an internal combustion engine, is already known. In order, for example, to directly actuate a valve needle of the injection valve, use is here made of the linear expansion which the actuator undergoes owing to the applied drive voltage. In the case of indirect use, the valve needle is by contrast opened through the impact of a shut-off valve (servo valve). The linear expansion (elongation) is by dint of the underlying physical principle a very small quantity. To achieve a useful linear expansion, multilayer actuators such as PMAs (piezoelectric multilayer actuator), for example, have been developed and the applied drive voltage selected to be as high as possible, for example 160V. The linear expansion of an actuator of said type is nevertheless only 0.12% to 0.14% of the length of the actuator in the discharged condition. The stroke increases less than proportionally when higher voltages are applied. The field strengths in the individual layers of the piezoceramic, customarily 80 μm thick, by contrast then exceed 2 kV/m. This could then lead to new problems such as electric voltage punctures that would irreversibly damage the piezoceramic. A large piezoceramic stroke, and hence valve needle stroke, is basically desirable particularly in the case of directly operated high-pressure injection valves since a large volume of injected material can also be achieved with a large stroke. This is a requirement in the case of, for instance, particularly powerful engines or racing engines. A large valve needle stroke is desirable in the case of indirectly operated injection valves particularly because production tolerances can be increased with cost advantages being achieved thereby. Attempts have also already been made to increase the actuator's overall length with the aim of increasing the valve needle stroke. Effective though this solution is, the piezoceramic is relatively expensive owing to the above-cited small elongation factor. It is furthermore known how to control the volume of injected material by means of a voltage pulse that is as long as possible. The length of the injection pulse is, however, very constrained in the case of an internal combustion engine by the physical boundary conditions, in particular by the optimal injection instant, exhaust gas requirements, temperature, engine-running culture etc. Only a very short injection pulse can be selected especially in the case of multiple injection where up to five injections take place in a single cycle at very short intervals. With known injection valves a hydraulic element (hydraulic bearing) is frequently also used as the play-compensating element for the purpose of avoiding parasitic gaps. The available actuator stroke can thereby be transmitted virtually to its full extent to the valve needle. By contrast, the method according to the invention for operating a hydraulic injection valve or, as the case may be, the control unit having the characterizing features of the independent claims 1 and 7 offers the advantage that the elongation of the actuator and hence the stroke of the displaceable component can be increased without the need to increase the effective electric field strength. Damage to the actuator is effectively precluded by the applied bias voltage. It is seen as particularly advantageous here that no physical design changes are needed on the injection valve itself so that the method according to the invention can be applied generally to commercially available injection valves. A larger volume of injected material is moreover also advantageously achieved on account of the increased stroke of the displaceable component. Advantageous developments of and improvements to the method cited in the independent claims 1 and 7 or, as the case may be, of and to the control circuit are provided by the measures cited in the dependent claims. It is seen as particularly advantageous here that the bias voltage is lower than a voltage that would result in changing the polarity of the actuator. This is because the actuator becomes shorter in this voltage range through the application of the bias voltage so that this shortening can be used as an additional elongation of the actuator when the drive voltage is applied. Since owing to the hydraulic element in the injection valve the additional elongation of the actuator is transmitted virtually fully to the displaceable component, its stroke is advantageously larger without the need to make mechanical changes to the injection valve. A further advantage is seen in the possibility also of achieving a reduction in energy consumption through the bias voltage. By displacing the drive voltage into the partially negative range energy consumption is reduced since, viewed in physical terms, this rises proportionally to the square of the voltage. A favorable solution is also seen in using the drive voltage employing the bias voltage for the purpose of setting a defined stroke of the displaceable component. A volume of fuel requiring to be injected into an internal combustion engine, for example, can be advantageously controlled in a simple manner by the defined stroke without the need to vary the length of the injection pulses. The volume of injected material can thus be controlled in a very simple manner by way of the amplitude of the drive voltage and/or bias voltage. An injection valve by means of which fuel such as gasoline or diesel is to be injected into an internal combustion engine under high pressure can be controlled particularly advantageously by means of the control unit. Owing to the low capacitances of the PMA piezoceramic, a very large number of switching times can be achieved with the actuator that are shorter than in the case of, for example, a solenoid valve, so that very large volumes are also possible in the case of multiple injections with precise fuel dosing. The object of the invention is to disclose a method for operating a hydraulic injection valve having a piezoelectric actuator or, as the case may be, to disclose a control unit that can manage large rates of flow. Said object is achieved by means of the features of the independent claims 1 and 7. An exemplary embodiment of the invention is shown in the drawing and is explained in more detail in the description that follows. FIG. 1 is a chart in which the elongation of a piezoelectric actuator is shown schematically as a function of the applied drive voltage, FIG. 2 shows two charts wherein one curve shows the elongation of the actuator without the use of a bias voltage and a second curve shows the elongation with the use of a bias voltage, FIG. 3a shows two charts in which the voltage curve for a control pulse is plotted over time, FIG. 3b shows two charts in which the valve needle stroke is plotted over time, FIG. 4 is a schematic of an injection valve where a bias voltage is not used and the displaceable component (valve needle) is closed, FIG. 5 shows the case presented in FIG. 3 using a bias voltage, FIG. 6 is a schematic of an injection valve where a bias voltage is not used but where the valve needle is open, and FIG. 7 shows the injection valve according to the invention having an open valve needle and using a bias voltage according to the invention. To better understand the invention it will first be explained with the aid of the charts in FIG. 1 how owing to the physical conditions the length Δl0 of an actuator changes as a function of an applied drive voltage U. The length of a PMA actuator depends not only on its outer electric field in keeping with the applied voltage but also on its previous electric history and its polarization state. In conjunction with the applied outer electric field, these two factors determine the current length of the PMA actuator. The invention now shows how the useful stroke of the actuator can be increased through skillful use of these relationships. A voltage whose polarity is opposed to the actuator's preferred polarization is understood to be a negative voltage. A positive voltage correspondingly acts in the actuator's preferred direction. The chart in FIG. 1 shows a total of four curves a to d which effect a corresponding linear expansion or stroke when a voltage is applied to an actuator that is, say, 30 mm long. Curve a shows the known standard case where the drive voltage is initially driven from a value of 0V to 160V as indicated by the direction of the arrow. The stroke is here typically 0 . . . 50 μm. If the voltage is returned from 160V to 0V, the result will be the typical top hysteresis loop. The actuator returns in the process to its original length, accordingly 0 μm at 0V. However, the stroke does not return immediately to 0 μm at the end of the voltage cycle. It is not the intention to deal in greater detail here with this effect known as slow ‘creeping’. Curve a therefore displays an amassing of measuring points in the area of the zero point. If a voltage 0V . . . −160V is then applied to the actuator in a second step according to the triangular curve b, the result in keeping with the lower branch of curve b will be a negative stroke of up to approximately −35 μm, which is to say a contraction of the actuator. The shortening of the actuator continues up to approximately −70V. The individual domains of the PMA actuator begin to reverse their polarity as the drive voltage U further increases negatively so that the length of the actuator will increase up to a value of −160V and a positive stroke of approximately 50 μm will be restored (left-hand rising branch of curve b). If the drive voltage is then returned from −160V to 0V, the stroke will also return to 0 μm. Another completion of the voltage cycle from 0V to −160V and back to 0V will produce curve c, whose course mirrors that of curve a. In a fourth step the drive voltage U was driven from 0V to +160V according to curve d, the result of which was again initially a further shortening of the actuator by approximately 35 μm at approximately 70V (curve d, lower branch). Polarity reversal again occurred at higher voltages so that the actuator expanded again. Returning the voltage U to 0V restored the original actuator length. The invention makes use of the range within which the actuator is shortened by the application of a bias voltage UB. The bias voltage UB is here lower than the voltage that results in polarity reversal and hence in elongation. In our example it is possible to use the bias voltage UB between 0 and down to almost −70V, and correspondingly between 0 and up to almost +70V with reversed polarity. A stroke of up to 85 μm is thus achieved according to the invention, while the stroke would only be 50 μm without a bias voltage UB. Provision is further made for controlling the elongation of the actuator and hence a predefined stroke of the displaceable component by way of the level of the bias voltage UB and/or of the drive voltage U. Said targeted controlling of the volume of fuel to be injected into an internal combustion engine is especially advantageous. The example given is naturally dependent on the selected piezoceramic and area of application used, which may also be temperature-dependent. However, a distinct increase in stroke is in principle always possible as the result of applying the bias voltage UB. The two hysteresis curves in the chart in FIG. 2 show how a PMA actuator can be operated with a negative bias (bias voltage). Curve e first shows a known drive cycle as previously described in connection with curve a in FIG. 1. The drive voltage U is again pulsed between 0 and 160V. The stroke is approximately 38 μm at most. The hysteresis curve f shows how the stroke can be increased to approximately 48 μm by applying a bias voltage UB=−30V. The useful stroke could thus be increased by 10 μm, equating to 26%. It is also of interest here to consider the actuator's energy requirements. The energy consumption is generally E=U2*C/2, where C is the actuator's capacitance requiring to be charged. If, for example, the operating voltage is lowered by just 20V, which is to say from U=0 . . . 160V to U=−20 . . . 140V, with the same stroke, then the two energies will behave in the manner (202+1402)/1602=0.78. The energy requirement in the displaced range is thus approximately 22% lower than when no bias voltage is applied. FIGS. 3a and 3b show charts of the type that can be used for, for example, PMA actuators (injectors) which are suitable for direct gasoline injection. The top curve g in FIG. 3a shows a drive voltage U in the range 0 . . . 160V as is known from the prior art. The lower curve h shows a drive curve according to the invention having a bias voltage UB=−20V, so that the drive voltage U passes through a cycle of between −20V and +160V. The corresponding stroke curves for the displaceable component were shown in FIG. 3b. The lower curve k corresponds to the drive voltage according to curve g in FIG. 3a. The top curve i shows an increased stroke of the type expected according to the invention in keeping with curve h in FIG. 3a. In this exemplary embodiment the stroke has therefore been increased by approximately 15%, with only a minimal load increase for the actuator since the lower voltage level was set to −20V. A twofold advantage can therefore be achieved by means of the invention: The stroke is increased although the load for the actuator remains virtually constant. To further illustrate the invention, the effects of the bias voltage UB on an injection valve 1 (injector), as used for, for example, injecting fuel into an internal combustion engine, are explained with the aid of FIGS. 4 to 7. For reasons of clarity, only a simple hydraulic high-pressure valve that can be used for, for instance, injecting gasoline has been shown for the injection valves illustrated here. The illustrations are not true to scale; they are in part shown enlarged since the changes in the actuator's length are in practice only in the μm range. FIG. 4 first shows the injection valve 1 known per se having an actuator 2, a hydraulic element 9 and a displaceable component 3, all of which are disposed in a common housing 8. The displaceable component 3 is in this case embodied as a valve needle which opens downward with the elongation of the actuator 3. In the rest condition, which is to say without the application of a drive voltage U, the valve head is pressed against a discharge aperture by a resetting spring 5 so that said aperture is closed. The actuator 2 is furthermore permanently connected to the shaft of the valve needle 3. The top end of said actuator is in contact with a hydraulic element 9 which can be filled via a leakage gap from a high-pressure fuel line 7. The hydraulic element 9 here acts as a hydraulic bearing having a very long time constant compared to the discharge time of the actuator 2, which can be 1 to 5 ms. The displaceable parts are appropriately sealed against the housing 8 by means of a bellows. The actuator 2 is supplied with power via leads 4. The pulsed drive voltage U is switched during the powering process from 0V to a required value, for example +160V, and is switched back to 0V on completion of a pre-specified pulse duration (see FIG. 3a). In the known injection valve 1 the hydraulic bearing 9 has a fluid level h0 which can slowly change via the leakage gap. The actuator 2 is of length l0 in the rest condition. The valve needle 3 opens according to curve k when the drive voltage U=160V is applied (see FIG. 3b). Alternative provision is however also made for opening the valve needle 3 inward through redesigning the injector 1. In particular for diesel injection, where even greater pressures are generated, the injector 3 can also be embodied having a servo valve, with said valve acting upon a hydraulic element then embodied as a hydraulic transmission system. The various types of injection valves are known per se, so their functioning does not have to be explained further. The mode of operation of the invention when used with an injection valve 1 according to FIG. 4 will now be explained with reference to FIG. 5. The designations are again the same as those used in FIG. 4. A bias voltage UB-having a polarity opposing the polarization direction of the actuator 2 is now, however, applied to the actuator 2 with the aid of a control unit 10. Let it be assumed in this example that the preferred polarization in the piezoceramic is positively oriented so that the bias voltage UB is <0V, for example −30V. As a result of this, the actuator 2 reduces its length to l0-δ. The hydraulic bearing 9 slowly fills up by the difference in length 5 until the hydraulic bearing 9 assumes the height h0+δ. The actuator 2 remains in this state until the control unit 10 generates a positive drive voltage U that effects a corresponding elongation of actuator 2. The two FIGS. 6 and 7 compare the functioning in the case of the known drive (FIG. 6) and in the case of the drive according to the invention (FIG. 7). According to FIG. 6 the length l0 of the actuator 2 now changes by the stroke Δl0 when the drive voltage U=160V is applied. The stroke Δl0 is in reality only approximately 0.13% of the length l0 and is here shown greatly enlarged. The hydraulic bearing 9 substantially retains its height h0. The small losses due to gap leakage are virtually negligible owing to the short operating time of typically 1 . . . 5 ms. The valve is likewise opened by the stroke Δl0 owing to its permanent connection to the valve needle 3. FIG. 7 shows the method according to the invention where a bias voltage UB that has shortened the actuator 2 has been applied to the injection valve 1. This case was explained previously in connection with FIG. 5. If, proceeding from the negative bias voltage UB, the drive voltage U=160V is likewise then applied by the control unit 10, the length of the actuator 2 will change to the value Δl0+δ. The stroke of the valve needle 3 will hence also increase to the value Δl0+δ and, compared to the known method, will exhibit a significant increase. The change in height δ of the hydraulic bearing 9 will be transmitted almost completely to the needle stroke if second-order effects such as the slightly altered rigidity of the hydraulic bearing resulting from the change in height are ignored. The needle stroke Δl0+δ according to the invention will in any event always be greater than in the case of the prior art. FIG. 7 shows an idealized snapshot of the condition immediately after the injector 2 has opened. The hydraulic bearing 9 empties over time and slowly drifts back. Specifying of the time constants should therefore be matched as precisely as possible to the real conditions. However, this harmonizing is of no fundamental significance for the method according to the invention.
20050502
20091229
20060119
63833.0
B05B108
0
GORDON, BRYAN P
OPERATING METHOD FOR A HYDRAULIC INJECTION VALVE COMPRISING A PIEZOELECTRIC ACTUATOR AND A CONTROL UNIT
UNDISCOUNTED
0
ACCEPTED
B05B
2,005
10,534,054
ACCEPTED
Pain relief agents
The present invention concerns the use of a heat shock polypeptide and/or an encoding nucleic acid sequence in the manufacture of a medicament for use in the relief of pain. In particular the invention concerns the use of chaperonin. The invention further provides methods of relieving pain medicaments containing the heat shock polypeptides.
1-28. (canceled) 29. A method of relieving pain comprising administering, to a subject in need thereof, a heat shock polypeptide or a nucleotide molecule encoding a heat shock polypeptide. 30. The method of claim 29, wherein the heat shock polypeptide is a chaperonin. 31. The method of claim 29, wherein the heat shock polypeptide is derived from a bacterium. 32. The method of claim 31, wherein the bacterium is a Mycobacterium. 33. The method of claim 32, wherein the Mycobacterium is Mycobacterium tuberculosis. 34. The method of any one of claims 29 to 33, wherein the nucleotide molecule comprises: (i) the nucleotide sequence of FIG. 1 and /or FIG. 2 and/or FIG. 3, or (ii) a sequence which has more than 66% identity to sequence (i), or a sequence which hybridises to sequence (i) under conditions of 2×SSC, 65° C. (wherein SCC=0.15M NaCl, 0.15M sodium citrate, pH 7.2), which encodes a functionally equivalent polypeptide to the sequence encoded by the nucleotide sequence of FIG. 1 and/or FIG. 2 and/or FIG. 3, or (iii) a fragment of sequence (i) or (ii) encoding a functionally equivalent polypeptide fragment. 35. The method of any one of claim 29 or 30, wherein the polypeptide comprises: (i) the amino acid sequence of FIG. 1 and/or FIG. 2 and/or FIG. 3, or (ii) a sequence which has more than 60% identity to sequence (i) which provides a functionally equivalent polypeptide, or (iii) a functionally equivalent fragment of sequence (i) or (ii). 36. The method of claim 35, wherein the functionally equivalent fragment is from 3 to 400 residues in length. 37. The method of claim 36, wherein the functionally equivalent fragment is from 3 to 100 residues in length. 38. The method of claim 34, wherein the nucleotide molecule encodes a functionally equivalent polypeptide fragment. 39. The method of claim 29, wherein the a heat shock polypeptide or a nucleotide molecule is administered in a composition comprising a pharmaceutically acceptable excipent, diluent or carrier. 40. The method of claim 29, wherein the a heat shock polypeptide or a nucleotide molecule is administered in a composition comprising at least one additive for assisting or augmenting the action of the nucleotide molecule or polypeptide. 41. The method of claim 40, wherein the additive is selected from at least one member of the group consisting of paracetamol, aspirin, ibuprofen, another non-steroidal anti-inflammatory drug (NSAID), a cylooxygenase-2-selective inhibitor (CSI), and an opiate. 42. The method of claim 40, wherein the composition is in a form which provides prolonged or sustained pain relief. 43. The method of claim 29, wherein said heat shock polypeptide or nucleotide molecule encoding a heat shock polypeptide are administered in single or divided doses at a daily dosage level of from 0.0001 to 100,000 mg. 44. The method of claim 43, wherein said daily dosage level is from 0.0001 to 1000 mg. 45. The method of claim 43, wherein the divided doses are administered between six and twelve hours apart. 46. The method of claim 45, wherein the divided doses are administered between nine and twelve hours apart. 47. The method of claim 43, wherein the divided doses are administered between twelve hours and twelve days apart. 48. The method of claim 43, wherein the divided doses are administered between twelve days and six months apart. 49. The method of claim 39, wherein the composition is formulated to permit administration by at least one route selected from the group consisting of intranasal, oral, parenteral, topical, ophthalmic, suppository, pessary and inhalation. 50. The method of claim 49, wherein the composition is formulated to permit administration by inhalation. 51. The method of claim 29, wherein the subject is a human or animal. 52. The method of claim 51, wherein the subject is a human. 53. The method of claim 29, wherein the pain is due to at least one member selected from the group consisting of backache, headache, toothache, earache, arthritis, gout, soft tissue trauma, ligament/tendon traumatic damage, a broken bone, cancer, post operative pain, menstrual pain, obstetric pain, renal tract pain, visceral pain, a burn, an abscess and an infection.
The present invention relates to pain relief agents and, in particular, pain relief agents which comprise one or more heat shock polypeptides. Heat shock polypeptides are a family of molecules found in all organisms, whose function is to aid the biological processing and stability of biological molecules (Zugel & Kauffman (1999) Role of heat shock polypeptides in protection from and pathogenesis of infectious diseases. Clin. Microbiol. Rev. (12)1: 19-39; Ranford et al. (2000) Chaperonins are cell signaling polypeptides:—the unfolding biology of molecular chaperones. Exp. Rev. Mol. Med., 15 September, www.ermn.cbcu.cam.ac.uk/00002015h.htm). Heat shock polypeptides are located in every cellular compartment, and possess the ability to interact with a wide range of biological molecules. In particular, the heat shock polypeptides aid and influence polypeptide folding and polypeptide translocation at any time from assembly through to disassembly of the polypeptide and any complexes thereof. The helper nature of the heat shock polypeptides has led to them to also being known as molecular chaperones (Laskey et al. (1978) Nucleosomes are assembled by an acidic polypeptide, which binds histones and transfers them to DNA. Nature (275): 416-420). Heat shock polypeptides are synthesised by cells in response to environmental stress, which includes, but is not limited to temperature changes (both increases and decreases), and pathophysiological signals such as cytokines. In response to the environmental stress, heat shock polypeptides use their ability to process other polypeptides to protect such polypeptides from any denaturation that may occur due to the presence of the stress. This mechanism also serves to protect cells which contain the protein. Chaperonin polypeptides are a subgroup of heat shock polypeptides whose role in polypeptide folding is well known. There are two families of chaperonin polypeptide, the chaperonin 60 (approximately 60 kDa) and chaperonin 10 (approximately 10 kDa) families (Ranford, 2000). The best characterised chaperonins are those derived from E. coli, from which the characteristic structure of chaperonin 60 and chaperonin 10 has been established. The chaperonin complexes of most other organisms also substantially conform to this characteristic structure. The characteristic structure of chaperonins is a complex formed from two heptamer rings (composed of seven chaperonin 60 monomers) which face one another and are capped by a heptamer ring composed of chaperonin 10 monomers. Conventionally, chaperonins assist polypeptide folding when the target polypeptide enters the central core of the ringed heptamers, and on the subsequent release of energy from ATP the target polypeptide is released from the central core by a conformational change in the chaperonin structure (Ranson et al. (1998) Review Article: Chaperones. Biochem. J (333): 233-242). Mycobacterium tuberculosis (M. tuberculosis) produces Chaperonin 60.1 (cpn 60.1), a polypeptide that is named based on its amino acid sequence identity to other known chaperoning. Further M. tuberculosis chaperonin polypeptides are chaperonin 10 (cpn 10) and chaperonin 60.2 (cpn 60.2). Chaperonin 60.2 exhibits 59.6% amino acid sequence identity and 65.6% nucleic acid sequence identity to cpn 60.1. Pain relief is usually achieved by oral or parenteral medication. Effective pain relief can be achieved in most cases with widely known pain relief drugs such as paracetamol, aspirin and other non-steroidal anti-inflammatory drugs (NSAIDS) such as ibuprofen, and cylooxygenase-2-selective inhibitors (CSIs). Narcotic analgesics act on specific receptors in the Central Nervous System (CNS). Codeine and dihydrocodeine are moderately potent narcotic analgesics and have a low potential for addiction. Other more potent narcotic analgesics, such as morphine and methadone can be used to control severe pain. A variety of problems exist with presently known pain relief agents. The drugs are relatively short acting and analgesia lasts for only a few hours. Repeated doses of the drug are usually necessary to control the pain. Sub-optimal pain relief is another common problem, leading to the patient increasing the dose, or changing medication. In the case of NSAIDS, unpleasant gastrointestinal side-effects such as dyspepsia and ulcers are common, and about two-thirds of users change brands of NSAIDS at least once because of adverse effects and poor efficacy (Steinfeld S and Bjorke P A. Results from a patient survey to assess gastrointestinal burden of non-steroidal anti-inflammatory drug therapy contrasted with a review of data from EVA to determine satisfaction with rofecoxib. Rheumatology (Oxford) 2002, 41(S1), 23-27.). In addition, NSAIDs and CSIs can give rise to cardiovascular complications (Hillis W S, (2000) Areas of emerging interest in analgesia: cardiovascular complications. Am. J. Ther. 9 (3) 259-69). Aspirin can cause Reye Syndrome in a small proportion of children, and thus aspirin is not available for use in children. Paracetamol has to be used with caution since, an overdose, is hepatotoxic (Cranswick, N., Coghlan D. Paracetamol efficacy and safety in children: the first 40 years (2000) Am. J. Ther. 7(2) 135-41). Narcotic analgesics have a variety of side-effects including drowsiness, constipation, nausea, headache and vertigo. Repeated administration of potent narcotic analgesics such as morphine can cause addiction. The present invention seeks to solve these problems in the following ways. An advantage of chaperonins as pain relief agents over current pain relief drugs is that they may have fewer adverse side-effects. It has been estimated that two billion people carry M. tuberculosis without developing Tuberculosis. Carriage of M. tuberculosis has not been associated with the side effects which are seen with commonly known pain-relief medication such as gastro-intestinal side-effects, cardiovascular complications, hepatotoxicity, Reye Syndrome or addiction. A further advantage over previously known pain relief agents is that, the analgesic affect of chaperonins will last longer. In a first aspect, the present invention provides the use of a heat shock polypeptide and/or its encoding nucleic acid sequence, in the manufacture of a medicament for use in the relief of pain. Preferably the heat shock polypeptide is a chaperonin. More preferably the chaperonin is derived from a bacterium. Yet more preferably the chaperonin is derived from Mycobacterium. Most preferably the chaperonin is derived from Mycobacterium tuberculosis. Preferably the nucleic acid comprises: (i) the nucleotide sequence of FIG. 1 and/or FIG. 2 and/or FIG. 3, or (ii) a sequence which has more than 66% identity to sequence (i), or a sequence which hybridises to sequence (i) under conditions of 2×SSC, 65° C. (wherein SCC=0.15M NaCl, 0.15M sodium citrate, pH 7.2) which encodes a functionally equivalent polypeptide to the sequence encoded by the nucleotide sequence of FIG. 1 and/or FIG. 2 and/or FIG. 3, or (iii) a fragment of sequence (i) or (ii) encoding a functionally equivalent polypeptide fragment. Preferably the heat shock polypeptide comprises: (i) the amino acid sequence of FIG. 1 and/or FIG. 2 and/or FIG. 3, or (ii) a sequence which has more than 60% identity to sequence (i) which provides a functionally equivalent polypeptide, or (iii) a functionally equivalent fragment of sequence (i) or (ii). Preferably the functionally equivalent fragments are from 3 to 400 residues in length. Yet more preferably the functionally equivalent fragments are from 3 to 100 residues in length. Preferably the nucleic acid molecule encodes a functionally equivalent fragment as defined above. Preferably the medicament further comprises a pharmaceutically acceptable excipent, diluent or carrier. More preferably the medicament is provided in combination with at least one additive for assisting or augmenting the action of the nucleic acid molecules or polypeptides. Yet more preferably the additive is selected from at least one of paracetamol, aspirin and other non-steroidal anti-inflammatory drugs (NSAIDS) such as ibuprofen, and cylooxygenase-2-selective inhibitors (CSIs), opiates, such as morphine and heroin. Preferably the medicament provides prolonged or sustained relief. Preferably the daily dosage level of will be from 0.0001 to 100,000 mg, administered in single or divided doses. More preferably the daily dosage level is 0.0001 to 1000 mg. In a preferred embodiment the time between dose administrations to the patient is between six and twelve hours. Preferably the time between dose administrations to the patient is between nine and twelve hours after the previous dose. In a further embodiment the time between dose administrations to the patient is between 12 days to 6 months. In a yet further preferred embodiment the time between dose administrations is between 12 hours to 12 days. Preferably the compositions of the invention are formulated to permit administration by at least one selected from the intranasal, oral, parenteral, topical, ophthalmic, suppository, pessary or inhalation routes. More preferably the compositions of the invention are formulated to permit administration by inhalation. Preferably the medicament is used in pain relief of a human or animal patient. Most preferably the patient is a human. In a second aspect, the present invention additionally provides a method comprising administering to a patient an amount of a medicament for the relief of pain, as described according to the first aspect of the invention. DEFINITIONS By “use in the relief of pain” we include any treatment which influences the pain felt by an individual, such influence including a delay in the onset, a reduction in the severity, a reduction of the duration, and/or the removal of the feeling of pain. By “additive” we mean an ingredient that is provided in addition to the main medicament that is pharmacologically active either independently or in combination with the main medicament, whereby its presence in the medicament assists or augments the action of the main medicament. By “hyperalgesia” we mean an earlier onset, an increase in the severity, an increase of the duration, and/or increased susceptibility to the feeling of pain. By “functionally equivalent” we mean polypeptides and polypeptide fragments, which possess a pain relieving activity. This activity is preferably substantially the same or more preferably greater than the pain relieving activity of chaperonins derived from Mycobacterium tuberculosis. Functional equivalence can be measured using the methods as described in the examples e.g. Paw latency on a heated plate. By “polypeptide” we also include peptides, proteins and peptidomimetic compounds. The term “peptidomimetic” refers to a compound that mimics the conformation and desirable features of a particular peptide as a therapeutic agent, but that avoids the undesirable features. By “identity” we mean the number or percentage (dependent on presentation of the results) of nucleic acid residues in a candidate sequence that are identical with the nucleic acid residues of the sequence of interest, after aligning the sequences and introducing gaps, if necessary to achieve maximum percent sequence identity, and not considering any conservative substitutions as part of the sequence identity. The percent sequence identity between two polypeptides may be determined using suitable computer programs, for example the GAP program of the University of Wisconsin Genetic Computing Group and it will be appreciated that percent identity is calculated in relation to polypeptides whose sequence has been aligned optimally. The alignment may alternatively be carried out using the Clustal W program (Thompson et al., (1994) Nucleic Acids Res. 22, 4673-80). The parameters used may be as follows: Fast pairwise alignment parameters: K-tuple(word) size; 1, window size; 5, gap penalty; 3, number of top diagonals; 5. Scoring method: x percent. Multiple alignment parameters: gap open penalty; 10, gap extension penalty; 0.05. Scoring matrix: BLOSUM. Preferred Embodiments Examples embodying certain preferred aspects of the invention will now be described with reference to the following figures in which:— PWL=Paw withdrawal latency PWD=Paw withdrawal duration VFF 4.31=Von Frey monofilament—4.31 calibre VFF 5.07=Von Frey monofilament—5.07 calibre FIG. 1—Amino acid and nucleic acid sequences of Mycobacterium tuberculosis Chaperonin 60.1. FIG. 2—Amino acid and nucleic acid sequences of Mycobacterium tuberculosis Chaperonin 60.2. FIG. 3—Amino acid and nucleic acid sequences of Mycobacterium tuberculosis Chaperonin 10. FIG. 4—Vomes Fry testing of Cpn 60.1. Shows the number of paw withdrawals per 10 trials with two different Von Frey monofilaments (4.31 and 5.07) in the presence and absence of Mtcpn60.1. FIG. 5—PWL/PWD testing of Cpn 60.1. Shows the duration of the responses of paw withdrawal in animals on the hot plate (upper panel) and on the cold plate (lower panel). FIG. 6—Vomes Fry testing of Cpn 60.2. Shows the number of paw withdrawals per 10 trials with two different Von Frey microfilament calibers in the presence and absence of Mtcpn60.2. FIG. 7—PWL/PWD testing of Cpn 60.2. Shows the duration of the responses of paw withdrawal in animals on the hot plate (upper panel) and on the cold plate (lower panel). FIG. 8—Vomes Fry testing of Cpn 10. Shows the number of paw withdrawals per 10 trials with two different Von Frey monofilaments in the presence and absence of Mtcpn10. FIG. 9—PWL/PWD testing of Cpn 10. Shows the duration of the responses of paw withdrawal in animals on the hot plate (upper panel) and on the cold plate (lower panel). EXAMPLE 1 Experimental Testing of Heat Shock Polypeptides In Vivo Experimental testing of heat shock polypeptides was investigated in test animals, separated into groups. Certain groups had induced hyperalgesia (i.e. an increased sensitivity to pain) and the effects of heat shock polypeptides on normal and hyperalgesic animals was observed and measured. Methods and Materials The analgesic effect of chaperonins can be measured using the model for inflammatory pain described in Kanaan et al. (1996) Pain 66, p 373-379, the disclosure of which is incorporated herein by reference. This model is based on endotoxin (ET)-induced inflammatory hyperalgesia in rats and mice. A brief description of the methods employed are presented below. Adult (200-250 g) male Sprague-Dawley rats and adult (20-30 g) male Balb/c mice were used. The animals were separated into four groups: Group 1—No injection. Group 2—Endotoxin only. Group 3—Endotoxin and Heat shock polypeptide. Group 4—Heat shock polypeptide only. Injection of Test Substrates Groups 2 and 3 were injected subcutaneously into the left hind paw with 1.25 μg ET prepared from Salmonella typhosa, 0901 (Difco, Detroit, Mich., USA). Groups 1 and 4 received no endotoxin but instead received sterile physiological saline injected in the same manner. Groups 3 and 4 additionally received 1 μg/ip of heat shock polypeptide injected in the same manner but not same mixture. Behavioral Observation After injection, each animal was observed 48 hours. Temperature Plate Test The animals were individually placed on a hot surface plate in which the temperature was adjusted between 52.8 and 53.3° C., or a cold surface plate in which the temperature was adjusted between 4.8 and 5.3° C. The latency of the first sign of paw licking or jumping to avoid heating pain was taken as an index of the pain threshold. Von Free Monofilament Testing for Mechanical Allodynia The method of Von Frey testing is disclosed in El-Khoury C et al. Neuroscience 2002, 112: 541-553 as incorporated herein. Briefly, rats are placed in individual compartments of an elevated cage with a floor made of wire grid. The plantar surface of the hind paws is stimulated by Von Frey monofilaments (VFF) with increasing force. Two different monofilaments are used of different calibers (VFF 4.31(lowest) and VFF 5.07(highest)) in the range of 15-18.5 mN and 100-110 mN respectively. Paw withdrawals per 10 trials are recorded. Experimental Protocols and Data Analysis To determine the effects of an ET and/or heat shock polypeptide, a set (n=5) of animals with representatives of each group (1 to 4) were subjected to the pain test for 3 consecutive days. Each animal was subjected to pain tests at the time intervals of 3, 6, 9 and 24 hours after the ET injection. The degree of significance of variations between control and experimental values for each pain test was assessed by ANOVA test. Heat Shock Polypeptides Tested The preferred methods were tested with the Mycobacterium tuberculosis chaperonin polypeptides, Cpn 60.1, Cpn 60.2 and Cpn 10. Synthesis of these proteins can be achieved by using the sequences encoding the polypeptide constituting the compound of the invention as disclosed herein in accordance with known techniques, appropriately modified in view of the teachings contained herein, to construct an expression vector, which is then used to transform an appropriate host cell for the expression and production of the polypeptide of the invention. Such techniques include those disclosed in U.S. Pat. No. 4,440,859 issued 3 Apr. 1984 to Rutter et al, U.S. Pat. No. 4,530,901 issued 23 Jul. 1985 to Weissman, U.S. Pat. No. 4,582,800 issued 15 Apr. 1986 to Crowl, U.S. Pat. No. 4,677,063 issued 30 Jun. 1987 to Mark et al, U.S. Pat. No. 4,678,751 issued 7 Jul. 1987 to Goeddel, U.S. Pat. No. 4,704,362 issued 3 Nov. 1987 to Itakura et al, U.S. Pat. No. 4,710,463 issued 1 Dec. 1987 to Murray, U.S. Pat. No. 4,757,006 issued 12 Jul. 1988 to Toole, Jr. et al, U.S. Pat. No. 4,766,075 issued 23 Aug. 1988 to Goeddel et al and U.S. Pat. No. 4,810,648 issued 7 Mar. 1989 to Stalker, all of which are incorporated herein by reference. Results The results are shown in FIGS. 4 to 9 and it is clear that all three of the chaperonins tested exhibit a strong analgesic effect. EXAMPLE 2 Analgesic Effect of cpn 60.1 FIG. 4 shows the number of paw withdrawals per 10 trials with two different Von Frey monofilaments (4.31 and 5.07) in the presence and absence of M. tuberculosis cpn 60.1. Both tests gave the same broad pattern of results. In track one of each time point, the negative control had a background of approximately one PWD. In track two, the positive control (injected ET or lipopolysacccharide) increased to a maximum of about 6 (VFF 4.31) and 9.5(VFF 5.07) PWD. Track three, demonstrates the effect of cpn60.l treatment of ET induced hyperalgesia, and shows a general reduction to background levels in PWD at time points 3-9 hours. Track 4 shows the effect of cpn60.1 injected on its own, i.e. that there is no difference over that seen in the non-injected control group. These results demonstrate that cpn60.1 reduces the hyperalgesia which is induced by endotoxin. FIG. 5 shows the duration of the responses of paw withdrawal in animals on the hot plate (PWL/Heat) and on the cold plate (PWD/Cold). The hot plate results show that there is no difference between the different time points and treatments, except for ET treated animals at time points 3-9 hours when the duration of latency is reduced to 4-5 seconds. The cold plate results show that none of the PWD are above the background with the exception of endotoxin injection, which shows a raised PWD at time points 3-9 hours. These results indicate that cpn 60.1 reduces hyperalgesia which is induced by endotoxin. EXAMPLE 3 Analgesic Effect of cpn 60.2 FIG. 6 shows the number of paw withdrawals per 10 trials with two different Von Frey microfilament calibers (VFF 4.31 and VFF 5.07) in the presence and absence of M. tuberculosis cpn60.2. Both tests broadly give the same pattern of results. In track one of each time point, the negative control had a background of approximately less than one PWD in VFF4.31 and less than 2.5 PWD in VFF 5.07. In track two, the positive control (injected ET or lipopolysacccharide) increased to a maximum of about 6 (VFF4.31) and 7.5 (VFF5.07) PWD. In track three, the effect of cpn60.2 treatment on ET induced hyperalgesia is shown, this demonstrates a reduction to background levels (control levels) in PWD at time points 3-9 hours. Track 4 shows the effect of cpn60.2 injected on its own such that there is no effect over that seen in the non-injected control group. These results demonstrate that cpn60.2 reduces the hyperalgesia which is induced by endotoxin. FIG. 7 shows the duration of the responses of paw withdrawal in animals on the hot plate (PWL/Heat) and on the cold plate (PWD/Cold). The hot plate results show that there is no difference between the different time points and treatments, except for ET treated animals at time points 3 and 6 hours when the duration of latency is reduced to 4-5 seconds. The cold plate results show that none of the PWD are above the background with the exception of ET which is considerably raised at time points 3-9 hours. These results indicate that this cpn 60.2 reduces hyperalgesia which is induced by endotoxin. EXAMPLE 4 Analgesic Effect of cpn 10 FIG. 8 shows the number of paw withdrawals per 10 trials with two different Von Frey monofilaments (VFF 4.31 and VFF 5.07) in the presence and absence of M. tuberculosis cpn10. Both tests broadly give the same pattern of results. In track one of each time point, the negative control had a background of approximately less than one PWD. In track two, the positive control (injected ET or lipopolysacccharide) increased to a maximum of about 6 (VFF 4.31) and 8 (VFF 5.07) PWD. In track three, the effect of cpn10 treatment of ET induced hyperalgesia on PWD is shown, for VFF 4.31 there is a reduction to background levels in PWD at time point 3 hours and just above background at time points 6 and 9 hours. For VFF 5.07 cpn10 shows a smaller reduction, to 3.5 at 3 hours, to 3 at 6 hours, to 2.5 at 9 hours and no reduction at 24 hours. Track 4 shows the effects of cpn10 injected on its own which demonstrates no effect over that seen in the non-injected group, except for VFF 4.31 where cpn10 induced approximately one PWD at the 3 hour time point. These results demonstrate that cpn10 reduces the hyperalgesia which is induced by ET. FIG. 9 shows the duration of the responses of paw withdrawal in animals on the hot plate (PWL/Heat) and on the cold plate (PWD/Cold). The heat plat test shows that there is no marked difference between the different time points and treatments, except for ET treated animals at time points 3-9 hours when the duration is reduced to 4-5 seconds. The cold plate test shows that none of the PWD are above the background with the exception of ET and ET in combination with cpn10 which is considerably raised at time points 3-9 hours. At these time points cpn10 still reduced the duration by about 50%. Hence, Cpn 10 is effective at reducing endotoxin induced hyperalgesia. EXAMPLE 5 Pharmaceutical Compositions A further aspect of the invention provides a pharmaceutical formulation comprising a heat shock polypeptide (the medicament) in admixture with a pharmaceutically or veterinarily acceptable adjuvant, diluent or carrier that is selected with regard to the intended route of administration and standard pharmaceutical practice. The carrier(s) must be “acceptable” in the sense of being compatible with the compound of the invention and not deleterious to the recipients thereof. Typically, the carriers will be water or saline which will be sterile and pyrogen free. The formulations may conveniently be presented in unit dosage form containing a daily dose or unit or an appropriate fraction thereof, of the medicament and may be prepared by any of the methods well known in the art of pharmacy. Such methods include the step of bringing into association the medicament with the carrier which constitutes one or more accessory ingredients. In general the formulations are prepared by uniformly and intimately bringing into association the medicament with liquid carriers or finely divided solid carriers or both, and then, if necessary, shaping the product. The compounds of the invention can be administered orally or by any parenteral route, in the form of a pharmaceutical formulation comprising the medicament, optionally in the form of a non-toxic organic, or inorganic, acid, or base, addition salt, in a pharmaceutically acceptable dosage form. Depending upon the disorder and patient to be treated, as well as the route of administration, the compositions may be administered at varying doses. The compounds of the invention can be administered alone but will generally be administered in admixture with a suitable pharmaceutical excipient diluent or carrier selected with regard to the intended route of administration and standard pharmaceutical practice. For example, the compounds of the invention can be administered orally, buccally or sublingually in the form of tablets, capsules, ovules, elixirs, solutions or suspensions, which may contain flavouring or colouring agents, for immediate-, delayed- or controlled-release applications. The compounds of invention may also be administered via intracavernosal injection. Such tablets may contain excipients such as microcrystalline cellulose, lactose, sodium citrate, calcium carbonate, dibasic calcium phosphate and glycine, disintegrants such as starch (preferably corn, potato or tapioca starch), sodium starch glycollate, croscarmellose sodium and certain complex silicates, and granulation binders such as polyvinylpyrrolidone, hydroxypropylmethylcellulose (HPMC), hydroxy-propylcellulose (HPC), sucrose, gelatine and acacia. Additionally, lubricating agents such as magnesium stearate, stearic acid, glyceryl behenate and talc may be included. Solid compositions of a similar type may also be employed as fillers in gelatine capsules. Preferred excipients in this regard include lactose, starch, a cellulose, milk sugar or high molecular weight polyethylene glycols. For aqueous suspensions and/or elixirs, the compounds of the invention may be combined with various sweetening or flavouring agents, colouring matter or dyes, with emulsifying and/or suspending agents and with diluents such as water, ethanol, propylene glycol and glycerin, and combinations thereof. The compounds of the invention can also be administered parenterally, for example, intravenously, intra-arterially, intraperitoneally, intrathecally, intraventricularly, intrasternally, intracranially, intra-muscularly or subcutaneously, or they may be administered by infusion techniques. They are best used in the form of a sterile aqueous solution which may contain other substances, for example, enough salts or glucose to make the solution isotonic with blood. The aqueous solutions should be suitably buffered (preferably to a pH of from 3 to 9), if necessary. The preparation of suitable parenteral formulations under sterile conditions is readily accomplished by standard pharmaceutical techniques well-known to those skilled in the art. Formulations suitable for parenteral administration include aqueous and non-aqueous sterile injection solutions which may contain anti-oxidants, buffers, bacteriostats and solutes which render the formulation isotonic with the blood of the intended recipient; and aqueous and non-aqueous sterile suspensions which may include suspending agents and thickening agents. The formulations may be presented in unit-dose or multi-dose containers, for example sealed ampoules and vials, and may be stored in a freeze-dried (lyophilised) condition requiring only the addition of the sterile liquid carrier, for example water for injections, immediately prior to use. Extemporaneous injection solutions and suspensions may be prepared from sterile powders, granules and tablets of the kind previously described. For oral and parenteral administration to human patients, the daily dosage level of the compounds of the invention will usually be from 0.0001 to 100,000 mg per adult, administered in single or divided doses. Thus, for example, the tablets or capsules of the compound of the invention may contain from 0.0001 mg to 100,000 mg of active compound for administration singly or two or more at a time, as appropriate. It is envisaged that a 500 mg tablet or capsule would be appropriate for single, repeat doses of one or more tablets or capsules. The physician in any event will determine the actual dosage, which will be most suitable for each individual patient, and it will vary with the age, weight and response of the particular patient. The above dosages are exemplary of the average case. There can, of course, be individual instances where higher or lower dosage ranges are merited and such are within the scope of this invention. The compounds of the invention can also be administered intranasally or by inhalation and are conveniently delivered in the form of a dry powder inhaler or an aerosol spray presentation from a pressurised container, pump, spray or nebuliser with the use of a suitable propellant, e.g. dichlorodifluoromethane, trichlorofluoromethane, dichlorotetrafluoro-ethane, a hydrofluoroalkane such as 1,1,1,2-tetrafluoroethane (HFA 134A, or 1,1,1,2,3,3,3-heptafluoropropane (HFA 227EA,), carbon dioxide or other suitable gas. In the case of a pressurised aerosol, the dosage unit may be determined by providing a valve to deliver a metered amount. The pressurised container, pump, spray or nebuliser may contain a solution or suspension of the active compound, e.g. using a mixture of ethanol and the propellant as the solvent, which may additionally contain a lubricant, e.g. sorbitan trioleate. Capsules and cartridges (made, for example, from gelatine) for use in an inhaler or insufflator may be formulated to contain a powder mix of a compound of the invention and a suitable powder base such as lactose or starch. Aerosol or dry powder formulations are preferably arranged so that each metered dose or “puff” contains between 0.001 mg and 2 g of a compound of the invention for delivery to the patient. It will be appreciated that he overall daily dose with an aerosol will vary from patient to patient, and may be administered in a single dose or, more usually, in divided doses throughout the day. Alternatively, the compounds of the invention can be administered in the form of a suppository or pessary, or they may be applied topically in the form of a lotion, solution, cream, ointment or dusting powder. The compounds of the invention may also be transdermally administered, for example, by the use of a skin patch. They may also be administered by the ocular route, particularly for treating diseases of the eye. For ophthalmic use, the compounds of the invention can be formulated as micronised suspensions in isotonic, pH adjusted, sterile saline, or, preferably, as solutions in isotonic, pH adjusted, sterile saline, optionally in combination with a preservative such as a benzylalkonium chloride. Alternatively, they may be formulated in an ointment such as petrolatum. For application topically to the skin, the compounds of the invention can be formulated as a suitable ointment containing the active compound suspended or dissolved in, for example, a mixture with one or more of the following: mineral oil, liquid petrolatum, white petrolatum, propylene glycol, polyoxyethylene polyoxypropylene compound, emulsifying wax and water. Alternatively, they can be formulated as a suitable lotion or cream, suspended or dissolved in, for example, a mixture of one or more of the following: mineral oil, sorbitan monostearate, a polyethylene glycol, liquid paraffin, polysorbate 60, cetyl esters wax, cetearyl alcohol, 2-octyldodecanol, benzyl alcohol and water. Formulations suitable for topical administration in the mouth include lozenges comprising the medicament in a flavoured basis, usually sucrose and acacia or tragacanth; pastilles comprising the medicament in an inert basis such as gelatine and glycerin, or sucrose and acacia; and mouth-washes comprising the medicament in a suitable liquid carrier. Generally, in humans, oral, topical or inhalation administration of the compounds of the invention is preferred, being the most convenient. In circumstances where the recipient suffers from a swallowing disorder or from impairment of drug absorption after oral administration, the drug may be administered parenterally, e.g. sublingually or buccally. For veterinary use, a compound of the invention is administered as a suitably acceptable formulation in accordance with normal veterinary practice and the veterinary surgeon will determine the dosing regimen and route of administration that will be most appropriate for a particular animal. EXAMPLE 6 Methods of Pain Relief The compounds of the invention will provide effective pain relief in the following incidences of pain: backache, headache, toothache, earache, Arthritis, Gout, soft tissue trauma, ligament/tendon traumatic damage, broken bones, Cancer, post operative pain, menstrual pain, obstetric pain, renal tract pain, visceral pain, burns, abscesses and other infections. The suggested treatment route and regimen for the treatment of any of these conditions is the administration of 0.1 mg to 1 gram once every 12 hours by inhalation delivered via an inhaler. However the skilled person would know that the most appropriate treatment regime would be dependent on the individual and the severity of the pain being felt.
20060322
20100629
20061109
79139.0
A61K3817
0
SWARTZ, RODNEY P
PAIN RELIEF AGENTS
UNDISCOUNTED
0
ACCEPTED
A61K
2,006
10,534,106
ACCEPTED
Antenna device
An antenna apparatus in which a combination of rectangular waveguides 9a and 10a and a combination of rectangular waveguides 9b and 10b are disposed bilateral symmetrically to each other, and a waveguide orthomode transducer 13 is disposed above a waveguide orthomode transducer 8 is provided. Therefore, the profile of the antenna apparatus can be reduced and the stability of installation of the antenna apparatus can be improved without impairing the electric characteristics of the antenna apparatus. Since the antenna apparatus has a bilateral symmetric structure, it excels in weight balance and offers stable performance from the viewpoint of mechanism.
1. An antenna apparatus comprising: a first orthomode transducer for combining first and second linearly polarized wave signals into a circularly polarized wave signal and for outputting the circularly polarized wave signal; a second orthomode transducer disposed above said first orthomode transducer, for separating the circularly polarized wave signal outputted thereto from said first orthomode transducer into third and fourth linearly polarized wave signals, and for outputting them; a first rectangular waveguide for propagating the third linearly polarized wave signal outputted thereto from said second orthomode transducer; a second rectangular waveguide disposed bilateral symmetrically to said first rectangular waveguide, for propagating the fourth linearly polarized wave signal outputted thereto from said second orthomode transducer; a third orthomode transducer disposed below said second orthomode transducer, for combining the third and fourth linearly polarized wave signals respectively propagated thereto by said first and the second rectangular waveguides into a circularly polarized wave signal, and for outputting the circularly polarized wave signal; and a radiator disposed above said third orthomode transducer, for emitting the circularly polarized wave signal outputted thereto from said third orthomode transducer to a reflector. 2. The antenna apparatus according to claim 1, characterized in that when said radiator receives a circularly polarized wave signal from said reflector, said third orthomode transducer separates the circularly polarized wave signal into third and fourth linearly polarized wave signals and outputs them, and, when receiving third and fourth linearly polarized wave signals from the first and the second rectangular waveguides, respectively, said second orthomode transducer combines said third and fourth linearly polarized wave signals into a circularly polarized wave signal, and outputs it, and said first orthomode transducer separates the circularly polarized wave signal into first and second linearly polarized wave signals and outputs them. 3. The antenna apparatus according to claim 2, characterized in that an elevation angle rotary member for supporting rotation of said radiator and said reflector in a direction of an elevation angle is inserted into each of said first and second rectangular waveguides. 4. The antenna apparatus according to claim 3, characterized in that an azimuth rotary member for supporting rotation of said radiator and said reflector in a direction of an azimuth angle is inserted between said first orthomode transducer and said second orthomode transducer. 5. The antenna apparatus according to claim 3, characterized in that said elevation angle rotary member is constructed using a coaxial-cable rotary joint. 6. The antenna apparatus according to claim 1, characterized in that each of said orthomode transducers comprises an electric wave branching means for, when receiving a circularly polarized wave signal, making a horizontally polarized electric wave included in the input circularly polarized wave signal branch toward first horizontal symmetrical directions, and making a vertically polarized electric wave included in the circularly polarized wave signal branch toward second horizontal symmetrical directions, a first electric wave propagating means for propagating a part of the horizontally polarized electric wave and a remaining part of the horizontally polarized electric wave branched by said electric wave branching means, for combining both the parts of the horizontally polarized electric wave into a linearly polarized wave signal, and for outputting it, and a second electric wave propagating means for propagating a part of the vertically polarized electric wave and a remaining part of the vertically polarized electric wave branched by said electric wave branching means, for combining both the parts of the vertically polarized electric wave into a linearly polarized wave signal, and for outputting it. 7. The antenna apparatus according to claim 2, characterized in that an RF module for amplifying a linearly polarized wave signal inputted thereto is inserted into each of said first and second rectangular waveguides. 8. The antenna apparatus according to claim 7, characterized in that said RF module comprises an amplification path for amplifying the linearly polarized wave signal outputted from said third orthomode transducer and for outputting the amplified, linearly polarized wave signal to said second orthomode transducer, and a passage path for outputting the linearly polarized wave signal outputted from said second orthomode transducer to said third orthomode transducer. 9. The antenna apparatus according to claim 2, characterized in that said apparatus is provided with an input/output means for inputting and outputting the first and second linearly polarized wave signals to and from the first orthomode transducer. 10. The antenna apparatus according to claim 3, characterized in that said reflector has a rectangular aperture having a larger size in a direction of an elevation angle axis than a size in a direction perpendicular to the elevation angle axis.
FIELD OF THE INVENTION The present invention relates to an antenna apparatus used in, for example, a VHF band, a UHF band, a microwave band, a millimeter wave band, etc. BACKGROUND OF THE INVENTION A prior art antenna apparatus is equipped with a circularly polarized wave generator and a polarizer, which are mounted on a rotary joint or a rotary mechanism, so as to allow integral rotation of a reflector and a primary radiator (refer to the following non-patent reference 1). [Non-Patent Reference 1] Takashi Kitsuregawa, ‘Advanced Technology in Satellite Communication Antennas: Electrical & Mechanical Design’, ARTECH HOUSE INC., pp. 232 to 235, 1990. A problem with the prior art antenna apparatus constructed as mentioned above is that while it can rotate both the reflector and the primary radiator in a direction of an elevation angle or in a direction of an azimuth angle, the part of the prior art antenna apparatus which is arranged above the rotary mechanism has a very large size and has a high position, and therefore the prior art antenna apparatus lacks in installation stability because the circularly polarized wave generator and the polarizer are placed on the rotary joint or the rotary mechanism. The present invention is made in order to solve the above-mentioned problem, and it is therefore an object of the present invention to provide an antenna apparatus having a low profile and high installation stability without impairing its electric characteristics. DISCLOSURE OF THE INVENTION An antenna apparatus in accordance with the present invention includes a first rectangular waveguide for propagating a third linearly polarized wave signal outputted thereto from a second orthomode transducer, a second rectangular waveguide for propagating a fourth linearly polarized wave signal outputted thereto from the second orthomode transducer, and a third orthomode transducer for combining the third and fourth linearly polarized wave signals respectively propagated thereto by the first and the second rectangular waveguides into a circularly polarized wave signal, and for outputting the circularly polarized wave signal to a radiator, the first and second rectangular waveguides being disposed bilateral symmetrically to each other and the third orthomode transducer being disposed below the second orthomode transducer. Therefore, the present embodiment offers an advantage of being able to reduce the profile of the antenna apparatus and to improve the installation stability without impairing the electric characteristics of the antenna apparatus. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 is a side view showing an antenna apparatus according to embodiment 1 of the present invention; FIG. 2 is a top plan view showing the antenna apparatus of FIG. 1; FIG. 3 is a side view showing an antenna apparatus according to embodiment 2 of the present invention; FIG. 4 is a top plan view showing waveguide orthomode transducers 1 and 8 of an antenna apparatus according to embodiment 3 of the present invention; FIG. 5 is a perspective diagram showing a waveguide orthomode transducer of FIG. 4; FIG. 6 is a top plan view showing a waveguide orthomode transducer of an antenna apparatus according to embodiment 4 of the present invention; FIG. 7 is a perspective diagram showing the waveguide orthomode transducer of FIG. 6; FIG. 8 is a side view showing an antenna apparatus according to embodiment 5 of the present invention; FIG. 9 is a top plan view showing the antenna apparatus of FIG. 8; FIG. 10 is a block diagram showing an RF module; FIG. 11 is a block diagram showing an RF module; and FIG. 12 is a side view showing an antenna apparatus according to embodiment 7 of the present invention. PREFERRED EMBODIMENTS OF THE INVENTION Hereafter, in order to explain this invention in greater detail, the preferred embodiments of the present invention will be described with reference to the accompanying drawings. Embodiment 1 FIG. 1 is a side view showing an antenna apparatus according to embodiment 1 of the present invention, and FIG. 2 is a top plan view showing the antenna apparatus of FIG. 1. In the figure, a waveguide orthomode transducer 1 constitutes a first orthomode transducer that when receives both a linearly polarized wave signal L1 (i.e., a first linearly polarized wave signal) via an input/output terminal P1 and a linearly polarized wave signal (i.e., a second linearly polarized wave signal) L2 having the same amplitude as the linearly polarized wave signal L1 via an input/output terminal P2 and having a phase difference of 90 degrees with respect to the linearly polarized wave signal L1, combines the linearly polarized wave signal L1 and the linearly polarized wave signal L2 into a composite signal and then outputs a circularly polarized wave signal C1 that is the composite signal via an input/output terminal P3. A rectangular-to-circular waveguide transformer 4 is connected to the waveguide orthomode transducer 1, and propagates the circularly polarized wave signal C1 outputted from the input/output terminal P3 of the waveguide orthomode transducer 1 to another rectangular-to-circular waveguide transformer 6. The other rectangular-to-circular waveguide transformer 6 propagates the circularly polarized wave signal C1 propagated thereto by the rectangular-to-circular waveguide transformer 4 to a waveguide orthomode transducer 8. A rectangular waveguide rotary joint 5 is inserted between the rectangular-to-circular waveguide transformer 4 and the other rectangular-to-circular waveguide transformer 6, and constitutes an azimuth rotary member that supports rotation of members (for example, a primary radiator 14, a main reflector 16, and a subreflector 15), which are disposed above the rectangular waveguide rotary joint 5, in a direction of an azimuth angle under the control of an azimuth rotary mechanism 7. It is assumed that the rectangular waveguide rotary joint 5 is constructed so that a circular-waveguide TE11 mode is defined as a propagation mode. The azimuth rotary mechanism 7 is a mechanical unit for rotating the rectangular waveguide rotary joint 5 about an azimuth axis D. The waveguide orthomode transducer 8 is disposed above the waveguide orthomode transducer 1, and constitutes a second orthomode transducer that, when receiving the circularly polarized wave signal C1 outputted thereto from the rectangular-to-circular waveguide transformer 6 via the input/output terminal P4, separates the circularly polarized wave signal C1 into a linearly polarized wave signal (i.e., a third linearly polarized wave signal) L3 and a linearly polarized wave signal (i.e., a fourth linearly polarized wave signal) L4 having the same amplitude as the linearly polarized wave signal L3 and having a phase difference of 90 degrees with respect to the linearly polarized wave signal L3, and then outputs the third and fourth linearly polarized wave signals L3 and L4 via input/output terminals P5 and P6, respectively. A rectangular waveguide 9a propagates the linearly polarized wave signal L3 outputted thereto via the input/output terminal P5 of the waveguide orthomode transducer 8 to another rectangular waveguide 10a, and the other rectangular waveguide 10a the propagates the linearly polarized wave signal L3 to a waveguide orthomode transducer 13. The rectangular waveguides 9a and 10a constitute a first rectangular waveguide. A rectangular waveguide 9b propagates the linearly polarized wave signal L4 outputted thereto via the input/output terminal P6 of the waveguide orthomode transducer 8 to another rectangular waveguide 10b, and the other rectangular waveguide 10b then propagates the linearly polarized wave signal L4 to a waveguide orthomode transducer 13. The rectangular waveguides 9b and 10b constitute a second rectangular waveguide. The rectangular waveguides 9a and 9b are formed so that they are bilateral symmetric to each other, and the rectangular waveguides 10a and 10b are formed so that they are bilateral symmetric to each other. A rectangular waveguide rotary joint 11a is inserted between the rectangular waveguide 9a and the rectangular waveguide 10a, and constitutes an elevation angle rotary member that supports rotation of the waveguide orthomode transducer 13, the primary radiator 14, the subreflector 15, and the main reflector 16 in a direction of an elevation angle under the control of an elevation angle rotary mechanism 12a. The elevation angle rotary mechanism 12a is a mechanical unit for rotating the rectangular waveguide rotary joint 11a around an elevation angle axis E. Another rectangular waveguide rotary joint 11b is also inserted between the rectangular waveguide 9b and the rectangular waveguide 10b, and constitutes an elevation angle rotary member that supports rotation of the waveguide orthomode transducer 13, the primary radiator 14, the subreflector 15, and the main reflector 16 in the direction of the elevation angle under the control of an elevation angle rotary mechanism 12b. The elevation angle rotary mechanism 12b is a mechanical unit for rotating the rectangular waveguide rotary joint 11b around the elevation angle axis E. The waveguide orthomode transducer 13 is disposed below the waveguide orthomode transducer 8, and constitutes a third orthomode transducer that when receiving both the linearly polarized wave signal L3 propagated by the rectangular waveguide 10a via an input/output terminal P7 and the linearly polarized wave signal L4 propagated by the rectangular waveguide 10b via an input/output terminal P8, combines the linearly polarized wave signals L3 and L4 into a composite signal, and then outputs a circularly polarized wave signal C2 which is the composite signal via an input/output terminal P9. The primary radiator 14 is disposed above the waveguide orthomode transducer 13, and emits the circularly polarized wave signal C2 outputted thereto via the input/output terminal P9 of the waveguide orthomode transducer 13 to the subreflector 15. The subreflector 15 is disposed so that its reflecting surface is oriented in a downward direction and reflects the circularly polarized wave signal C2 emitted from the primary radiator 14 toward the main reflector 16. The main reflector 16 is disposed so that its reflecting surface is oriented in an upward direction and emits the circularly polarized wave signal C2 reflected by the subreflector 15 in the air. A supporting structure 17 supports the subreflector 15 and the main reflector 16 so that they are apart from each other and are aligned along the azimuth axis. Next, the operation of the antenna apparatus in accordance with this embodiment of the present invention will be explained. A case where the antenna apparatus emits a circularly polarized wave signal C2 toward a target will be explained first. When receiving both a linearly polarized wave signal L1 via the input/output terminal P1 and a linearly polarized wave signal L2 having the same amplitude as the linearly polarized wave signal L1 via the input/output terminal P2 and having a phase difference of 90 with respect to the linearly polarized wave signal L1, the waveguide orthomode transducer 1 combines the linearly polarized wave signals L1 and L2 into a composite signal and then outputs a circularly polarized wave signal C1 that is the composite signal via the input/output terminal P3. When receiving the circularly polarized wave signal C1 from the input/output terminal P3 of the waveguide orthomode transducer 1, the rectangular-to-circular waveguide transformer 4 propagates the circularly polarized wave signal C1 to the rectangular-to-circular waveguide transformer 6, and the rectangular-to-circular waveguide transformer 6 then propagates the circularly polarized wave signal C1 propagated by the rectangular-to-circular waveguide transformer 4 to the waveguide orthomode transducer 8. When receiving the circularly polarized wave signal C1 propagated by the rectangular-to-circular waveguide transformer 6 from the input/output terminal P4, the waveguide orthomode transducer 8 separates the circularly polarized wave signal C1 into linearly polarized wave signals L3 and L4, and then outputs the linearly polarized wave signal L3 via the input/output terminal P5 and outputs the linearly polarized wave signal L4 having the same amplitude as the linearly polarized wave signal L3 and having a phase difference of 90 degrees with respect to the linearly polarized wave signal L3 via the input/output terminal P6. When receiving the linearly polarized wave signal L3 from the input/output terminal P5 of the waveguide orthomode transducer 8, the rectangular waveguide 9a propagates the linearly polarized wave signal L3 to the rectangular waveguide 10a, and the rectangular waveguide 10a then propagates the linearly polarized wave signal L3 to the waveguide orthomode transducer 13. On the other hand, when receiving the linearly polarized wave signal L4 from the input/output terminal P6 of the waveguide orthomode transducer 8, the rectangular waveguide 9b propagates the linearly polarized wave signal L4 to the rectangular waveguide 10b, and the rectangular waveguide 10b then propagates the linearly polarized wave signal L4 to the waveguide orthomode transducer 13. When receiving both the linearly polarized wave signal L3 propagated by the rectangular waveguide 10a via the input/output terminal P7 and the linearly polarized wave signal L4 propagated by the rectangular waveguide 10b via the input/output terminal P8, the waveguide orthomode transducer 13 combines the linearly polarized wave signals L3 and L4 into a composite signal, and then outputs a circularly polarized wave signal C2 which is the composite signal via the input/output terminal P9. When receiving the circularly polarized wave signal C2 from the input/output terminal P9 of the waveguide orthomode transducer 13, the primary radiator 14 emits the circularly polarized wave signal C2 to the subreflector 15. As a result, the circularly polarized wave signal C2 is reflected toward the main reflector 16 by the subreflector 15, and is further reflected toward the air by the main reflector 16. Although the rectangular waveguide rotary joints 11a and 11b rotate the waveguide orthomode transducer 13, the primary radiator 14, the subreflector 15, and the main reflector 16 around the elevation angle axis E under the control of the elevation angle rotary mechanisms 12a and 12b, and the rectangular waveguide rotary joint 5 rotates the waveguide orthomode transducer 8, the rectangular waveguides 9a, 9b, 10a, and 10b, the waveguide orthomode transducer 13, the primary radiator 14, the subreflector 15, and the main reflector 16 around the azimuth axis D under the control of the azimuth rotary mechanism 7, the amplitude and phase relationship between the linearly polarized wave signals L3 and L4 inherits the amplitude and phase relationship between the linearly polarized wave signals L1 and L2 because the rectangular waveguides 9a and 9b are formed so that they are bilateral symmetric to each other and the rectangular waveguides 10a and 10b are formed so that they are bilateral symmetric to each other. In other words, the linearly polarized wave signal L3 and the linearly polarized wave signal L4 are equal in amplitude, and are 90 degrees out of phase with each other. Therefore, even if the waveguide orthomode transducer, the primary radiator, the subreflector, and the main reflector are driven over a large angle range with respect to the direction of the elevation angle, the good circularly polarized wave state of the circularly polarized wave signal C2 outputted from the input/output terminal P9 of the waveguide orthomode transducer 13 can be maintained. The antenna apparatus can thus emit a good-quality circularly polarized wave signal in a wide band. Since the rectangular waveguide rotary joint 5 is constructed so that the circular-waveguide TE11 mode is defined as the propagation mode, it can drive the waveguide orthomode transducer, the rectangular waveguides, the other waveguide orthomode transducer, the primary radiator, the subreflector, and the main reflector over a large angle range with respect to the direction of the azimuth angle without impairing the electrical characteristics of the antenna apparatus of this embodiment. Therefore, the antenna apparatus can transmit the circularly polarized wave signal while carrying out scanning of the antenna beam over a wide angle. It can be further expected that the antenna apparatus exhibits good passage and reflection characteristics over a wide band. Next, a case where the antenna apparatus receives a circularly polarized wave signal C2 reflected from a target will be explained. When receiving the circularly polarized wave signal C2, the main reflector 16 reflects the circularly polarized wave signal C2 toward the subreflector 15. The circularly polarized wave signal C2 is then reflected by the subreflector 15 and is made to be incident upon the primary radiator 14. When receiving the circularly polarized wave signal C2, the primary radiator 14 outputs the circularly polarized wave signal C2 to the waveguide orthomode transducer 13. When receiving the circularly polarized wave signal C2 outputted from the primary radiator 14 via the input/output terminal P9, the waveguide orthomode transducer 13 separates the circularly polarized wave signal C2 into linearly polarized wave signals L3 and L4, and then outputs the linearly polarized wave signal L3 via the input/output terminal P7 and also outputs the linearly polarized wave signal L4 having the same amplitude as the linearly polarized wave signal L3 and having a phase difference of 90 degrees with respect to the linearly polarized wave signal L3 via the input/output terminal P8. When receiving the linearly polarized wave signal L3 from the input/output terminal P7 of the waveguide orthomode transducer 13, the rectangular waveguide 10a propagates the linearly polarized wave signal L3 to the rectangular waveguide 9a, and the rectangular waveguide 9a then propagates the linearly polarized wave signal L3 to the waveguide orthomode transducer 8. On the other hand, when receiving the linearly polarized wave signal L4 from the input/output terminal P8 of the waveguide orthomode transducer 13, the rectangular waveguide 10b propagates the linearly polarized wave signal L4 to the rectangular waveguide 9b, and the rectangular waveguide 9b then propagates the linearly polarized wave signal L4 to the waveguide orthomode transducer 8. When receiving the linearly polarized wave signal L3 propagated by the rectangular waveguide 9a via the input/output terminal P5 and also receiving the linearly polarized wave signal L4 propagated by the rectangular waveguide 9b via the input/output terminal P6, the waveguide orthomode transducer 8 combines the linearly polarized wave signals L3 and L4 into a composite signal, and then outputs a circularly polarized wave signal C1 which is the composite signal via the input/output terminal P4. When receiving the circularly polarized wave signal C1 from the input/output terminal P4 of the waveguide orthomode transducer 8, the rectangular-to-circular waveguide transformer 6 propagates the circularly polarized wave signal C1 to the other rectangular-to-circular waveguide transformer 4, and the other rectangular-to-circular waveguide transformer 4 then propagates the circularly polarized wave signal C1 propagated by the rectangular-to-circular waveguide transformer 6 to the waveguide orthomode transducer 1. When receiving the circularly polarized wave signal C1 propagated by the rectangular-to-circular waveguide transformer 4 from the input/output terminal P3, the waveguide orthomode transducer 1 separates the circularly polarized wave signal C1 into linearly polarized wave signals L1 and L2, and then outputs the linearly polarized wave signal L1 via the input/output terminal P1 and also outputs the linearly polarized wave signal L2 having the same amplitude as the linearly polarized wave signal L1 and having a phase difference of 90 degrees with respect to the linearly polarized wave signal L1 via the input/output terminal P2. The antenna apparatus carries out reception of a circularly polarized wave signal in this way. As in the case of transmission of a circularly polarized wave signal, the antenna apparatus can drive the waveguide orthomode transducer, the rectangular waveguides, the other waveguide orthomode transducer, the primary radiator, the subreflector, and the main reflector over a wide angle range in both the direction of the elevation angle and the direction of the azimuth angle so as to receive a circularly polarized wave signal in good condition. As shown in FIG. 2, the main reflector 16 is an antenna having a rectangular aperture having a length “M” which is a size in the direction of the elevation angle axis of rotation E and a length “W” (M>W) which is a size in a direction (referred to as a width direction from here on) perpendicular to the elevation angle axis of rotation E. The subreflector 15 is also an antenna having a rectangular aperture whose size in the direction of the elevation angle axis of rotation E is larger than its size in the width direction. The elevation angle axis of rotation E is made to pass through an almost central position of the distance (i.e., the height) H between the main reflector and the subreflector in the direction (i.e., the height direction) of the azimuth axis of rotation D of the main reflector 16 (refer to FIG. 1), and to pass through an almost central position of the main reflector 16 with respect to the width direction. Therefore, when the main reflector 16 and the subreflector 15 are rotated around the elevation angle axis of rotation E, a movable area in which the main reflector 16 and the subreflector 15 can be moved exists within a circle which is delineated by the outermost edge of the main reflector 16, the circle having a center oh the elevation angle axis of rotation E. The movable area defined by this circle is very small as compared with that provided by prior art antenna apparatus, and the profile of the antenna apparatus of this embodiment does not increase even if the main reflector 16 and the subreflector 15 are made to rotate around the elevation angle axis of rotation E. The main reflector 16 and the subreflector 15 are shaped, and receive and reflect almost all of electromagnetic waves supplied thereto. Since a concrete procedure for shaping the main reflector 16 and the subreflector 15 is well known in this technical field, the detailed explanation of the concrete procedure for shaping the main reflector 16 and the subreflector 15 will be omitted hereafter. The procedure for shaping the main reflector and the subreflector is a technique for controlling the aperture shape and aperture distribution of an antenna, which is described in detail in, for example, IEE Proc. Microw. Antennas Propag. Vol. 146, No. 1, pp. 60 to 64, 1999. In this embodiment, the main reflector and the subreflector are shaped so that the aperture of the antenna has a nearly rectangular shape and the aperture distribution becomes uniform. As can be seen from the above description, in accordance with this embodiment 1, the rectangular waveguides 9a and 10a are formed so that they are bilateral symmetric to each other, the rectangular waveguides 9b and 10b are formed so that they are bilateral symmetric to each other, and the waveguide orthomode transducer 13 is disposed below the waveguide orthomode transducer 8. Therefore, the present embodiment offers an advantage of being able to reduce the profile of the antenna apparatus and to improve the installation stability without impairing the electric characteristics of the antenna apparatus. In other words, the present embodiment offers an advantage of being able to achieve a downsizing and a low profile of the antenna apparatus by reducing the profile of the antenna apparatus. In addition, since the antenna apparatus has a bilateral symmetric structure, it excels in weight balance and offers stable performance from the viewpoint of mechanism. Embodiment 2 In above-mentioned embodiment 1, the rotation of the antenna apparatus around the elevation angle axis of rotation E is implemented by inserting each of the rectangular waveguide rotary joints 11a and 11b between rectangular waveguides, as previously mentioned. As shown in FIG. 3, the rotation of the antenna apparatus around the elevation angle axis of rotation E can be alternatively implemented by inserting each of coaxial-cable rotary joints 22a and 22b between rectangular waveguides. In other words, a coaxial-cable-to-rectangular-waveguide converter 21a is connected to a rectangular waveguide 9a and another coaxial-cable-to-rectangular-waveguide converter 23a is connected to a rectangular waveguide 10a, and the coaxial-cable rotary joint 22a is inserted between the coaxial-cable-to-rectangular-waveguide converter 21a and the other coaxial-cable-to-rectangular-waveguide converter 23a. In addition, a coaxial-cable-to-rectangular-waveguide converter 21b is connected to a rectangular waveguide 9b and another coaxial-cable-to-rectangular-waveguide converter 23b is connected to a rectangular waveguide 10b, and the coaxial-cable rotary joint 22b is inserted between the coaxial-cable-to-rectangular-waveguide converter 21b and the other coaxial-cable-to-rectangular-waveguide converter 23b. Thus, the antenna apparatus according to this embodiment is partially constructed of coaxial cables. Therefore, the present embodiment offers an advantage of being able to transmit and receive a good-quality circularly polarized wave signal in a further wide band without impairing a downsizing and a low profile of the antenna apparatus, and without preventing wide angle scanning. Embodiment 3 In either of above-mentioned embodiments 1 and 2, the internal structure of each of the waveguide orthomode transducers 1, 8, and 13 is not illustrated. Each of the waveguide orthomode transducers 1, 8, and 13 can have an internal structure as shown in FIGS. 4 and 5. The waveguide orthomode transducers 1, 8, and 13 can have the same structure. For the sake of simplicity, FIGS. 4 and 5 show the structure of the waveguide orthomode transducer 8. In FIGS. 4 and 5, when receiving a circularly polarized wave signal C1 outputted thereto by a rectangular-to-circular waveguide transformer 6 via an input/output terminal P4, a square main waveguide 31 transmits the circularly polarized wave signal (including a vertically polarized electric wave and a horizontally polarized electric wave) C1. Another square main waveguide 32 has an aperture diameter larger than that of the square main waveguide 31 and a level difference at a connecting portion where it is connected to the square main waveguide 31, the level difference being sufficiently smaller than the free space wavelength of an available frequency band. The other square main waveguide 32 transmits the circularly polarized wave signal (including a vertically polarized electric wave and a horizontally polarized electric wave) C1 transmitted thereto by the square main waveguide 31. A short-circuit plate 33 blocks one terminal of the square main waveguide 32, and a quadrangular-pyramid-shaped metallic block 34 is disposed on the short-circuit plate 33 and separates the circularly polarized wave signal into the vertically polarized electric wave and the horizontally polarized electric wave. An electric wave branching means comprises the square main waveguides 31 and 32, the short-circuit plate 33, and the quadrangular-pyramid-shaped metallic block 34. Rectangular waveguide branching units 35a to 35d are connected to the square main waveguide 32 so that they are perpendicular to the four waveguide axes of the square main waveguide 32, respectively. Rectangular waveguide multi-stage transformers 36a to 36d are connected to the rectangular waveguide branching units 35a to 35d, respectively, and have waveguide axes that are curved in an H plane and have aperture diameters which decrease with distance from the rectangular waveguide branching units 35a to 35d, respectively. A rectangular waveguide E-plane T-branching circuit 37 combines a horizontally polarized electric wave transmitted by the rectangular waveguide multi-stage transformer 36a and a horizontally polarized electric wave transmitted by the rectangular waveguide multi-stage transformer 36b into a composite signal, and then outputs a linearly polarized wave signal L3 which is the composite signal via the input/output terminal P5. Another rectangular waveguide E-plane T-branching circuit 38 combines a vertically polarized electric wave transmitted by the rectangular waveguide multi-stage transformer 36c and a vertically polarized electric wave transmitted by the rectangular waveguide multi-stage transformer 36d into a composite signal, and then outputs a linearly polarized wave signal L4 which is the composite signal via the input/output terminal P6. A first electric wave propagating means comprises the rectangular waveguide branching units 35a and 35b, the rectangular waveguide multi-stage transformers 36a and 36b, and the rectangular waveguide E-plane T-branching circuit 37, and a second electric wave propagating means comprises the rectangular waveguide branching units 35c and 35d, the rectangular waveguide multi-stage transformers 36c and 36d, and the rectangular waveguide E-plane T-branching circuit 38. Next, the operation of the waveguide orthomode transducer in accordance with this embodiment of the present invention will be explained. When the antenna apparatus receives a horizontally polarized electric wave H of basic mode (i.e., TE01 mode) via the input/output terminal P4, the square main waveguides 31 and 32 transmit the horizontally polarized electric wave H to the quadrangular-pyramid-shaped metallic block. When the horizontally polarized electric wave H then reaches the quadrangular-pyramid-shaped metallic block 34, the quadrangular-pyramid-shaped metallic block causes it to branch toward both the direction of the rectangular waveguide branching unit 35a and the direction of the rectangular waveguide branching unit 35b (in the figures, the directions of H: first horizontal symmetrical directions). In other words, since each of the rectangular waveguide branching units 35c and 35d has upper and lower walls having a gap which is equal to or smaller than one half of the free space wavelength of the available frequency band, the horizontally polarized electric wave H is not made to branch toward the directions of the rectangular waveguide branching units 35c and 35d (in the figures, in the directions of V: second horizontal symmetrical directions) due to the interception effect of the rectangular waveguide branching units 35c and 35d, but is made to branch toward the directions of the rectangular waveguide branching units 35a and 35b (in the figures, in the directions of H). Since the orientation of the electric field is changed along the quadrangular-pyramid-shaped metallic block 34 and the short-circuit plate 33, the electric field has a distribution equivalent to an electric field distribution provided by two rectangular waveguide E-plane miter bends having excellent reflective characteristics which are placed so that they are symmetric to each other. Therefore, the horizontally polarized electric wave H is efficiently outputted in the directions of the rectangular waveguide branching units 35a and 35b while leakage of the horizontally polarized electric wave H in the directions of the rectangular waveguide branching units 35c and 35d is suppressed. The level difference between the square main waveguides 31 and 32 at the connecting portion where the square main waveguide 31 is connected to the square main waveguide 32 is so designed as to be sufficiently small as compared with the free space wavelength of the available frequency band, and the connecting portion between the square main waveguides 31 and 32 has reflection characteristics in which there is a large reflection loss in a frequency band near the cut-off frequency of the basic mode of the horizontally polarized electric wave H and there is a very small reflection loss in a frequency band to some extent higher than the cut-off frequency. The reflection characteristics are similar to the reflection characteristics of the above-mentioned branching portion at which the horizontally polarized electric wave H is made to branch toward the directions of the rectangular waveguide branching units 35a and 35b, and the above-mentioned connecting portion is positioned so that a reflected wave from the branching portion and a reflected wave from the above-mentioned connecting portion cancel each other out in a band close to the cut-off frequency. Therefore, any degradation in the reflection characteristics in the frequency band near the cut-off frequency can be suppressed without impairing the good reflection characteristics in the frequency band to some extent higher than the cut-off frequency of the basic mode of the horizontally polarized electric wave H. Each of the rectangular waveguide multi-stage transformers 36a and 36b has a waveguide axis which is curved, and has an upper wall in which two or more level differences are formed and the level differences are arranged at intervals of about one quarter of the wavelength of an electric wave propagating therethrough with respect to a centerline of the waveguide. After all, the two components in the directions of the rectangular waveguide branching units 35a and 35b toward which the electric wave H is made to branch are combined into a composite wave signal by the rectangular waveguide E-plane T-branching circuit 37 and the composite wave signal is efficiently outputted via the input/output terminal P5 without the reflection characteristics of the waveguide orthomode transducer being impaired. On the other hand, when the waveguide orthomode transducer receives a vertically polarized electric wave V of basic mode (i.e., TE10 mode) via the input/output terminal P4, the square main waveguides 31 and 32 transmit the vertically polarized electric wave V to the quadrangular-pyramid-shaped metallic block. When the vertically polarized electric wave V then reaches the quadrangular-pyramid-shaped metallic block 34, the quadrangular-pyramid-shaped metallic block makes it branch toward both a direction of the rectangular waveguide branching unit 35c and a direction of the rectangular waveguide branching unit 35d (in the figures, the directions of V). In other words, since each of the rectangular waveguide branching units 35a and 35b has upper and lower walls having a gap which is equal to or smaller than one half of the free space wavelength of the available frequency band, the vertically polarized electric wave V is not made to branch toward the directions of the rectangular waveguide branching units 35a and 35b (in the figures, in the directions of H) due to the interception effect of the rectangular waveguide branching units 35a and 35b, but is made to branch toward the directions of the rectangular waveguide branching units 35c and 35d (in the figures, in the directions of V). Since the orientation of the electric field is changed along the quadrangular-pyramid-shaped metallic block 34 and the short-circuit plate 33, the electric field has a distribution equivalent to an electric field distribution provided by two rectangular waveguide E-plane miter bends having excellent reflection characteristics which are placed so that they are symmetric to each other. Therefore, the vertically polarized electric wave V is efficiently outputted in the directions of the rectangular waveguide branching units 35c and 35d while leakage of the vertically polarized electric wave V in the directions of the rectangular waveguide branching units 35a and 35b is suppressed. The level difference between the square main waveguides 31 and 32 at the connecting portion where the square main waveguide 31 is connected to the square main waveguide 32 is so designed as to be sufficiently small as compared with the free space wavelength of the available frequency band, and the connecting portion between the square main waveguides 31 and 32 has reflection characteristics in which there is a large reflection loss in a frequency band near the cut-off frequency of the basic mode of the vertically polarized electric wave V and there is a very small reflection loss in a frequency band to some extent higher than the cut-off frequency. The reflection characteristics are similar to the reflection characteristics of the above-mentioned branching portion at which the vertically polarized electric wave V is made to branch toward the directions of the rectangular waveguide branching units 35c and 35d, and the above-mentioned connecting portion is positioned so that a reflected wave from the branching portion and a reflected wave from the above-mentioned connecting portion cancel each other out in a band close to the cut-off frequency. Therefore, any degradation in the reflection characteristics in the frequency band near the cut-off frequency can be suppressed without impairing the good reflection characteristics in the frequency band to some extent higher than the cut-off frequency of the basic mode of the vertically polarized electric wave V. Each of the rectangular waveguide multi-stage transformers 36c and 36d has a waveguide axis which is curved, and has a lower wall in which two or more level differences are formed and the level differences are arranged at intervals of about one quarter of the wavelength of an electric wave propagating therethrough with respect to a centerline of the waveguide. After all, the two components in the directions of the rectangular waveguide branching units 35c and 35d toward which the electric wave V is separated made to branch are combined into a composite wave signal by the rectangular waveguide E-plane T-branching circuit 38 and the composite wave signal is efficiently outputted via the input/output terminal P6 without the reflection characteristics of the waveguide orthomode transducer being impaired. Although the explanation of the principle of operation of the waveguide orthomode transducer is made as to the case where the input/output terminal P4 is used as an input terminal and the input/output terminals P5 and P6 are used as output terminals, the waveguide orthomode transducer of this embodiment operates on the same principle of operation even in a case where the input/output terminals P5 and P6 are used as input terminals and the input/output terminal P4 is used as an output terminal. As can be seen from the above description, this embodiment 3 offers an advantage of being able to provide good reflection characteristics and isolation characteristics in a wide frequency band including a frequency range close to the cut-off frequency of the basic mode of the square main waveguide 32. Since the length of the square main waveguide 31 in the direction of its waveguide axis can be shortened in each of the waveguide orthomode transducers 1, 8, and 13, the physical size of the antenna apparatus can be reduced. Embodiment 4 The antenna apparatus in accordance with above-mentioned embodiment 3 uses the waveguide orthomode transducers 1, 8, and 13 each having a structure shown in FIGS. 4 and 5, as previously explained. As an alternative, the antenna apparatus uses waveguide orthomode transducers 1, 8, and 13 each having a structure shown in FIGS. 6 and 7. The waveguide orthomode transducers 1, 8, and 13 can have the same structure. For the sake of simplicity, FIGS. 6 and 7 show the structure of the waveguide orthomode transducer 13. In FIGS. 6 and 7, the same reference numerals as shown in FIGS. 4 and 5 denote the same components or like components, and therefore the explanation of these components will be omitted hereafter. When receiving a circularly polarized wave signal C2 outputted thereto from a primary radiator 14 via an input/output terminal P9, a circular main waveguide 41 transmits the circularly polarized wave signal (including a vertically polarized electric wave and a horizontally polarized electric wave) C2. Another square main waveguide 42 is connected to the circular main waveguide 41, and has an aperture diameter larger than that of a square main waveguide 32 and a level difference at a connecting portion where it is connected to the square main waveguide 32, the level difference being sufficiently smaller than the free space wavelength of an available frequency band. The square main waveguide 42 transmits the circularly polarized wave signal (including a vertically polarized electric wave and a horizontally polarized electric wave) C2 transmitted thereto by the square main waveguide 42. When the antenna apparatus receives a horizontally polarized electric wave H of basic mode (i.e., TE01 mode) via the input/output terminal P9, the circular main waveguide 41 and the square main waveguides 42 and 32 transmit the horizontally polarized electric wave H to a quadrangular-pyramid-shaped metallic block. When the horizontally polarized electric wave H then reaches the quadrangular-pyramid-shaped metallic block 34, the quadrangular-pyramid-shaped metallic block makes it branch toward both the direction of a rectangular waveguide branching unit 35a and the direction of a rectangular waveguide branching unit 35b (in the figures, in the directions of H). In other words, since each of rectangular waveguide branching units 35c and 35d has upper and lower walls having a gap which is equal to or smaller than one half of the free space wavelength of the available frequency band, the horizontally polarized electric wave H is not made to branch toward the directions of the rectangular waveguide branching units 35c and 35d (in the figures, in the directions of V) due to the interception effect of the rectangular waveguide branching units 35c and 35d, but is made to branch toward the directions of the rectangular waveguide branching units 35a and 35b (in the figures, in the directions of H). Since the orientation of the electric field is changed along the quadrangular-pyramid-shaped metallic block 34 and a short-circuit plate 33, the electric field has a distribution equivalent to an electric field distribution provided by two rectangular waveguide E-plane miter bends having excellent reflective characteristics which are placed so that they are symmetric to each other. Therefore, the horizontally polarized electric wave H is efficiently outputted in the directions of the rectangular waveguide branching units 35a and 35b while leakage of the horizontally polarized electric wave H in the directions of the rectangular waveguide branching units 35c and 35d is suppressed. A connecting portion where the circular main waveguide 41 is connected to the square main waveguide 42, the square main waveguide 42, and a connecting portion where the square main waveguide 42 is connected to the square main waveguide 32 serve as a circular-to-rectangular waveguide multi-stage transformer. Therefore, when the diameter of the circular main waveguide 41, the diameter of the square main waveguide 42 and the length of the waveguide axis of the square main waveguide 42 are properly designed, the circular-to-rectangular waveguide multi-stage transformer has reflection characteristics in which there is a large reflection loss in a frequency band near the cut-off frequency of the basic mode of the horizontally polarized electric wave H and there is a very small reflection loss in a frequency band to some extent higher than the cut-off frequency. The reflection characteristics are similar to the reflection characteristics of the above-mentioned branching portion at which the horizontally polarized electric wave H is made to branch toward the directions of the rectangular waveguide branching units 35a and 35b, and the above-mentioned circular-to-rectangular waveguide multi-stage transformer is positioned so that a reflected wave from the branching portion and a reflected wave from the above-mentioned circular-to-rectangular waveguide multi-stage transformer cancel each other out in a band close to the cut-off frequency. Therefore, any degradation in the reflection characteristics in the frequency band near the cut-off frequency can be suppressed without impairing the good reflection characteristics in the frequency band to some extent higher than the cut-off frequency of the basic mode of the horizontally polarized electric wave H. Each of the rectangular waveguide multi-stage transformers 36a and 36b has a waveguide axis which is curved, and has an upper wall in which two or more level differences are formed and the level differences are arranged at intervals of about one quarter of the wavelength of an electric wave propagating therethrough with respect to a centerline of the waveguide. After all, the two components in the directions of the rectangular waveguide branching units 35a and 35b toward which the electric wave H is made to branch toward are combined into a composite wave signal by a rectangular waveguide E-plane T-branching circuit 37 and the composite wave signal is efficiently outputted via an input/output terminal P7 without the reflection characteristics of the waveguide orthomode transducer being impaired. On the other hand, when the waveguide orthomode transducer receives a vertically polarized electric wave V of basic mode (i.e., TE10 mode) via the input/output terminal P9, the circular main waveguide 41 and the square main waveguides 42 and 32 transmit the vertically polarized electric wave V to the quadrangular-pyramid-shaped metallic block. When the vertically polarized electric wave V then reaches the quadrangular-pyramid-shaped metallic block 34, the quadrangular-pyramid-shaped metallic block makes it branch toward both a direction of the rectangular waveguide branching unit 35c and a direction of the rectangular waveguide branching unit 35d (in the figures, in the directions of V). In other words, since each of the rectangular waveguide branching units 35a and 35b has upper and lower walls having a gap which is equal to or smaller than one half of the free space wavelength of the available frequency band, the vertically polarized electric wave V is not made to branch toward the directions of the rectangular waveguide branching units 35a and 35b (in the figures, in the directions of H) due to the interception effect of the rectangular waveguide branching units 35a and 35b, but is made to branch toward the directions of the rectangular waveguide branching units 35c and 35d (in the figures, in the directions of V). Since the orientation of the electric field is changed along the quadrangular-pyramid-shaped metallic block 34 and the short-circuit plate 33, the electric field has a distribution equivalent to an electric field distribution provided by two rectangular waveguide E-plane miter bends having excellent reflection characteristics which are placed so that they are symmetric to each other. Therefore, the vertically polarized electric wave V is efficiently outputted in the directions of the rectangular waveguide branching units 35c and 35d while leakage of the vertically polarized electric wave V in the directions of the rectangular waveguide branching units 35a and 35b is suppressed. The connecting portion where the circular main waveguide 41 is connected to the square main waveguide 42, the square main waveguide 42, and the connecting portion where the square main waveguide 42 is connected to the square main waveguide 32 serve as a circular-to-rectangular waveguide multi-stage transformer. Therefore, when the diameter of the circular main waveguide 41, the diameter of the square main waveguide 42 and the length of the waveguide axis of the square main waveguide 42 are properly designed, the circular-to-rectangular waveguide multi-stage transformer has reflection characteristics in which there is a large reflection loss in a frequency band near the cut-off frequency of the basic mode of the vertically polarized electric wave V and there is a very small reflection loss in a frequency band to some extent higher than the cut-off frequency. The reflection characteristics are similar to the reflection characteristics of the above-mentioned branching portion at which the vertically polarized electric wave V is made to branch toward the directions of the rectangular waveguide branching units 35c and 35d, and the above-mentioned circular-to-rectangular waveguide multi-stage transformer is positioned so that a reflected wave from the branching portion and a reflected wave from the above-mentioned circular-to-rectangular waveguide multi-stage transformer cancel each other out in a band close to the cut-off frequency. Therefore, any degradation in the reflection characteristics in the frequency band near the cut-off frequency can be suppressed without impairing the good reflection characteristics in the frequency band to some extent higher than the cut-off frequency of the basic mode of the vertically polarized electric wave V. Each of the rectangular waveguide multi-stage transformers 36c and 36d has a waveguide axis which is curved, and has a lower wall in which two or more level differences are formed and the level differences are arranged at intervals of about one quarter of the wavelength of an electric wave propagating therethrough with respect to a centerline of the waveguide. After all, the two components in the directions of the rectangular waveguide branching units 35c and 35d toward which the electric wave V is made to branch are combined into a composite wave signal by a rectangular waveguide E-plane T-branching circuit 38 and the composite wave signal is efficiently outputted via an input/output terminal P6 without the reflection characteristics of the waveguide orthomode transducer being impaired. Although the explanation of the principle of operation of the waveguide orthomode transducer is made as to the case where the input/output terminal P9 is used as an input terminal and the input/output terminals P7 and P8 are used as output terminals, the waveguide orthomode transducer of this embodiment operates on the same principle of operation even in a case where the input/output terminals P7 and P8 are used as input terminals and the input/output terminal P9 is used as an output terminal. As can be seen from the above description, this embodiment 4 offers an advantage of being able to provide good reflection characteristics and isolation characteristics in a wide frequency band including a frequency range close to the cut-off frequency of the basic mode of the square main waveguide 32. Since the length of the square main waveguide 32 in the direction of its waveguide axis can be shortened in each of the waveguide orthomode transducers 1, 8, and 13, the physical size of the antenna apparatus can be reduced. Embodiment 5 FIG. 8 is a side view showing an antenna apparatus according to embodiment 5 of the present invention, and FIG. 9 is a top plan view showing the antenna apparatus of FIG. 8. In FIGS. 8 and 9, the same reference numerals as shown in FIGS. 1 and 2 denote the same components as shown in the figures or like components, the explanation of these components will be omitted hereafter. RF modules 51a and 51b are inserted into rectangular waveguides 10a and 10b, and amplify linearly polarized wave signals L3 and L4, respectively. FIG. 10 is a block diagram showing the RF modules 51a and 51b, and each of the RF modules 51a and 51b is provided with waveguide branching filters 52 and 53 and a low noise amplifier 54. Since the antenna apparatus according to this embodiment has the same structure as that according to above-mentioned embodiment 1 with the exception that the RF modules 51a and 51b are inserted into the rectangular waveguides 10a and 10b, respectively, only the operation of each of the RF modules 51a and 51b will be explained hereafter. In accordance with above-mentioned embodiment 1, the rectangular waveguides 9a, 10a, 9b, and 10b are routed so that the waveguide orthomode transducer 13 is disposed below the waveguide orthomode transducer 8, and therefore the linearly polarized wave signals L3 and L4 outputted from the waveguide orthomode transducer 13 decrease in magnitude with increase in the sizes of the rectangular waveguides 9a, 10a, 9b, and 10b. In contrast, in accordance with this embodiment 5, the RF modules 51a and 51b amplify linearly polarized wave signals L3 and L4 outputted from the waveguide orthomode transducer 13, respectively, and also make linearly polarized wave signals L3 and L4 outputted from the waveguide orthomode transducer 8 pass therethrough, just as they are, respectively. In other words, the waveguide branching filter 52 of the RF module 51a branches the linearly polarized wave signal L3 outputted from an input/output terminal P7 of the waveguide orthomode transducer 13 toward the low noise amplifier 54 without branching it toward the waveguide branching filter 53. As a result, the low noise amplifier 54 amplifies the linearly polarized wave signal L3, and the waveguide branching filter 53 then outputs the amplified linearly polarized wave signal L3 to an input/output terminal P5 of the waveguide orthomode transducer 8. On the other hand, the waveguide branching filter 53 of the RF module 51a does not branch the linearly polarized wave signal L3 outputted from the input/output terminal P5 of the waveguide orthomode transducer 8 toward the low noise amplifier 54, but branches it toward the waveguide branching filter 52. The waveguide branching filter 52 then outputs the linearly polarized wave signal L3 to the input/output terminal P7 of the waveguide orthomode transducer 13. Similarly, the waveguide branching filter 52 of the RF module 51b branches the linearly polarized wave signal L4 outputted from an input/output terminal P8 of the waveguide orthomode transducer 13 toward the low noise amplifier 54 without branching it toward the waveguide branching filter 53. As a result, the low noise amplifier 54 amplifies the linearly polarized wave signal L4, and the waveguide branching filter 53 then outputs the amplified linearly polarized wave signal L4 to an input/output terminal P6 of the waveguide orthomode transducer 8. On the other hand, the waveguide branching filter 53 of the RF module 51b does not branch the linearly polarized wave signal L4 outputted from the input/output terminal P6 of the waveguide orthomode transducer 8 toward the low noise amplifier 54, but branches it toward the waveguide branching filter 52, and the waveguide branching filter 52 then outputs the linearly polarized wave signal L4 to the input/output terminal P8 of the waveguide orthomode transducer 13. This embodiment 5 offers an advantage of being able to suppress degradation in quality due to a transmission loss of the linearly polarized wave signals L3 and L4 caused by the rectangular waveguides 9a, 10a, 9b, and 10b. Embodiment 6 In accordance with above-mentioned embodiment 5, each of the RF modules 51a and 51b is provided with the waveguide branching filters 52 and 53 and the low noise amplifier 54. In contrast, in accordance with this embodiment, the RF module 51b can have a structure as shown in FIG. 11. The RF module 51a can have the same structure as the RF module 51b, though the RF module 51a is not illustrated in the figure. FIG. 11(a) is a cross-sectional view showing each of the RF modules 51a and 51b, FIG. 11(b) is a side view of a single-sided corrugated rectangular waveguide low pass filter 65 of FIG. 11(a) when viewed from the left side of the figure, FIG. 11(c) is a side view of a single-sided corrugated rectangular waveguide low pass filter 66 of FIG. 11(a) when viewed from the right side of the figure, FIG. 11(d) is a plan view of a low noise amplifier 71 and so on of FIG. 11(a) when viewed from the upper side of the figure. When a linearly polarized wave signal L4 outputted from an input/output terminal P8 of a waveguide orthomode transducer 13, i.e., a basic mode (i.e., a rectangular waveguide TE01 mode) of an electric wave of a first frequency band is inputted to each RF module via an input/output terminal P11, this electric wave propagates through a rectangular main waveguide 61, a stepped rectangular waveguide E-plane T-branching circuit 63, and the single-sided corrugated rectangular waveguide low pass filter 65, and is then inputted into the low noise amplifier 71 constructed of an MIC via a rectangular-waveguide-to-MIC converter 69. This electric wave is then amplified by the low noise amplifier 71. The amplified electric wave is then outputted from another rectangular-waveguide-to-MIC converter 70, propagates through the single-sided corrugated rectangular waveguide low pass filter 66, another stepped rectangular waveguide E-plane T-branching circuit 64, and a rectangular main waveguide 62, and is outputted, as the basic mode of the rectangular waveguide, to an input/output terminal P6 of a waveguide orthomode transducer 8 via an input/output terminal P12. On the other hand, when a linearly polarized wave signal L4 outputted from the input/output terminal P6 of the waveguide orthomode transducer 8, i.e., a basic mode (i.e., a rectangular waveguide TE01 mode) of an electric wave of a second frequency band higher than the first frequency band is inputted to each RF module via the input/output terminal P12, this electric wave propagates through the rectangular main waveguide 62, the stepped rectangular waveguide E-plane T-branching circuit 64, inductive iris coupled rectangular waveguide band pass filters 68 and 67, the stepped rectangular waveguide E-plane T-branching circuit 63, and the rectangular main waveguide 61, and is outputted, as the basic mode of the rectangular waveguide, to the input/output terminal P8 of the waveguide orthomode transducer 13 via the input/output terminal P11. Each of the single-sided corrugated rectangular waveguide low pass filters 65 and 66 is so designed as to allow any electric wave of the first frequency band to pass therethrough and to reflect any electric wave of the second frequency band. In contrast, each of the inductive iris coupled rectangular waveguide band pass filters 67 and 68 is so designed as to allow any electric wave of the second frequency band to pass therethrough and to reflect any electric wave of the first frequency band. In addition, the stepped rectangular waveguide E-plane T-branching circuit 63 has a matching step that is disposed at a branching portion thereof and is designed so that both a reflected wave caused thereby when an electric wave of the first frequency band is incident thereupon from the rectangular main waveguide 61, and a reflected wave caused thereby when an electric wave of the second frequency band is incident thereupon from the inductive iris coupled rectangular waveguide band pass filter 67 are reduced as much as possible, respectively. Similarly, the stepped rectangular waveguide E-plane T-branching circuit 64 has a matching step that is disposed at a branching portion thereof and is designed so that both a reflected wave caused thereby when an electric wave of the first frequency band is incident thereupon from the single-sided corrugated rectangular waveguide low pass filter 66, and a reflected wave caused thereby when an electric wave of the second frequency band is incident thereupon from the rectangular main waveguide 62 are reduced as much as possible, respectively. As a result, the electric wave of the first frequency band inputted to each RF module via the input/output terminal P11 is efficiently inputted into the low noise amplifier 71 while both reflection of the electric wave to the input/output terminal P11, and direct leakage of the electric wave to the stepped rectangular waveguide E-plane T-branching circuit 64 are suppressed. Furthermore, the electric wave of the first frequency band amplified by the low noise amplifier 71 is efficiently outputted via the input/output terminal P12 without being sent back to the stepped rectangular waveguide E-plane T-branching circuit 63. In addition, the electric wave of the second frequency band inputted to each RF module via the input/output terminal P11 is efficiently outputted via the input/output terminal P11 while both reflection of the electric wave to the input/output terminal P12 and leakage of the electric wave to the low noise amplifier 71 are suppressed. According to this embodiment 6, at the same time that each RF module efficiently amplifies and makes an electric wave of the first frequency band inputted thereto via the input/output terminal P11 pass therethrough without making the electric wave oscillate, each RF module can make most of an electric wave of the second frequency band inputted thereto via the input/output terminal P12 pass therethrough with almost no loss of the electric wave. In addition, when the number of resonators included in each of the inductive iris coupled rectangular waveguide band pass filters 67 and 68 is properly reduced, the distance between the input/output terminal P11 to the input/output terminal P12 is shortened. In this case, the physical size and weight of each RF module can be reduced and the performance of each RF module can be enhanced. Embodiment 7 In the antenna apparatus according to either of above-mentioned embodiments 1 to 6, a linearly polarized wave signal L1 is outputted or inputted via the input/output terminal P1 of the waveguide orthomode transducer 1, and a linearly polarized wave signal L2 is outputted and inputted via the input/output terminal P2, as previously mentioned. In contrast, an antenna apparatus according to this embodiment is provided with an input/output means for outputting or inputting a linearly polarized wave signal L1 via an input/output terminal P1 of a waveguide orthomode transducer 1, and for outputting or inputting a linearly polarized wave signal L2 via an input/output terminal P2 of the waveguide orthomode transducer 1, as shown in FIG. 12. In this embodiment, the input/output means comprises waveguide branching filters 81 and 82, a waveguide 90-degree hybrid circuit 83, a coaxial-cable 90-degree hybrid circuit 84, high power amplifiers 85 and 86, low noise amplifiers 87 and 88, variable phase shifters 89 to 92, coaxial-cable 90-degree hybrid circuits 93 and 94, and coaxial-cable-to-waveguide converters 95 and 96. Thus, by using the input/output means, the antenna apparatus can receive a right-hand circularly polarized wave signal and a left-hand circularly polarized wave signal, and can also transmit and receive a linearly polarized wave having an arbitrary angle. INDUSTRIAL APPLICABILITY As mentioned above, the antenna apparatus in accordance with the present invention can be used in a VHF band, a UHF band, a microwave band, a millimeter wave band, etc.
<SOH> BACKGROUND OF THE INVENTION <EOH>A prior art antenna apparatus is equipped with a circularly polarized wave generator and a polarizer, which are mounted on a rotary joint or a rotary mechanism, so as to allow integral rotation of a reflector and a primary radiator (refer to the following non-patent reference 1). [Non-Patent Reference 1] Takashi Kitsuregawa, ‘Advanced Technology in Satellite Communication Antennas: Electrical & Mechanical Design’, ARTECH HOUSE INC., pp. 232 to 235, 1990. A problem with the prior art antenna apparatus constructed as mentioned above is that while it can rotate both the reflector and the primary radiator in a direction of an elevation angle or in a direction of an azimuth angle, the part of the prior art antenna apparatus which is arranged above the rotary mechanism has a very large size and has a high position, and therefore the prior art antenna apparatus lacks in installation stability because the circularly polarized wave generator and the polarizer are placed on the rotary joint or the rotary mechanism. The present invention is made in order to solve the above-mentioned problem, and it is therefore an object of the present invention to provide an antenna apparatus having a low profile and high installation stability without impairing its electric characteristics.
<SOH> BRIEF DESCRIPTION OF THE FIGURES <EOH>FIG. 1 is a side view showing an antenna apparatus according to embodiment 1 of the present invention; FIG. 2 is a top plan view showing the antenna apparatus of FIG. 1 ; FIG. 3 is a side view showing an antenna apparatus according to embodiment 2 of the present invention; FIG. 4 is a top plan view showing waveguide orthomode transducers 1 and 8 of an antenna apparatus according to embodiment 3 of the present invention; FIG. 5 is a perspective diagram showing a waveguide orthomode transducer of FIG. 4 ; FIG. 6 is a top plan view showing a waveguide orthomode transducer of an antenna apparatus according to embodiment 4 of the present invention; FIG. 7 is a perspective diagram showing the waveguide orthomode transducer of FIG. 6 ; FIG. 8 is a side view showing an antenna apparatus according to embodiment 5 of the present invention; FIG. 9 is a top plan view showing the antenna apparatus of FIG. 8 ; FIG. 10 is a block diagram showing an RF module; FIG. 11 is a block diagram showing an RF module; and FIG. 12 is a side view showing an antenna apparatus according to embodiment 7 of the present invention. detailed-description description="Detailed Description" end="lead"?
20050506
20060822
20060126
76315.0
H01Q1300
0
TRAN, CHUC
ANTENNA DEVICE
UNDISCOUNTED
0
ACCEPTED
H01Q
2,005
10,534,133
ACCEPTED
Articles
An article for sequential dispensing of vapours, notably evaporable fragrances, comprises separated first and second liquids (22, 24). Liquid (22) issues first. Its evaporation may be assisted by a wick (26). The simultaneous evaporation of the second liquid is prevented by an intermediate liquid phase (20). As liquid (22) issues the liquid levels change and there comes a point at which the intermediate phase can no longer prevent the second liquid (24) from flowing past it, to the region from which it can be evaporated. Solids, especially gels, may be employed instead of liquids (22, 24).
1. An article for the release of a plurality of vapours, the article containing: a first liquid or solid phase comprising a first vaporisable agent; a second liquid or solid phase comprising a second vaporisable agent; and a third phase which constitutes a barrier between the first and second phases; wherein the first and second phases are such that if placed in contact with each other one phase or one or more component thereof would mix or migrate into the other phase wherein the article comprises an enclosure having a partition wall between the first phase and the second phase at the commencement of use of the article, the partition wall terminating above the bottom wall of the enclosure the third phase being at the bottom of the enclosure, wherein the lower edge of the partition wall extends into the third phase at the commencement of use of the article; wherein the commencement of vaporisation of the second phase is delayed by the third phase and wherein when the first phase has issued from the article in use, the third phase is exposed to the air and can shrink whereby the second phase can flow around the third phase and then evaporate from the article. 2. An article for the release of a plurality of vapours, the article containing: a first liquid or solid phase comprising a first vaporisable agent; a second liquid or solid phase comprising a second vaporisable agent; and a third phase which constitutes a barrier between the first and second phases; wherein the first and second phases are such that if placed in contact with each other one phase or one or more component thereof would mix or migrate into the other phase wherein the article comprises an enclosure having two upright limbs connected together, wherein at the commencement of use the first phase is located in one limb the second phase is located in the other limb and the third phase is located therebetween such that commencement of the vaporisation of the second phase is delayed by the third phase; such that, in use, initially vaporisation of the first agent commences, and subsequently vaporisation of the second agent commences, the commencement of vaporisation of the second agent being delayed by the third phase. 3. An article according to claim 1, wherein the first phase is adapted to evaporate substantially completely. 4. An article according to claim 1, wherein the second phase is adapted to evaporate substantially completely. 5. An article according to claim 1, wherein the first phase is a liquid. 6. An article according to claim 1, wherein the first phase is a gel. 7. An article according to claim 1, wherein the second phase is a liquid. 8. An article according to claim 1, wherein the second phase is a gel. 9. An article according to claim 1, wherein the third phase is a liquid. 10. An article according to claim 1, wherein the third phase is a gel. 11. An article according to claim 1, wherein at leaset one of the first and second phases comprises as an evaporable agent a fragrance. 12. An article according to claim 1, wherein at least one of the first and second phases comprises as an evaporable agent a compound selected from an insecticide, insect repellent, miticide or anti-allergenic compound. 13. An article according to claim 1, where the third phase comprises a third evaporable agent. 14. A composition according to claim 1, wherein the third phase is a liquid or gel whose volume reduces when exposed to air. 15. A method of dispensing at least two active agents, using an article according to claim 1, wherein the commencement of evaporation of the first evaporable agent precedes the commencement of evaporation of the second evaporable agent. 16. A method as claimed in claim 15 wherein evaporation of the second evaporable agent commences substantially at the point at which evaporation of the first evaporable agent is complete. 17. A method as claimed in claim 15, wherein evaporation of the second evaporable agent commences before evaporation of the first evaporable agent is complete. 18. An article according to claim 2 wherein the second phase is adapted to evaporate substantially completely. 19. A method of dispensing at least two active agents, using an article according to claim 2 wherein the commencement of evaporation of the first evaporable agent precedes the commencement of evaporation of the second evaporable agent. 20. A method as claimed in claim 19 wherein evaporation of the second evaporable agent commences substantially at the point at which evaporation of the first evaporable agent is complete. 21. A method as claimed in claim 19, wherein evaporation of the second evaporable agent commences before evaporation of the first evaporable agent is complete.
This invention relates to articles for the release of vapours. It would be desirable to provide one article which could emit more than one vapour, for example fragrance or other active agent, automatically and in a sequential manner. In accordance with a first aspect of the present invention there is provided an article for the release of a plurality of vapours, the article containing: a first liquid or solid phase comprising a first vaporisable agent; a second liquid or solid phase comprising a second vaporisable agent; and a third phase which constitutes a barrier between the first and second phases; wherein the first and second phases are such that if placed in contact with each other one phase or one or more component thereof would mix or migrate into the other phase; and wherein the article is such that, in use, initially vaporisation of the first agent commences, and subsequently vaporisation of the second agent commences, the commencement of vaporisation of the second agent being delayed by the third phase. The article of the present invention is useful when it is wished to release different vapours, or a different blend of vapours, at different times. When the vapours are fragrances this may help to avoid “nasal attenuation” (anosmia) of a user—the process by which the user becomes so accustomed to a single fragrance that he or she no longer perceives it. When the vapours are insecticides, insect repellents or miticides the release of different vaporised active agents, at different times, may increase the effectiveness by challenging the insects or mites with a different or more complex active agent, and may assist in reducing the onset of resistance. The invention is useful in situations where the first phase and the second phase could mix or migrate into each other, if placed in contact together. The third phase performs the function of a barrier, preventing this. Clearly, in situations in which the first phase and the second phase remain entirely separate from each other even when in contact with each other, there would be no need for a barrier; the present invention would be of no benefit in this situation. On the other hand, the degree of mixing or migration of the first and second phases does not have to be very great for the placement together to be undesirable; accordingly in such embodiments a third phase acting as a barrier is required. The present invention is highly applicable to situations in which the first and second phases are liquids which are miscible with each other. However it is also applicable to situations in which the first liquid is slightly miscible in the second liquid; and/or in which the second liquid is slightly miscible in the first liquid. Similar considerations apply when one of the first and second phases is a solid, for example a gel, and the other of the first and second phases is a liquid. If such phases are placed together one can have the situation that the liquid phase is absorbed entirely into the solid phase; or the solid phase is dissolved entirely in the liquid phase. The result could be a single phase—probably a liquid due to break up of the gel. As an alternative, there could remain two distinct phases but with the composition of one or both phases modified by mixing or migration of one into the other. In all such embodiments the provision of a barrier layer to provide the controlled sequential release of vapours is usefully employed, in accordance with the invention. In situations where the first and second phases are both solids, for example gels, it may be the case that one solid, or one or more component of it, mixes or migrates into the other solid. This may happen continuously due to the process of diffusion. Alternatively or additionally it may arise as a result of the manufacture, as one solid is laid on top of the other solid. In such embodiments a barrier is provided in the form of a third phase, to prevent premature mixing or migration. Preferably an article in accordance with the present invention provides automatic release of a desired vapour. Preferably the article does not have electrical connections. Preferably there is no consumer intervention once the operation is started. Furthermore, operation is typically started by exposing the first phase to the atmosphere, for example by the simple measure of removing a cap or seal and in certain embodiments, opening an aperture to provide an air vent into an otherwise closed space in communication with the second phase. The first evaporable agent may be released into the air by evaporation from the first phase. This may occur, for example, when the first phase is a non-volatile gel into which the evaporable agent is releasably absorbed. Preferably, however, the first phase is itself evaporated, thereby releasing the first evaporable agent. The second evaporable agent may be released into the air by evaporation from the second phase. This may occur, for example, when the second phase is a non-volatile gel into which the second evaporable agent is releasably absorbed. Preferably, however, the second phase itself evaporates, thereby releasing the second evaporable agent. In the following passages the context will make clear whether we are discussing an embodiment in which an evaporable agent is released from its associated phase or one in which it evaporates with it. Preferred articles of the invention are fragrancing articles. Suitably the first liquid phase is an evaporable fragrance. Preferably the second phase is an evaporable fragrance. In other embodiments the articles may be insecticidal, insect-repelling, miticidal or anti-allergenic. At least one of the phases may contain an appropriate evaporable agent for such a use. If wished the third phase may contain an evaporable agent as mentioned above; preferably a fragrance. The third phase may be an aqueous phase (including a hydrogel). It may be a liquid phase, for example water. It may be a solid liquid-rich, preferably water-rich, phase. It is preferably a hydrogel. When the third phase is an aqueous phase the first and second phases are both phases substantially immiscible in water, under ambient conditions. When the phases are liquids the density of the third phase exceeds the densities of the first and second phases. The first phase could be a solid which is not a gel, for example an impregnated wax which has a wick and is burnt in the manner of a candle. The first phase could be an oil which is heated, for example by burning a wick therein. In other embodiments the first and second phases could be aqueous phases and the third phase could be a gel. Suitably this could be a non-aqueous phase, preferably a hydrophobic gel. However, it could be a water-containing gel provided that it keeps the first and second phases apart. When the third phase is a gel, where it contacts the article it may in preferred embodiments be bound to it. In other embodiments it need not be bound to it, provided that it can keep the first and second phases apart. In embodiments which employ a hydrogel for one or more of the phases, the hydrogel suitably includes a hydrogel-forming polymeric material, optionally of plant, animal or synthetic origin. The material interacts with water by absorbing the water and swelling or expanding to an equilibrium state. The hydrogel preferably exhibits the ability to retain a significant fraction of imbibed water in its polymeric molecular structure. Preferably the hydrogel is a gel polymer that can swell or expand to a very high degree; for example it can have a 2- to 50-fold volume increase. A suitable gel polymer is a swellable, hydrophilic polymer (or an osmopolymer) which is optionally either non-cross-linked or lightly cross-linked. The cross-links can be covalent, ionic or hydrogen bonds so that the polymer possesses the ability to swell in the presence of water but does not dissolve in the water. A hydrogel suitable for use is, for example, a poly(hydroxyalkylmethacrylate) having a molecular weight from 5,000 to 5,000,000; poly(vinylpyrrolidone) having molecular weight from 10,000 to 360,000; an anionic and/or cationic hydrogel; a poly(electrolyte) complex; poly(vinyl alcohol) having a low acetate residual; a mixture of agar and carboxymethyl cellulose; a composition comprising methyl cellulose mixed with a sparingly cross-linked agar; a copolymer produced by a dispersion of finely divided copolymer of maleic anhydride with styrene, ethylene, propylene or isobutylene; an N-vinyl lactam polymer; a sodium salt of carboxymethyl cellulose; a pectin having a molecular weight ranging from 30,000 to 300,000; a polysaccharide such as agar, acacia, karaya, tragacenth, carrageenans, algins and guar; an acidic carboxy polymer or its salt derivative such as one sold under the trade name CARBOPOL; a polyacrylamide; an indene maleic anhydride polymer; a polyacrylic acid having a molecular weight of 80,000 to 200,000 such as one sold under the trade name GOOD-RITE; a polyethylene oxide polymer having a molecular weight of 100,000 to 5,000,000 such as one sold under the trade name GOOD-RITE; a starch graft copolymer; an acrylate polymer with water absorbability of about 400 times its original weight such as one sold under the trade name AQUA-KEEP; a diester of polyglucan; a mixture of cross-linked poly(vinyl alcohol) and poly(N-vinyl 2-pyrrolidone); and poly(ethylene glycol) having a molecular weight of 4,000 to 100,000. Other suitable hydrogels are disclosed in U.S. Pat. Nos. 3,865,108, 4,002,173, 4,207,893, 4,220,152, 4,327,725 and 4,350,271, and in Scott et al, Handbook of Common Polymers, CRC Press, Cleveland, Ohio (1971); all of which are incorporated herein by reference. Another type of gel which is useful for one or more of the phases is a crosslinked polymeric gel. Especially suitable is a gel comprising a maleinised polybutadiene and an amine crosslinking agent, suitably a tri-amine or, especially, a di-amine compound; and preferably having the property that when exposed to air it shrinks. Such a gel is especially useful as the third phase, selected to shrink sufficiently, when exposed to air, for the gel to be breached. Preferably the article, especially one employing liquid phases, has an emanating device, for example a wick, located to assist the release of at least the first evaporable agent. A wick, preferably the same wick, may also assist the release of the second evaporable agent. In one embodiment employing evaporable liquid phases the article is generally U-shaped, with the first and second phases initially in the respective limbs, and with the third phase in the bottom region of the article, between the limbs. The first phase is released from the article at the top of one limb. The top region of the other limb is provided with an air vent, which is sufficiently small that the release of a second active agent is negligible. The air vent may be covered with a gas-permeable liquid-impermeable membrane. As the first phase is released from the article the interface between the second phase and the third phase adopts a progressively lower position, and there comes a time when second phase can flow from its limb, through the bottom region of the article, into the other limb. At this point the second phase can start to issue from the article. In an alternative embodiment employing liquid phases an article in accordance with the invention comprises a bottom wall, and a side wall (if cylindrical) or side walls (if not). At the top of the side wall or walls there is an inwardly extending top wall, which surrounds an aperture. Extending downwardly from the inner edge of the top wall is a central tubular body, whose bottom end is open. The tubular body constitutes a kind of well. The second phase is located in the space between the tubular body and the side wall, or walls, of the article. The second phase is located within the tubular body. The third phase is located at the bottom of the article, underneath the first phase and the second phase. The amount of the third phase present is such that it, in conjunction with the wall of the tubular body, keeps separate the first phase and the second phase. However as the first phase issues the liquid level changes and there comes a point where the interface between the second phase and the third phase has moved sufficiently low, that the second phase can flow under the bottom edge of the wall which defines the tubular body, and into the tubular body. From the tubular body it can issue from the article, for example by evaporation. In another embodiment an article in accordance with the invention is in the form of a box-like enclosure, having a partition wall extending from its top wall to a position somewhat spaced from its bottom wall. The third phase is located at the bottom of the article, and the lower edge of the partition wall is immersed in it. The first phase is located above the third phase on one side of the partition wall. The second phase is located above the third phase on the other side of the partition wall. The first phase may be associated with suitable delivery means, for example a wick extending through the top wall. The volume above the second phase may be vented by, for example, an upper pin hole. The movement of the second phase to a position from which it can issue from the article may be assisted by selection of a gel for the third phase, having a tendency to shrink over time and/or when exposed to air. In certain embodiments the third phase is a gel which is in fixed position within the article, being bound to surfaces of the article. When the first phase has issued the third phase is exposed to air and can shrink. After a certain degree of shrinkage a liquid second phase can flow through or around the third phase, and the second phase may then evaporate from the article. In related embodiments the shrinkage of the third phase could be initiated prematurely by the user. For example a patch may be provided, which a user may remove in order to expose the third phase to the air, preferably through a gas-permeable liquid-impermeable membrane, for example if an early change of fragrance is desired. This may be readily achieved when the article is generally U-shaped, having a gel which constitutes the third phase. The patch can be provided in an upper part of the link between the limbs. Preferably the first and second phases are of different colour. Preferably the third phase is of a different colour again. When the first and second phases are liquids and the article is designed such that when the second phase passes the third phase there is some of the first phase left, the mixing of the second phase and the remaining first phase produces a different colour again. This may be a mixing effect or may be a substantive chemical effect. In all embodiments operation of the article may employ a heat source (for example a flame, indirect or direct—for example by burning a wick, or an electrical heater) and/or a fan. In accordance with a second aspect of the present invention there is provided a method of releasing at least two vapours, the commencement of the release of a first vapour preceding the commencement of the release of a second vapour, using an article in accordance with the first aspect of the present invention. The invention will now be further described, by way of example, with reference to the accompanying drawings in which: FIG. 1 is a perspective view of a first article in accordance with the present invention; FIG. 2 is a schematic cross-sectional view of the article of FIG. 1; FIG. 3 is a schematic sectional view of a second article in accordance with the present invention; FIG. 4 is a schematic view of a third article in accordance with the present invention. FIG. 5 is a schematic view of a fourth article in accordance with the present invention; and FIG. 6 is a schematic view of a fifth article in accordance with the present invention. The article shown in FIGS. 1 and 2 has a cylindrical side wall 2 and a circular base wall 4. It has an annular top wall 6 joined with the side wall. The inner periphery of the annular top wall 6 is connected to a cylindrical inner wall 8, co-axial with the side wall 2, and forming a well, extending into the article. The well is open at its top end and at its bottom end. Its bottom end terminates a little way above the bottom wall 4 of the article. With reference to FIG. 2, water 10 fills the bottom section of the article contains tinted water 10, and the bottom region of the inner wall 8 forming the well is immersed in the water. Water 10 is thus located in the bottom region of the well, and in the bottom part of the annular region around the well. Above the water within the well is a first hydrophobic phase 12, comprising a fragrance, and coloured. Above the water 10 within the annular section is a second hydrophobic phase 14, comprising a different fragrance, and differently coloured. The first and second hydrophobic phases are substantially immiscible with the water. The top wall 6 of the article has a peel-off venting film 16. On peeling off the venting film 16 a very small vent hole 18 is exposed. In some embodiments this may be covered by a gas-permeable liquid-impermeable membrane. In use, after the venting film 16 has been peeled off to expose the vent hole 18, and a peel-off sticker (not shown) over the top of the well is removed, the first phase 12 is free to evaporate, and release its fragrance. As it evaporates all the liquid levels adjust. The second phase 14 moves lower, within the annular region. Evaporation of the first phase 12 continues and a point is reached when the second phase can bleed under the bottom edge of the inner wall 8, and into the well. It rises through the water to form a separate phase on the top of the water. As it evaporates, more of the second phase can bleed into the well, and then be evaporated. The vent hole 18 is so small that the passage through it of evaporated second phase is negligible. The geometry of the article and/or amounts of the phases may if desired be arranged such that substantially at the point where the first phase has been entirely removed by evaporation, the second phase can start to bleed into the well. In the second embodiment shown in FIG. 3 the article is a generally U-shaped tube. At the bottom of the “U” a water-swollen carrageenan hydrogel 20 is located. Above the hydrogel, and within the right-hand limb, as viewed, there is a first hydrophobic phase 22 comprising a first fragrance. Above the hydrogel, and within the left-hand limb, there is a second hydrophobic phase 24 comprising a second fragrance. The three phases are all coloured, differently. Within the right hand limb there is a wick 26. The wick 26 has a major portion that is located within the first phase, above the initial level of the interface between the first and second phases, and a minor portion projecting beyond the limb, and through an opening in the end wall 28 of the limb. If wished a wick may be employed extending to the bottom of the tube, in order to obtain wick-assisted emanation throughout the life of the product. The left-hand limb has a tiny vent hole 30 in its end wall. The vent hole 30 may be exposed by removal of a peel-off venting film, as described for FIGS. 1 and 2. It is important to note that at the commencement of use there is sufficient hydrogel 20 for the tube to be entirely occluded, in its lower region. The hydrogel is not bound to the wall of the tube. In use, once a cap (not shown) has been removed from the right limb, in order to expose the wick, and the venting film has been removed from the left limb, the first fragrance issues from the article by evaporation from the exposed portion of the wick 26. As evaporation continues the levels of the interfaces between the hydrogel 20 and the hydrophobic phases adjust. After substantial or complete evaporation of the first phase, the second phase is free to flow into the first limb, from which it then evaporates. An alternative embodiment is the same as that described with reference to FIG. 3, except that the hydrogel is bound to the wall of the tube. As the first phase evaporates there is no change in the levels of the interfaces between phases. After complete evaporation of the first phase the hydrogel is exposed to air and shrinks, by evaporation of water. After a certain degree of shrinkage the second phase can burst through or past the hydrogel, and into the right-hand limb, from which it evaporates. In FIG. 4 the article is of cuboid shape. It has an internal partition wall 32 which extends from its top wall to a position approaching its bottom wall. However there is a space left between the bottom edge of the partition 32, and the bottom wall. Water is present at the bottom of the article, and the water depth is such that the bottom edge of the partition wall is immersed in it. Above the water 34 to the right of the partition 32 is a first hydrophobic phase 36 comprising a first fragrance. Above the water 34 to the left of the partition is a second hydrophobic phase 38 comprising a second fragrance. A wick 40 has a major portion immersed in the first phase 36 and a minor portion exposed at the top of the article. The three phases are all coloured, differently. A small vent hole 42 is provided in the top wall, to the left of the partition 32. The vent hole may be exposed on peeling off a sticker (not shown). When the article of FIG. 4 is operational the first fragrance issues from the article first, by evaporation from the wick 40. After an interval, the second phase can start to bleed under the partition, and rise through the water. In this embodiment the first phase will not all have evaporated, when the second phase starts to bleed. The two fragrances are selected to be miscible, and to be olfactorily pleasant when blended; whereas the first and second phases are both immiscible with the water. It will be appreciated that once the second phase starts to bleed into the first phase there will form a composite fragrance, which will change as evaporation continues and bleeding of the second phase continues. If wished a wick may be employed extending to the bottom of the right-hand chamber of the article, in order to obtain wick-assisted emanation throughout the life of the product. In FIG. 5 the article is of cuboid shape. It has an internal partition wall 42 which extends from its top wall to its bottom wall. The partition wall 42 is made from a rigid impermeable plastics sheet material, except for a small section in contact with the bottom wall, this being a small plug 44 of a gel material which shrinks when in contact with air. The partition wall 42 divides the article into two chambers. The right-hand or first chamber 46 contains a concentrated liquid fragrance 48. A wick 50 is provided, having a lower end adjacent to the bottom wall of the first chamber and an upper end standing exposed from the chamber. A small aperture 52 is provided in the upper wall of the first chamber. The wick is sufficiently rigid as to be self-supporting. Thus it comprises a rigid body, typically a plastics rod, covered with a flock of fibrous material along which the liquid fragrance may wick. The bottom wall of the first chamber has on its inside a small circular wall 54, thereby forming a small pocket or well to receive the lower end of the wick. The wall 54 is directly beneath the hole 52 and so these parts keep the rigid wick in the desired upright location. The left-hand or second chamber 56 contains a second, different, liquid fragrance. A small vent hole 58 is provided in the top wall of this chamber. The vent hole is exposed on removing a plastics plug (not shown). When the article of FIG. 5 is operational the first fragrance issues from the article first, by evaporation from the wick 50. This continues until the evaporation of the first fragrance is complete, or nearly so. To be precise, it continues until the plug 44 which forms part of the partition 42 between the chambers is exposed to air. From that point the plug 44 starts to shrink. Depending on the effect required the gel material of the plug can be selected to shrink quickly and allow the second fragrance to burst past it and into the first chamber, while a small amount of the first fragrance remains; or to shrink slowly, so that by the time the second fragrance burst past the plug 44, the first fragrance has been exhausted. Once the plug 44 is breached the second fragrance floods into the first chamber, until the liquid levels in the first and second chambers are the same. Evaporation via the wick 50 now continues, until the article is entirely exhausted. In the article of FIG. 6 the article is U-shaped in cross-section, having a first upright limb 60, a second upright limb 62 and a horizontal connection limb 64. Thus the shape is of a somewhat squared-off U in cross-section (in contrast to the curved U-shape of the FIG. 3 embodiment). The article of FIG. 6 has a depth several times lager than the limb width shown in FIG. 6, such that it is stable against toppling when it is placed on a flat horizontal surface. The limb 60 is open at the top. It contains an evaporable gel 70, comprising a first fragrance. The limb 62 contains a liquid 68, comprising a second fragrance. Phases 60, 68 are kept apart by a gel 70 in the horizontal limb 64. The gel is of a type which shrinks when exposed to air. The connecting limb 64 has at its uppermost surface a liquid-impermeable gas-permeable membrane 72 and, covering that membrane 72, a gas-and-liquid-impermeable barrier membrane 74, in the form of a peel-off sticker. As with the other embodiments, the second limb is closed at its upper end except for a small vent hole 76 which in this embodiment is selectively opened and closed by a liftable/lowerable cover piece 78. To use the article of FIG. 6, a foil seal (not shown) is first removed from the upper end of the first limb. The fragranced gel 66 slowly evaporates. Once the gel 66 has gone the barrier gel 70 in the connecting limb 64 is exposed to air and it shrinks back, progressively along its upper surface, until there is a passage for the liquid 68 to flow, over the shrunken gel, into the limb 60. As the liquid 68 evaporates from the limb 60, further liquid 68 flows to the limb 60, as the liquid levels continually equilibrate, until all of the liquid 68 has evaporated. If the consumer wishes to accelerate the evaporation of the liquid 68 and/or to procure a mixed fragrance they can remove the sticker 74, exposing the gas-permeable membrane 72. The gel 70 is now exposed to air via the membrane 72 and will shrink back. Again, it will happen that there forms a passage for liquid 68 to flow from the second limb 62 to the first limb 60. The gel 66 in the first limb 60 is such that it can be impregnated by the liquid fragrance 68, by capillary action.
20050601
20130917
20060629
66231.0
A61L9015
0
AHMED, HASAN SYED
ARTICLES FOR THE RELEASE OR EMANATION OF VAPORS
UNDISCOUNTED
0
ACCEPTED
A61L
2,005
10,534,540
ACCEPTED
Instrument panel for a motor vehicle having an airbag device integrated in a ventilation arrangement
An airbag module and instrument panel assembly for a motor vehicle having at least one ventilation outlet and a ventilation duct attached thereto and arranged behind an instrument panel. The airbag module is fastened behind the instrument patent and has a gas generator and a folded airbag arranged within its housing wherein a ventilation outlet is closed by a grid that opens when the airbag module is triggered and is provided within the instrument panel for the unfolding airbag. The airbag module is arranged adjacent to the ventilation duct in such a manner that when the airbag module is triggered, the airbag unfolds into the ventilation duct and from there unfolds out of the instrument panel through the ventilation outlet. The pressure of the unfolding airbag moves away from the ventilation outlet which is arranged within the instrument panel.
1. An airbag module and instrument panel assembly for a motor vehicle having at least one ventilation outlet and a ventilation duct attached thereto and arranged behind an instrument panel, and an airbag module which is fastened behind the instrument panel and having a gas generator and a folded airbag and further having a ventilation outlet opening, which is closed by a grill, the assembly comprising the airbag module is arranged adjacent to the ventilation duct in such a manner that, when the airbag module is triggered, the airbag unfolds into the ventilation duct and from there unfolds out of the instrument panel through the ventilation outlet opening, the pressure of the unfolding airbag moving away the grill arranged within the instrument panel. 2. An airbag module and instrument panel assembly according to claim 1, further comprising a housing wall of the airbag module that is adjacent to the ventilation duct forms a dividing wall for the ventilation duct and, when the airbag module is triggered, the dividing wall moves into the ventilation duct in such a manner that there is formed an escape channel leading from the airbag module to the ventilation outlet. 3. An airbag module and instrument panel assembly according to claim 1, further comprising in that the dividing wall of the ventilation duct is adjacent to the airbag module and forms a housing wall for the airbag module and that, when the airbag module is triggered, the dividing wall moves into the ventilation duct in such a manner that there is formed an escape channel leading from the airbag module to the ventilation outlet. 4. An airbag module and instrument panel assembly according to claim 3, further comprising in that the airbag module is arranged laterally next to the ventilation duct and that the dividing and housing wall swings into the ventilation duct around a fixed point. 5. An airbag module and instrument panel assembly according to claim 3, further comprising in that the ventilation outlet partially overlaps the airbag module and that a region of the dividing wall that faces the instrument panel forms a diagonal kink leading to an edge of the ventilation outlet located adjacent the module, and the dividing and housing wall running behind the ventilation outlet. 6. An airbag module and instrument panel assembly according to claim 5, further comprising in that the kink is dimensioned such that the kink fits into place on an opposite edge of the ventilation outlet during the swinging of the dividing wall, thus forming and delimiting the escape channel for the unfolding airbag. 7. An airbag module and instrument panel assembly according to claim 3, further comprising in that the airbag module is arranged on a side of a ventilation duct opposite the instrument panel. 8. An airbag module and instrument panel assembly according to claim 7, further comprising in that the airbag module is designed L-shaped with a first section located laterally next to the ventilation duct and a second section located on the side of the ventilation duct opposite the instrument panel, the dividing walls of the ventilation duct (12) adjacent to the swinging into the ventilation duct when the airbag module is triggered. 9. An airbag module and instrument panel assembly according to claim 1, further comprising in that a partition wall arranged within a housing of the airbag module divides the airbag, which is folded into the housing, into a first and second package, the first folding package being arranged adjacent to the ventilation outlet. 10. An airbag module and instrument panel assembly according to claim 9, further comprising in that the first folding package adjacent to the ventilation outlet has a smaller dimension than the second folding package and acts as a starting bubble for the pulling out of the second folding package when the airbag module is triggered. 11. An airbag module and instrument panel assembly according to claim 9 further comprising in that the partition wall divides the folded airbag into the first and second folding packages. 12. An airbag module and instrument panel assembly according to claim 1, further comprising in that a holding device attaches the airbag module to the ventilation duct and fastens the airbag module to the interior of the instrument panel. 13. An airbag module and instrument panel assembly according to claim 1, further comprising in that a cover covers and holds the airbag in the vicinity where the airbag module is connected to the dividing wall, the airbag being folded into the housing and the cover opening when the airbag unfolds and lying down as protection between the airbag and edges of the ventilation outlet. 14. An airbag module and instrument panel assembly according to claim 1, further comprising in that predetermined breaking lines separate a segment of the instrument panel adjacent to the ventilation outlet from the remainder of the instrument panel so that the unfolding airbag separates the segments from the remainder of the instrument panel, and both the separated segment and the ventilation outlet form an escape hole for the airbag.
CROSS REFERENCE TO RELATED APPLICATION This application claims priority to PCT/EP2003/012613, filed Nov. 12, 2003 and GB 10253185.4, filed Nov. 15, 2002. FIELD OF THE INVENTION This invention relates to an instrument panel for a motor vehicle comprising of at least one ventilation outlet and a ventilation duct attached thereto and arranged behind the instrument panel, and further having an airbag module which is fastened behind the instrument panel and has a gas generator and a folded airbag arranged within its housing. An outlet opening, which is closed by a covering that opens when the airbag module is triggered, is provided within the instrument panel for the unfolding airbag. BACKGROUND OF THE INVENTION An instrument panel of the type related to this invention is known from U.S. Pat. No. 6,264,233. To the extent that an airbag module and a ventilation duct are arranged behind the instrument panel of a vehicle, there is provided a covering that covers both components and on the one hand forms the covering for the airbag module and on the other hand has integrated within itself a ventilation outlet having a ventilation cover covering the outlet the ventilation cover of that design being attached to the ventilation duct when the cover or ventilation outlet respectively is still in the position established within the instrument panel. The unfolding airbag forces the covering open when the airbag module is triggered, and the ventilation outlet also releases itself from the ventilation duct fastened to the instrument panel. The known instrument panel and the fitting arrangement of ventilation duct and airbag module of the type described above has the disadvantage that a correspondingly large space is required for accommodating an airbag module behind the instrument panel and that the common covering for the ventilation duct and airbag module features substantial dimensions, this covering to be opened when a trigger occurs. In view of the foregoing it is an object of the invention to reduce the space requirement for the fitting arrangement of the airbag module behind the instrument panel in an instrument panel. This object, including advantageous embodiments and further developments of the invention, is accomplished by the content of the claims that follow this description. SUMMARY OF THE INVENTION The basic concept of the invention provides an airbag module arranged adjacent to the ventilation duct in such a manner that, when the airbag module is triggered, the airbag unfolds into the ventilation duct and from there unfolds out of the instrument panel through the ventilation outlet, the pressure of the unfolding airbag moving away the ventilation outlet arranged within the instrument panel. The invention has the advantage that the opening in the instrument panel, which is necessary for providing ventilation is also used for the escape of the airbag from the airbag module, so that it is possible to dispense with an extra openable covering provided in the instrument panel for the escape of the airbag. Since the ventilation duct is simultaneously used as an escape channel for the airbag when the airbag unfolds, a much more space-saving packaging arrangement of the airbag module behind the instrument panel is possible. In one exemplary embodiment of the invention, housing wall of the airbag module is adjacent to the ventilation duct and forms a dividing wall for the duct and, when the airbag module is triggered, moves into the duct in such a manner that there is formed an escape channel leading from the airbag module to the ventilation outlet. In this exemplary embodiment, there remains open, within the wall enclosing the ventilation duct, a subregion that is closed by the assigned housing wall of the airbag module when the airbag module is installed. An alternative form of the invention may be provided that the dividing wall of the ventilation duct adjacent to the airbag module forms a housing wall for the airbag module and that, when the airbag module is triggered, the common dividing wall and housing wall moves into the ventilation duct in such a manner that there is formed an escape channel leading from the airbag module to the ventilation outlet. In this embodiment, the common dividing and housing wall is assigned to the ventilation duct, so that it is possible to dispense with an additional wall on the housing of the airbag. This has the advantage that the required motion of the common dividing and housing wall into the ventilation duct may already be taken into consideration during the design and manufacture of the ventilation duct. In one exemplary embodiment of the invention, it is provided that the airbag module is arranged laterally next to the ventilation duct and the dividing and housing wall swings into the ventilation duct around a fixed point located far from the instrument panel. In regard to the fitting arrangement of dividing and housing wall, it may here be provided that the ventilation outlet partially overlaps the airbag module and that that region of the dividing and housing wall that faces the instrument panel forms a diagonal kink leading to that edge of the ventilation outlet located on the module side, the mutual dividing and housing wall running behind the ventilation outlet may be further provided that the kink is dimensioned in such a manner that the kink fits into place on the opposite edge of the ventilation outlet during the swinging of the dividing and housing wall, thus forming the escape channel for the unfolding airbag. In an alternative embodiment, the invention provides that the airbag module is arranged on the side of the ventilation duct opposite the instrument panel. To reduce the overall depth of the fitting arrangement of ventilation duct and airbag module behind the instrument panel according to this invention in it may be provided that the airbag module is designed L-shaped with one section located laterally next to the ventilation duct and one section located the ventilation duct opposite the instrument panel, the common dividing and housing walls of the ventilation duct adjacent to the airbag module being integrally joined together and swinging into the ventilation duct when the airbag module is deployed. Since a separate direct opening in the instrument panel is not required as an escape hole for the airbag, measures are provided in one exemplary embodiment of the invention to ensure that the airbag reliably unfolds out of the airbag module through the ventilation duct. For this purpose, it is provided that a partition wall arranged within the housing of the airbag module divides the airbag, which is folded into the housing, into two folding packages, one folding package being arranged adjacent to the ventilation outlet. In this case it may be advantageous for the folding package adjacent to the ventilation outlet to have a smaller dimension than the second folding package and act as a starting bubble for pulling out the second folding package when the airbag module is triggered. Depending on the structural factors, the invention also includes the concept that the fitting arrangement of a plurality of partition walls divides the folded airbag into a plurality of folding packages. In regard to installing an airbag module onto the ventilation duct, it may be provided that a holding device attaches the airbag module to the ventilation duct and fastens it to the interior of the instrument panel. In one exemplary embodiment of the invention, it is provided that a cover covers and holds the airbag in the vicinity where the airbag module is connected to the mutual dividing and housing wall, the airbag being folded into the housing and the foil tearing open when the airbag unfolds and protection between the airbag and the edges of the ventilation outlet. Since a very narrowly designed ventilation outlet may cause problems in regard to the speed at which the airbag unfolds, it is provided in one exemplary embodiment of the invention that predetermined breaking lines separate the vicinity of the instrument panel adjacent to the ventilation outlet from the rest of the instrument panel so that the unfolding airbag separates, from the instrument panel, both the separated region and the ventilation outlet combining to act as escape hole for the airbag. In this case, the specified area of the instrument panel advantageously enlarges the escape hole for the airbag appropriately. BRIEF DESCRIPTION OF THE DRAWINGS The drawing depicts exemplary embodiments of the invention, which will be described below. The drawing shows: FIG. 1 is a longitudinal section of a subregion of an instrument panel having ventilation arrangement and airbag device according to a first embodiment of this invention prior to triggering of the airbag device, FIG. 2 shows the airbag device shown in FIG. 1 in a first stage of unfolding of the airbag during deployment of the airbag device, FIG. 3 shows the airbag device shown in FIG. 1 in an advanced stage of unfolding of the airbag during deployment of the airbag device, FIG. 4 is a cross-sectional view of a second embodiment of the airbag device of this invention, FIG. 5 shows the airbag device of FIG. 4 in a stage of partial unfolding of the airbag during deployment, FIG. 6 shows an airbag arrangement in accordance with a third embodiment of this invention, FIG. 7 shows an airbag arrangement in accordance with a fourth embodiment of this invention, FIGS. 8a-c shows different stages of installation of the airbag device in accordance with this invention on the ventilation duct and instrument panel. DETAILED DESCRIPTION OF THE INVENTION FIG. 1 depicts an instrument panel 11 contiguous to a windshield 10 of a motor vehicle in which an opening for both the ventilation outlet and escape of the airbag is arranged directed upwardly toward the windshield 10, so that in this fitting arrangement of the instrument panel, both the ventilation duct and airbag module are underneath the instrument panel 11 relative to the windshield. In particular, there is provided within the instrument panel a ventilation outlet 13, which is covered by a ventilation grill 4, which fits into the instrument panel 11 with positive fit. A ventilation duct 12, which is enclosed by walls 15 and for example spreads the air supply across the width of the vehicle underneath the instrument panel 11, is arranged underneath the ventilation outlet 13, the air supply being conveyed into the passenger compartment if necessary by a plurality of ventilation outlets 13 configured in the instrument panel 11. As still to be described in detail, an airbag module 16, within whose housing 17 a gas generator 19 and a folded airbag 18 are arranged, is positioned underneath the instrument panel 11 and directly adjacent to a ventilation duct 12. A partition wall 20 arranged in the housing 17 of the airbag module 16 divides the folded airbag 18 into two folded, and specifically into one folded package 21 directly adjacent to the ventilation outlet 13 and one folded package 22 arranged on the opposite side of the partition wall 20. To the extent that the ventilation duct 12 and airbag module 16 contact one another because of their directly adjacent arrangement, there is provided a mutual dividing and housing wall 23 which, as cooperating with walls 15 and defining the ventilation duct 12. The wall 23 is connected one of walls 15 of the ventilation duct 12 at a hinge connection 24 in such a manner that the pressure of the unfolding airbag 18 swings the dividing and housing wall 23 into the ventilation duct 12 when the airbag module 16 is triggered. In this case the dividing and housing wall 23 is arranged relative to the ventilation outlet 13 in such a manner that the ventilation outlet 13 overlaps the mutual dividing and housing wall 23, wherein the region of this wall that faces the instrument panel 11 and is contiguous with the instrument panel 11 forms a diagonal kink 25 leading to the edge of the ventilation outlet 13 running on the side of the airbag module 16, the dividing and housing wall 23 running behind the ventilation outlet 13. This kink 25 is dimensioned in such a manner, that the edge of wall 23 fits into place on the opposite edge 26 of the ventilation outlet 13 when the mutual dividing and housing wall 23 swings into the ventilation duct 12, thus forming and delimiting an escape channel 40 for the unfolding airbag 18. To the extent that the ventilation outlet 13 is closed by a ventilation grill 14, a rebound strap 28 holds the ventilation grill on the instrument panel 11 so that the ventilation grill 14 will not fly around the passenger compartment when instrument panel 11 releases the ventilation grill 14. The region of the ventilation grill 14 facing the airbag module 16 also includes an air baffle 27 extending behind the instrument panel 11 to the ventilation facing 14 to open forcefully. FIGS. 1 to 3 depict the triggering of the airbag module 16 in detail, FIG. 2 showing that the gas released by the gas generator 19 when the gas generator is ignited first pressurizes the first folded package 21 facing the instrument panel 11, so that this folding package exerts a corresponding pressure on the dividing and housing wall 23 toward the ventilation duct 12. This pressure presses the dividing and housing wall 23 around the hinge connection 24 inwards into the ventilation duct 12. At the same time, the folded package 21, which unfolds next, exerts a corresponding upwardly-directed pressure on the ventilation grill 14 because of the air baffle 27 located on the underside of the ventilation grill 14, forces the ventilation grill 14 to swing open in the direction of the windshield 10 and releases the ventilation outlet 13 as an unfolding hole for the airbag 18. In this respect, after the ignition of the gas generator 19, the first folding package 21 first acts as an extraction bubble that then pulls the second folding package 22 arranged underneath the partition wall 20 out of the housing 17 of the airbag module 16 during the further gas pressurization. In the case of very narrow ventilation outlet 13 and grill 14, it may be provided that predetermined breaking lines separate, from the rest of the instrument panel 11, in that region of the instrument panel 11 adjacent to the respective ventilation outlet 13 and preferably surrounding the ventilation outlet 13. In such a configuration, when the airbag module 16 unfolds, the unfolding airbag detaches both the region of the instrument panel 11 separated by predetermined breaking lines and the ventilation outlet 13 from the instrument panel 11 so that an appropriately larger escape hole is formed for the airbag 18. The exemplary embodiment that is depicted in FIG. 4 and whose triggering is depicted in FIG. 5 differs from the exemplary embodiment previously described in FIGS. 1 to 3 in that the airbag module 16 is configured L-shaped, having one section 30 located laterally next to ventilation duct 12 and one section 29 located behind the ventilation duct 12 opposite instrument panel 11, so that the airbag module 16 wraps partially around the ventilation duct 12. This provides a particularly space-saving fitting arrangement of ventilation duct 12 and airbag module 16. In this design of airbag module 16, two wall sections of ventilation duct 12 each form adjacent mutual dividing and housing walls 23 which are integrally joined together and again swing into the ventilation duct 12 around a hinge-like connection 24 when the airbag module is triggered. Because the fitting arrangement of partition wall 20, which is again provided, is matched to the shape of airbag module 16, the design takes care that the first folding package 21, which the gas generator 19 first pressurizes, acts as extraction bubble for the second unfolding package 22, as described in FIGS. 1 to 3. FIGS. 6 and 7 depict exemplary embodiments of the invention in which the partition wall 20 or plurality of partition walls 20, respectively, provided in housing 17 of airbag module 16 form corresponding first, second or further airbag folded packages in order to assure that the airbag 18 smoothly unfolds out of the airbag module 16 and ventilation duct 12, respectively, depending on the assignment of the airbag module 16 to the ventilation duct 12. Finally, FIGS. 8a-c show that simplified installation can be associated with the design of an instrument panel having the ventilation arrangement and airbag device according to invention. Here the ventilation duct 12 and its assigned walls 15 and 23 are fastened to the instrument panel 11. In this case the ventilation duct 12 is provided with a mounting plate 32, which is arranged to accommodate the airbag module 16 and has an opening 33 built therein, wherein a projecting part 34 configured on the airbag module 16 is used to insert the airbag module into the opening 30 of the mounting plate 32 and, after the airbag module has been swung toward the mutual dividing and housing wall 23, it is fastened to the instrument panel 11 using a fastener 35. For this installation procedure, the airbag module 16 is provided with a cover layer 31 for the folded airbag 18 when it fits into place on the dividing and housing wall 23, which is common with the ventilation duct 12, this cover layer preferably being made of a welded-on foil that tears open from the pressure of the unfolding airbag. As evident from FIG. 3, the cover 31 may be configured in such a manner that it lies as protection between the airbag 18 and the edges of the ventilation outlet in particular when the airbag 18 unfolds, so that the fabric of the airbag 18 is treated gently and there is a reduced danger that the fabric will tear. The characteristics of the object of these documents disclosed in the above description, the claims, the abstract and the drawing may be essential for the realization of the invention in its various embodiments both individually and in any desired combination with each other.
<SOH> BACKGROUND OF THE INVENTION <EOH>An instrument panel of the type related to this invention is known from U.S. Pat. No. 6,264,233. To the extent that an airbag module and a ventilation duct are arranged behind the instrument panel of a vehicle, there is provided a covering that covers both components and on the one hand forms the covering for the airbag module and on the other hand has integrated within itself a ventilation outlet having a ventilation cover covering the outlet the ventilation cover of that design being attached to the ventilation duct when the cover or ventilation outlet respectively is still in the position established within the instrument panel. The unfolding airbag forces the covering open when the airbag module is triggered, and the ventilation outlet also releases itself from the ventilation duct fastened to the instrument panel. The known instrument panel and the fitting arrangement of ventilation duct and airbag module of the type described above has the disadvantage that a correspondingly large space is required for accommodating an airbag module behind the instrument panel and that the common covering for the ventilation duct and airbag module features substantial dimensions, this covering to be opened when a trigger occurs. In view of the foregoing it is an object of the invention to reduce the space requirement for the fitting arrangement of the airbag module behind the instrument panel in an instrument panel. This object, including advantageous embodiments and further developments of the invention, is accomplished by the content of the claims that follow this description.
<SOH> SUMMARY OF THE INVENTION <EOH>The basic concept of the invention provides an airbag module arranged adjacent to the ventilation duct in such a manner that, when the airbag module is triggered, the airbag unfolds into the ventilation duct and from there unfolds out of the instrument panel through the ventilation outlet, the pressure of the unfolding airbag moving away the ventilation outlet arranged within the instrument panel. The invention has the advantage that the opening in the instrument panel, which is necessary for providing ventilation is also used for the escape of the airbag from the airbag module, so that it is possible to dispense with an extra openable covering provided in the instrument panel for the escape of the airbag. Since the ventilation duct is simultaneously used as an escape channel for the airbag when the airbag unfolds, a much more space-saving packaging arrangement of the airbag module behind the instrument panel is possible. In one exemplary embodiment of the invention, housing wall of the airbag module is adjacent to the ventilation duct and forms a dividing wall for the duct and, when the airbag module is triggered, moves into the duct in such a manner that there is formed an escape channel leading from the airbag module to the ventilation outlet. In this exemplary embodiment, there remains open, within the wall enclosing the ventilation duct, a subregion that is closed by the assigned housing wall of the airbag module when the airbag module is installed. An alternative form of the invention may be provided that the dividing wall of the ventilation duct adjacent to the airbag module forms a housing wall for the airbag module and that, when the airbag module is triggered, the common dividing wall and housing wall moves into the ventilation duct in such a manner that there is formed an escape channel leading from the airbag module to the ventilation outlet. In this embodiment, the common dividing and housing wall is assigned to the ventilation duct, so that it is possible to dispense with an additional wall on the housing of the airbag. This has the advantage that the required motion of the common dividing and housing wall into the ventilation duct may already be taken into consideration during the design and manufacture of the ventilation duct. In one exemplary embodiment of the invention, it is provided that the airbag module is arranged laterally next to the ventilation duct and the dividing and housing wall swings into the ventilation duct around a fixed point located far from the instrument panel. In regard to the fitting arrangement of dividing and housing wall, it may here be provided that the ventilation outlet partially overlaps the airbag module and that that region of the dividing and housing wall that faces the instrument panel forms a diagonal kink leading to that edge of the ventilation outlet located on the module side, the mutual dividing and housing wall running behind the ventilation outlet may be further provided that the kink is dimensioned in such a manner that the kink fits into place on the opposite edge of the ventilation outlet during the swinging of the dividing and housing wall, thus forming the escape channel for the unfolding airbag. In an alternative embodiment, the invention provides that the airbag module is arranged on the side of the ventilation duct opposite the instrument panel. To reduce the overall depth of the fitting arrangement of ventilation duct and airbag module behind the instrument panel according to this invention in it may be provided that the airbag module is designed L-shaped with one section located laterally next to the ventilation duct and one section located the ventilation duct opposite the instrument panel, the common dividing and housing walls of the ventilation duct adjacent to the airbag module being integrally joined together and swinging into the ventilation duct when the airbag module is deployed. Since a separate direct opening in the instrument panel is not required as an escape hole for the airbag, measures are provided in one exemplary embodiment of the invention to ensure that the airbag reliably unfolds out of the airbag module through the ventilation duct. For this purpose, it is provided that a partition wall arranged within the housing of the airbag module divides the airbag, which is folded into the housing, into two folding packages, one folding package being arranged adjacent to the ventilation outlet. In this case it may be advantageous for the folding package adjacent to the ventilation outlet to have a smaller dimension than the second folding package and act as a starting bubble for pulling out the second folding package when the airbag module is triggered. Depending on the structural factors, the invention also includes the concept that the fitting arrangement of a plurality of partition walls divides the folded airbag into a plurality of folding packages. In regard to installing an airbag module onto the ventilation duct, it may be provided that a holding device attaches the airbag module to the ventilation duct and fastens it to the interior of the instrument panel. In one exemplary embodiment of the invention, it is provided that a cover covers and holds the airbag in the vicinity where the airbag module is connected to the mutual dividing and housing wall, the airbag being folded into the housing and the foil tearing open when the airbag unfolds and protection between the airbag and the edges of the ventilation outlet. Since a very narrowly designed ventilation outlet may cause problems in regard to the speed at which the airbag unfolds, it is provided in one exemplary embodiment of the invention that predetermined breaking lines separate the vicinity of the instrument panel adjacent to the ventilation outlet from the rest of the instrument panel so that the unfolding airbag separates, from the instrument panel, both the separated region and the ventilation outlet combining to act as escape hole for the airbag. In this case, the specified area of the instrument panel advantageously enlarges the escape hole for the airbag appropriately.
20050511
20080205
20070125
92830.0
B60R21205
0
ILAN, RUTH
INSTRUMENT PANEL FOR A MOTOR VEHICLE HAVING AN AIRBAG DEVICE INTEGRATED IN A VENTILATION ARRANGEMENT
UNDISCOUNTED
0
ACCEPTED
B60R
2,005
10,534,626
ACCEPTED
Method for diagnosis and treatment of vascular disease
A method for diagnosing decreased vascular function is disclosed. The method includes assaying the number of endothelial progenitor cells. A method for detecting increased cardiovascular risk is also disclosed, as is a method for diagnosing atherosclerosis. In one example, the methods include assaying the number of endothelial progenitor cells. A method for treating a subject with decreased vascular function is disclosed. The method includes administering a therapeutically effective amount of endothelial progenitor cells to the subject. In one embodiment, the subject has atherosclerosis.
1. A method of diagnosing decreased vascular function or increased cardiovascular risk in a subject, comprising assaying the number of endothelial progenitor cells in a blood sample from the subject, wherein the subject does not have symptomatic cardiovascular disease, and wherein a decrease in the number of endothelial progenitor cells in the sample as compared to a control indicates decreased vascular function. 2. The method of claim 1, wherein assaying the number of endothelial progenitor cells comprises isolating the buffy coat from a blood sample of the subject; culturing the buffy coat on a solid support coated with a first substrate; isolating the non-adherent cells; culturing the non-adherent cells on a solid support coated with a second substrate; counting the number of colonies on the solid support. 3. The method of claim 2, wherein a lower number of colonies on the solid support as compared to a control indicates decreased vascular function. 4. The method of claim 1, wherein assaying the number of endothelial progenitor cells comprises determining the number of VEGFR2+CD31hi cells in the sample. 5. The method of claim 1, wherein the control is a blood sample from a subject that does not have atherosclerosis. 6. The method of claim 1, wherein the control is a standard value. 7. The method of claim 2, wherein the first substrate comprises fibronectin. 8. The method of claim 2, wherein the first and the second substrate comprise fibronectin. 9. A method of diagnosing increased vascular function in a subject, comprising assaying the number of endothelial progenitor cells in a blood sample from the subject, wherein an increase in the number of endothelial progenitor cells in the sample as compared to a control indicates increased vascular function. 10. The method of claim 9, wherein the subject has been treated with a cholesterol-lowering agent. 11. The method of claim 10, wherein the control is a blood sample from the subject prior to treatment with the cholesterol-lowering agent. 12. The method of claim 9, wherein assaying the number of endothelial progenitor cells comprises isolating the buffy coat from a blood sample of the subject; culturing the buffy coat on a solid support coated with a first substrate; isolating the non-adherent cells; culturing the non-adherent cells on a solid support coated with a second substrate; counting the number of colonies on the solid support. 13. The method of claim 12, wherein a higher number of colonies on the solid support as compared to a control indicates increased vascular function. 14. The method of claim 12, wherein the first substrate comprises fibronectin. 15. The method of claim 12, wherein the first substrate and the second substrate comprises fibronectin. 16. The method of claim 9, wherein assaying the number of endothelial progenitor cells comprises determining the number of VEGFR2+CD31hi cells in the sample. 17. A method of treating a subject with decreased vascular function, comprising, administering to the subject a therapeutically effective amount of endothelial progenitor cells, thereby increasing vascular function in the subject. 18. The method of claim 17, wherein the subject has atherosclerosis. 19. The method of claim 17, wherein the endothelial progenitor cells are VEGFR2+CD31hi cells. 20. A method for screening for an agent that affects vascular function or is of use in treating a cardiovascular disease, comprising administering a therapeutically effective amount of the agent to a subject, and assessing the number of endothelial progenitor cells in a sample from the subject; wherein an increased number of endothelial progenitor cells in the sample as compared to a control indicates that the agent affects vascular function or is of use in treating a cardiovascular disease. 21. The method of claim 20, wherein the subject is a non-human animal. 22. The method of claim 22, wherein the subject is a human. 23. The method of claim 20, wherein the agent is a cholesterol lowering agent. 25. The method of claim 20, wherein the control is the number of circulating endothelial cell in sample from a subject not administered the agent. 25. The method of claim 20, wherein the sample is a blood sample. 26. The method of claim 20, wherein the sample is a buffy coat sample. 27. The method of claim 20, wherein the endothelial progenitor cells are circulating endothelial progenitor cells. 28. The method of claim 20, wherein assaying the number of endothelial progenitor cells comprises isolating the buffy coat from a blood sample of the subject; culturing the buffy coat on a solid support coated with a first substrate; isolating the non-adherent cells; culturing the non-adherent cells on a solid support coated with a second substrate; enumerating the number of colonies on the solid support. 29. The method of claim 20, wherein assaying the number of endothelial progenitor cells comprises determining the number of VEGFR2+CD31hi cells in the sample. 30-47. (canceled) 28. A method of diagnosing increased cardiovascular risk or decreased vascular function in a subject, comprising assaying a number of senescent endothelial progenitor cells in a blood sample from the subject, wherein an increase in the number of senescent endothelial progenitor cells in the sample as compared to a control indicates increased cardiovascular risk or decreased vascular function. 49. The method of claim 48, wherein the control is a standard value. 50. The method of claim 48, wherein the control is a number of senescent endothelial progenitor cells in a blood sample from a subject known not to be affected by a disease or disorder. 51. A method for screening for an agent of use in treating a cardiovascular disease, comprising administering a therapeutically effective amount of the agent to a subject, and assessing the number of senescent endothelial progenitor cells in a sample from the subject; wherein a decreased number of senescent endothelial progenitor cells in the sample as compared to a control indicates that the agent is of use in treating the cardiovascular disease. 52. The method of claim 51, wherein the control is a standard value. 53. The method of claim 51, wherein the control is a number of senescent endothelial progenitor cells in a blood sample from a subject known to be affected by a disease or disorder.
FIELD This application relates to the field of vascular disease such as atherosclerosis, more specifically to methods for diagnosis of altered vascular function by assessing the number of endothelial progenitor cells. This application also relates to the use of endothelial progenitor cells in the treatment of vascular disease. BACKGROUND Cardiovascular disease is a major health risk throughout the industrialized world. Atherosclerosis, the most prevalent of cardiovascular diseases, is the principal cause of heart attack, stroke, and gangrene of the extremities. It is also the principal cause of death in the United States. Atherosclerosis is a complex disease involving many cell types and molecular factors (for review, see Ross, Nature 362:801-809, 1993). The process is believed to occur as a response to insults to the endothelial cell layer that lines the wall of the artery. The process includes the formation of fibrofatty and fibrous lesions or plaques, preceded and accompanied by inflammation. The advanced lesions of atherosclerosis may occlude an artery, and result from an excessive inflammatory-fibroproliferative response to numerous different forms of insult. For example, shear stresses are thought to be responsible for the frequent occurrence of atherosclerotic plaques in regions of the circulatory system where turbulent blood flow occurs, such as branch points and irregular structures. The first event that is observed in the formation of an atherosclerotic plaque occurs when blood-borne monocytes adhere to the vascular endothelial layer and transmigrate through to the sub-endothelial space. Adjacent endothelial cells at the same time produce oxidized low density lipoprotein (LDL). These oxidized LDL's are then taken up in large amounts by the monocytes through scavenger receptors expressed on their surfaces. In contrast to the regulated pathway by which native LDL (nLDL) is taken up by nLDL specific receptors, the scavenger pathway of uptake is not regulated by the monocytes. The lipid-filled monocytes are termed “foam cells,” and are the major constituent of the fatly streak. Interactions between foam cells and the endothelial and SMCs which surround them lead to a state of chronic local inflammation which can eventually lead to smooth muscle cell proliferation and migration, and the formation of a fibrous plaque. Such plaques occlude the blood vessel concerned and restrict the flow of blood, resulting in ischemia. Ischemia is characterized by a lack of oxygen supply in tissues of organs due to inadequate perfusion. The most common cause of ischemia in the heart is atherosclerotic disease of epicardial coronary arteries. By reducing the lumen of these vessels, atherosclerosis causes an absolute decrease in myocardial perfusion in the basal state or limits appropriate increases in perfusion when the demand for flow is augmented. The principal surgical approaches to the treatment of ischemic atherosclerosis are bypass grafting, endarterectomy, and percutaneous translumenal angioplasty (PCTA). The latter approach often fails due to restenosis, in which the occlusions recur and often become even worse. This is estimated to occur at an extraordinarily high (30-50%) rate. It appears that much of the restenosis is due to further inflammation, smooth muscle accumulation, and thrombosis. Thus, there remains a need for methods to diagnose and/or treat atherosclerosis. SUMMARY Methods for assessing the number of circulating endothelial progenitor cells are disclosed herein. Enumeration of the number of circulating endothelial progenitor cells can be used to detect alterations in vascular function, and can be used to identify agents that affect vascular function. These methods are of use in diagnosing and treating a variety of vascular disorders, including, but not limited to atherosclerosis. In one embodiment, a method is disclosed herein for diagnosing decreased vascular function in a subject. The method includes assaying the number of endothelial progenitor cells, for example from a blood sample from a subject. A decrease in the number of endothelial progenitor cells in the sample as compared to a control indicates decreased vascular function. In another embodiment, a method is also disclosed for detecting increased vascular function in a subject. The method includes assaying the number of endothelial progenitor cells, for example from a blood sample from a subject. An increase in the number of endothelial progenitor cells in the sample as compared to a control indicates increased vascular function. In yet another embodiment, a method for diagnosing future cardiovascular risk, such as the development of atherosclerosis, is disclosed. The method includes assaying the number of endothelial progenitor cells. A decrease in the number of endothelial progenitor cells in the sample as compared to a control indicates increased cardiovascular risk. A method is disclosed to screen for agents that affect vascular function. The method includes administering a therapeutically effective amount of the agent to a subject, and assessing the number of endothelial progenitor cells in a sample from the subject. An increased number of endothelial progenitor cells in the sample as compared to a control indicates that the agent affects vascular function. A method is also disclosed for screening for agents of use in treating cardiovascular disease. The method includes administering a therapeutically effective amount of the agent to a subject, and assessing the number of endothelial progenitor cells in a sample from the subject. An increased number of endothelial progenitor cells in the sample as compared to a control indicates that the agent is of use for the treatment of the cardiovascular disease. Also disclosed is a method for treating a subject with decreased vascular function. The method includes administering a therapeutically effective amount of endothelial progenitor cells to the subject. In one embodiment, the subject has atherosclerosis. A method is disclosed for diagnosing increased cardiovascular risk or decreased vascular function in a subject. The method includes assaying a number of senescent endothelial progenitor cells in a blood sample from the subject, wherein a increase in the number of senescent endothelial progenitor cells in the sample as compared to a control indicates increased cardiovascular risk or decreased vascular function. In addition, a method is disclosed for screening for an agent of use in treating a cardiovascular disease. The method includes administering a therapeutically effective amount of the agent to a subject, and assessing the number of senescent endothelial progenitor cells in a sample from the subject. A decreased number of endothelial progenitor cells in the sample as compared to a control indicates that the agent is of use in treating the cardiovascular disease. The foregoing and other features and advantages will become more apparent from the following detailed description of several embodiments, which proceeds with reference to the accompanying figures. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 is a digital image of a phase contrast micrograph of endothelial progenitor cell colony with central cluster of cells surrounded by characteristic spindle shaped cells. FIGS. 2A-B are a set of graphs showing association of cardiovascular risk factors on endothelial progenitor cell colony counts. FIG. 2A is a set of bar graphs showing the relationship between endothelial progenitor cell colony forming unit (CFU-endothelial progenitor cell) number and individual risk factors including hypertension, diabetes, total cholesterol levels and age. Individual risk factors were defined in accordance with the Framingham guidelines. FIG. 2B is a line graph of the relationship between calculated Framingham risk score and levels of circulating endothelial progenitor cells. Levels of endothelial progenitor cells were expressed as the mean number of colonies per well using at least four separate determinations for each individual. FIGS. 3A-C are a set of graphs showing the relationship between endothelial progenitor cell number and flow mediated brachial reactivity. FIG. 3A is a line graph showing the correlation of endothelial progenitor cell colony counts with measurements of flow mediated brachial reactivity. FIG. 3B is a bar graph of the tertiles based on measured flow mediated brachial reactivity. Significant differences in circulating endothelial progenitor cell levels are demonstrated. FIG. 3C is a bar graph of the levels of endothelial progenitor cells. A correlation is demonstrated with flow mediated brachial reactivity when corrected for endothelial independent vasodilation (flow mediated brachial reactivity/nitroglycerin). p value in panel 3B and 3C is from a t-test comparison of the highest and lowest tertile adjusted for multiple comparisons (n=3) using the Tukey-Kramer procedure. Age adjustment did not alter the calculated p values. FIG. 4 is a set of graphs of endothelial progenitor cell activity is a predictor of flow mediated brachial reactivity. All subjects were divided into four subsets based on endothelial progenitor cell counts and Framingham risk factor score. Endothelial progenitor cell activity is a stronger predictor of measured flow mediated brachial reactivity than the presence or absence of conventional cardiovascular risks. FIG. 5 is a table (Table 1) showing the characteristics of patients (n=45) analyzed according to the tertiles of circulating endothelial progenitor cells (EPCs). †The p value is from a t-test comparison of the highest and lowest tertile. Non-categorized results were verified with non-parametric tests and also underwent age adjustment. All statistically significant relationships retained significance following these analyses. DETAILED DESCRIPTION Terms Unless otherwise noted, technical terms are used according to conventional usage. Definitions of common terms in molecular biology may be found in Benjamin Lewin, Genes V, published by Oxford University Press, 1994 (ISBN 0-19-854287-9); Kendrew et al. (eds.), The Encyclopedia of Molecular Biology, published by Blackwell Science Ltd., 1994 (ISBN 0-632-02182-9); and Robert A. Meyers (ed.), Molecular Biology and Biotechnology: a Comprehensive Desk Reference, published by VCH Publishers, Inc., 1995 (ISBN 1-56081-569-8). In order to facilitate review of the various embodiments of this disclosure, the following explanations of specific terms are provided: AC 133 (CD 133): A 120 kDa five transmembrane domain glycoprotein (5-TM) expressed on primitive cell populations, such as CD34 bright hematopoietic stem and progenitor cells, neural and endothelial stem cells, and other primitive cells such as retina and retinoblastoma and developing epithelium. CD133 is expressed on hemagioblasts and developing endothelium, in addition to hematopoietic stem cells and neural stem cells. Adherent: A cell adheres to a surface if it sticks or clings to the surface. Conversely, a non-adherent cell does not stick to the surface. A non-adherent cell may settle on a surface (for example, due to the forces of gravity), but it can easily be removed from the surface (for example, by gentle agitation). Atherosclerosis: The progressive narrowing and hardening of a blood vessel over time. Atherosclerosis is a common form of ateriosclerosis in which deposits of yellowish plaques (atheromas) containing cholesterol, lipoid material, and lipophages are formed within the intima and inner media of large and medium-sized arteries. Blood vessel: The vessels through which blood circulates. In general, blood vessels are elastic tubular channels that are lined with endothelium. Blood vessels include the arteries, veins, and capillaries. Specific, non-limiting examples of a blood vessel include a vena cava, a thoracic aorta, a saphanous vein, a mammary artery, the brachial artery, and a capillary. In another embodiment, a blood vessel includes the smaller arteries and veins. In yet another embodiment, a blood vessel is a capillary of the microvascular circulation. Brachial reactitvity: The ability of the brachial artery to dilate in response to physiological or pharmacological stimulation. Brachial reactivity is a measure of vascular function or endothelial function. One of skill in the art can readily measure brachial reactivity (see the Examples section below). Previous studies have determined the utility of measuring brachial reactivity as an independent predictor of cardiovascular events. Buffy coat: A thin yellow or white layer of leukocytes that appears on top of a mass of packed red cells when whole blood is centrifuged. Cardiovascular: Pertaining to the heart and/or blood vessels. Cardiovascular risk: The likelihood of the development of disorders related to the cardiovascular system, such as, but not limited to, myocardial ischemia and infarction, intermittent claudication, bowel ischemia, retinal ischemia, transient ischemic attacks, ischemic strokes, and other conditions associated with cardiovascular dysfunction. In a specific non-limiting example, the disorder is myocaridal ishemia or infaction. CD31: A 130 to 140-kdalton single-chain integral membrane glycoprotein that is a member of the immunoglobulin gene superfamily, and is also known as PE-cell adhesion molecule (CAM). The CD31 antigen is composed of six extracellular immunoglobulin-like domains belonging to the C2 group. C2 domains are also found in other members of the immunoglobulin superfamily, the CAMs. The CD31 antigen is expressed on endothelial cells and platelets, T lymphocyte subsets, monocytes, and granulocytes, and is known to function as a vascular cell adhesion molecule and is involved in the process of leukocyte migration through the intercellular junctions of vascular endothelial cells (see Stockinger et al., J Immunol. 145(11):3889-3897, 1990). Cholesterol lowering agent: An agent, such as a pharmaceutical, vitamin, or small molecule, that lowers the level of cholesterol in a subject. One of skill in the art can readily identify assays, such as blood screening, to determine the effect of cholesterol. Agents include, but are not limited to, niacin, the statins (e.g., Zocor™, Lipitor™, Pravacol™, Lescor™, Mevacor™), binding resins (e.g., Questran™), and fibrates (e.g. Lopid™, Lipidil Micro™). Differentiation: The process by which cells become more specialized to perform biological functions. Differentiation is a property that is often totally or partially lost by cells that have undergone malignant transformation. Endothelial progenitor cell: A cell that can give rise to a differentiated endothelial cell. In one specific, non-limiting example, endothelial progenitor cells express a number of endothelial specific markers including receptors for vascular endothelial growth factor (VEGFR-2), CD31, Tie-2 and VE-Cadherin (Asahara et al., Science 275:964-967, 1997; Peichev et al., Blood 95:952-958, 2000). Endothelial progenitor cells can be isolated from circulating mononuclear cells (Asahara et al., Science 275:964-967, 1997; Lin et al., J Clin Invest 105:71-77, 2000; Peichev et al., Blood 95:952-958, 2000), bone marrow (Reyes et al., J Clin Invest 109:337-346, 2002) and cord blood (Murohara et al., J Clin Invest 105:1527-1536, 2000). Injection of these cells into animal models with active ischemia results in the incorporation of endothelial progenitor cells into sites of neovascularization (Asahara et al., Science 275:964-967, 1997; Murohara et al., J Clin Invest 105:1527-1536, 2000; Takahashi et al., Nat Med 5:434-438, 1999; Asahara et al., EMBO J 18:3964-3972, 1999; Asahara et al., Circ Res 85:221-228, 1999; Kocher et al., Nature Med 7:430-436, 2001; Grant et al., Nature Med 8:607-612, 2002; Luttun et al., Trends in Cardiovasc Med 12:88-96, 2002). In one example, these cells also possess a number of endothelial properties including an ability to incorporate modified lipids such as oxidized LDL and to release NO in response to VEGF stimulation (Asahara et al., Science 275:964-967, 1997). “Assaying the number of endothelial progenitor cells” refers to assaying the amount of endothelial progenitor cells in a sample. The assay can be direct (such as counting the cells) or indirect (such as counting the number of colonies grown from the sample). The absolute number of cells in the sample can be determined, or the number of cells can be determined relative to a control. The sample can be a sample from any subject that includes endothelial progenitor cells. Suitable samples include, for example, a whole blood sample or a population of cells isolated from the subject. The number of endothelial progenitor cells can be determined using any method known to one of skill in the art. Exemplary methods are disclosed herein to determine the number of endothelial progenitor cells. Framingham Risk Score: A risk factor score that is used for predicting future risk of coronary artery disease in individuals free of disease, based on the measurement of risk factors including age, gender, systolic blood pressure, cigarette smoking, glucose intolerance, left ventricular hypertrophy, as well as total cholesterol, low density lipoprotein (LDL) and high density lipoprotein (HDL) levels (Wilson et al., Am J Cardiol 59:91G-94G, 1987). Fibronectin: A dimeric glycoprotein of 430 kD (two chains of a molecular weight of about 250 kD) found in all vertebrates. The two subunits of fibronectin are joined by a pair of disulphide bonds near to their carboxyl termini. Fibronectin is a rod-like molecule composed of three different types of homologous repeating modules that constitute an independently folded unit. All three types of modules are composed exclusively of anti-parallel beta-sheets and turns with no alpha-helix. All fibronectin modules are highly conserved and are found in a wide array of other proteins. Twelve type-1 modules (approximately 45 amino acids) make up the amino-terminal and carboxy-terminal region of fibronectin. These modules are involved mainly in fibrin and collagen binding. Two type-2 modules (approximately 60 amino acids) are involved in binding collagen. The fifteen type III modules contain an RGD fibronectin receptor recognition sequence along with binding sites for other integrins and heparin. Fibronectin can serve as a general cell adhesion molecule by anchoring cells to collagen or proteoglycan substrates. Fibronectin plays a role in cell adhesion, cell morphology, and surface architecture. Granulocyte colony stimulating factor (G-CSF): An O-glycosylated 19.6 kDa glycoprotein with a pI of 5.5. The biologically active form is a monomer. The analysis of its cDNA has revealed a protein of 207 amino acids containing a hydrophobic secretory signal sequence of 30 amino acids. G-CSF contains 5 cysteine residues, four of which form disulfide bonds (positions 36-42; 64-74). The sugar moiety of G-CSF is not required for full biological activity. Human G-CSF is active in murine cells and vice versa. G-CSF stimulates the proliferation and differentiation of hematopoietic progenitor cells committed to the neutrophil/granulocyte lineage in a dose-dependent manner. At higher concentrations this factor induces the generation of colonies in soft agar cultures containing granulocytes and macrophages. The fully differentiated neutrophilic granulocytes are functionally activated by G-CSF. Granulocyte/macrophage colony-stimulating factor (GM-CSF): GM-CSF is a monomeric protein of about 127 amino acids with two glycosylation sites. The protein is synthesized as a precursor of about 144 amino acids, which includes a hydrophobic secretory signal sequence at the aminoterminal end. The human gene has a length of approximately 2.5 kb and contains four exons. The distance between the GM-CSF gene and the IL-3 gene is approximately 9 kb. The human GM-CSF gene maps to chromosome 5q22-31. GM-CSF was isolated initially as a factor stimulating the growth of macrophage/granulocyte-containing colonies in soft agar cultures. GM-CSF is also involved in the growth and development of granulocyte and macrophage progenitor cells. It stimulates myeloblasts and monoblasts and triggers irreversible differentiation of these cells. GM-CSF synergizes with erythropoietin in the proliferation of erythroid and megakaryocytic progenitor cells. GM-CSF has been used clinically for the physiological reconstitution of hematopoiesis in diseases characterized either by an aberrant maturation of blood cells or by a reduced production of leukocytes. In one example, the dose, route and schedules for GM-CSF are 5-10 micrograms/kg/day either by 4-6 hours intravenous infusion or by subcutaneous injection. GM-CSF has also been used clinically to promote collateral vessel growth. In another example, GM-CSF is administered by intravascular injection of about 10 to about 50 μg, such as about 40 μg. In yet another example, GM-CSF is administered subcutaneously at about 5 to 20 μg/kg, or at about 10 μg/kg (see also Seiler et al., Circulation 104(17):2012-7, 2001). Growth Factor: A “growth factor” is a substance that affects the growth of a cell or organism. In general, growth factors stimulate cell proliferation or maturation when they bind to their receptor (“growth factor receptor”). In one embodiment, growth factors are a complex family of polypeptide hormones or biological factors that control growth, division and maturation of hematopoietic cells. In another embodiment, growth factors regulate the division and proliferation of cells and influence the growth rate of neoplastic tissue (e.g. cancers). A growth factor can be a naturally occurring factor or a factor synthesized using molecular biology techniques. In one specific, non-limiting example, a growth factor can be used stimulate to lymphocyte production or differentiation, and thus can be used following chemotherapy or bone marrow transplantation. Leukocyte: Cells in the blood, also termed “white cells,” that are involved in defending the body against infective organisms and foreign substances. Leukocytes are produced in the bone marrow. There are 5 main types of white blood cell, subdivided between two main groups: polymorphonuclear leukocytes (neutrophils, eosinophils, basophils) and mononuclear leukocytes (monocytes and lymphocytes). When an infection is present, the production of leukocytes increases. Lymphocytes: A type of white blood cell that is involved in the immune defenses of the body. There are two main types of lymphocytes: B cell and T cells. Maturation: The process in which an immature cell, such as a precursor cell, changes in form or function to become a functional mature cell, such as a mature T or B cell. Mobilization Agent: A compound such as a naturally occurring protein or a derivative thereof, that acts on endothelial progenitor or stem cells to mobilize endothelial precursor cells. A mobilizing agent causes endothelial cell precursors to migrate from their tissue of origin such as the bone marrow, and move into other tissues or the peripheral blood. Specific, non-limiting examples of a mobilizing agent are GM-CSF, G-CSF, and AMD-3100 (Anormed, British Columbia, dosing information available on the Anormed website). Pharmaceutically acceptable carriers: The pharmaceutically acceptable carriers useful in this invention are conventional. Remington's Pharmaceutical Sciences, by E. W. Martin, Mack Publishing Co., Easton, Pa., 15th Edition, 1975, describes compositions and formulations suitable for pharmaceutical delivery of the fusion proteins herein disclosed. In general, the nature of the carrier will depend on the particular mode of administration being employed. For instance, parenteral formulations usually comprise injectable fluids that include pharmaceutically and physiologically acceptable fluids such as water, physiological saline, balanced salt solutions, aqueous dextrose, glycerol or the like as a vehicle. For solid compositions (e.g., powder, pill, tablet, or capsule forms), conventional non-toxic solid carriers can include, for example, pharmaceutical grades of mannitol, lactose, starch, or magnesium stearate. In addition to biologically-neutral carriers, pharmaceutical compositions to be administered can contain minor amounts of non-toxic auxiliary substances, such as wetting or emulsifying agents, preservatives, and pH buffering agents and the like, for example sodium acetate or sorbitan monolaurate. Polynucleotide: A linear nucleotide sequence, including sequences of greater than 100 nucleotide bases in length. Polypeptide: Any chain of amino acids, regardless of length or post-translational modification (e.g., glycosylation or phosphorylation). Progenitor cell: A “progenitor cell” is a cell that gives rise to progeny in a defined cell lineage. An “endothelial progenitor cell” is a cell that gives rise to cells of the endothelial lineage. In one specific, non-limiting example, an endothelial progenitor cell is a VDGRR2+CD31hi cell. A “circulating endothelial progenitor cell” is an endothelial progenitor cell found circulating in the body, such as endothelial progenitor cells in the blood. Purified: The term “purified” does not require absolute purity; rather, it is intended as a relative term. Thus, for example, a purified cell preparation is one in which the cell referred to is more pure than the cell in its natural environment within a tissue. In one embodiment, a “substantially purified” population of a specific cell type is a composition of cells that includes less than about 20%, less than about 15%, or less than about 10% of cells of a different phenotype. Thus, a substantially purified population of cells includes greater than 80%, greater than 85%, or greater than 90% of the cells of interest. In another embodiment, a process that produces a purified population of cells is a process that produces a population of cells so that more than 50% of the resulting population is the cell type of interest. Senescence: A state of a cell in which the cell reaches the end of its proliferative capacity and is unable to undergo subsequent cell division. A senescent cell is still viable, but does not divide. Subject: Any subject that has a vascular system and has hematopoietic cells. In one embodiment, the subject is a non-human mammalian subject, such as a monkey, mouse, rat, rabbit, pig, goat, sheep or cow. In another embodiment, the subject is a human subject. Therapeutically effective amount of a cell: An amount of a endothelial progenitor cell, that can be determined by various methods, including generating an empirical dose-response curve, predicting potency and efficacy by using modeling, and other methods used in the biological sciences. In general, a therapeutically effective amount of endothelial progenitor cell is an amount sufficient to improve vascular function. In one specific, non-limiting example, a therapeutically effective amount of an endothelial progenitor cell is an amount sufficient to treat atherosclerosis, or to delay or prevent an ischemic event. In one embodiment, a therapeutically effective amount of a endothelial progenitor cell is more than about 10,000 cells, more than about 20,000 cells, more than about 30,000 cells, or between about 5,000 cells and about 50,000 cells. The therapeutically effective amount of cells will be dependent on the subject being treated (e.g. the species or size of the subject), the degree that the vascular function is impaired in a subject, and the location of the survival of the transplanted cells in the subject. Specific assays for determining the therapeutically effective amount of endothelial cells are provided herein. The methods disclosed have equal application in medical and veterinary settings. Therefore, the general term “subject being treated” is understood to include all animals (e.g. humans, apes, dogs, cats, mice, rats, rabbits, sheep, pigs and cows) and vascular function is monitored using the assays described herein. Transduced and Transformed: A virus or vector “transduces” a cell when it transfers nucleic acid into the cell. A cell is “transformed” by a nucleic acid transduced into the cell when the DNA becomes stably replicated by the cell, either by incorporation of the nucleic acid into the cellular genome, or by episomal replication. As used herein, the term transformation encompasses all techniques by which a nucleic acid molecule might be introduced into such a cell, including transfection with viral vectors, transformation with plasmid vectors, and introduction of naked DNA by electroporation, lipofection, and particle gun acceleration. Transplantation: The transfer of a tissue or an organ, or cells, from one body or part of the body to another body or part of the body. An “allogeneic transplantation” or a “heterologous transplantation” is transplantation from one individual to another, wherein the individuals have genes at one or more loci that are not identical in sequence in the two individuals. An allogeneic transplantation can occur between two individuals of the same species, who differ genetically, or between individuals of two different species. An “autologous transplantation” is a transplantation of a tissue or cells from one location to another in the same individual, or transplantation of a tissue or cells from one individual to another, wherein the two individuals are genetically identical. Vascular function: The function of the blood vessels. Decreased vascular function is associated with atherosclerosis, myocardial infarction, intermittent claudication, bowel ischemia, retinal ischemia, transient ischemic attacks (TIAs), ischemic strokes, restenosis after angioplasty, transplant atherosclerosis, unstable angina, sudden death, and alterations in blood pressure. Vascular function assessment: An assay that measures the function of the vascular system. Assays include measurement of a parameter of the blood, assays of arterial hyperplasia, vascular contractility measurements, brachial reactivity measurements, and morphometric measurements. Similarly, an endothelial cell assessment is a test that measures a function or parameter of an endothelial cell. “Decreased vascular function” indicates a decrease in any function of the blood vessels, as compared to a standard value or a control sample. Thus, in one example, decreased vascular function is a decrease in a vascular contractility, as compared to a known value for normal vascular contractility. In another example, decreased vascular function is the lower contractility of a blood vessel as compared to the contractility of a vessel known to not be affected by as a disease or a disorder. In a further example, decreased vascular function is a lower vascular contractility as compared to the contractility of a vessel from the same subject at an earlier time point. Vascular tissue: Tissue consisting of, or containing, vessels as an essential part of a structure. Vascular tissue operates by means of, or is made up of an arrangement of, vessels. Vascular tissue includes the arteries, veins, capillaries, lacteals, microvasculature, etc. In one embodiment, vascular tissue includes a highly vascularized organ (e.g. the lung). In another embodiment, vascular tissue is a blood vessel, or a portion thereof. Cells isolated from a vascular tissue are a population of cells isolated from the remaining components of the tissue. One specific, non-limiting example of cells from a vascular tissue are endothelial cells isolated from vascular tissue, such as a blood vessel. Vascular Endothelial Growth Factor (VEGF): VEGF is a homodimeric heavily glycosylated protein of 46-48 kDa (24 kDa subunits). Glycosylation is not required, however, for biological activity. The subunits are linked by disulfide bonds. The human factor occurs in several molecular variants of 121 (VEGF-121), 165 (VEGF-165), 183 (VEGF-183), 189 (VEGF-189), 206 (VEGR-206) amino acids, arising by alternative splicing of the mRNA (for review see Neufeld et al., FASEB J. 13: 9, 1999) The human gene encoding VEGF has a length of approximately 12 kb and contains eight exons. Four species of mRNA encoding VEGF have been identified and found to be expressed in a tissue-specific manner. They arise from differential splicing with the 165 amino acid form of VEGF lacking sequences encoded by exon 6 and the 121 amino acid form lacking exon 6 and 7 sequences. The VEGF gene maps to human chromosome 6p12-p21. VEGF is a highly specific mitogen for vascular endothelial cells. In vitro the two shorter forms of VEGF stimulate the proliferation of macrovascular endothelial cells. VEGF does not appear to enhance the proliferation of other cell types. VEGF significantly influence vascular permeability and is a strong angiogenic protein in several bioassays and probably also plays a role in neovascularization under physiological conditions. A potent synergism between VEGF and beta-FGF in the induction of angiogenesis has been observed. It has been suggested that VEGF released from smooth muscle cells and macrophages may play a role in the development of arteriosclerotic diseases. VEGF can be assayed by an immunofluorometric test. An alternative and entirely different detection method is RT-PCR quantitation of cytokines. Methods for performing these assays are known (e.g. see Yeo et al., Clinical Chem. 38:71, 1992). VEGF receptor: A receptor found on the surface of a cell that specifically binds VEGF. VEGF receptors are high-affinity glycoprotein receptors of 170-235 kDa. VEGF receptors are expressed on vascular endothelial cells. The interaction of VEGF with heparin-like molecules of the extracellular matrix is required for efficient receptor binding. Protamine sulfate and suramin are capable of replacing the receptor-bound factor. The high-affinity receptor for VEGF, now known as VEGF-R1, has been identified as the gene product of the flt-1 gene. Another receptor for VEGF, now known as VEGF-R2, is KDR, also known as flk-1. This receptor is a receptor tyrosine kinase. The human gene maps to chromosome 4q31.2-q32 and encodes a transcript of approximately 7 kb. It has been shown that VEGF-R2 (flk-1) is expressed abundantly in proliferating endothelial cells of the vascular sprouts and branching vessels of embryonic and early postnatal brain and that its expression is reduced drastically in adult brain where proliferation has ceased. Flk-1 is expressed also in the blood islands in the yolk sac of embryos. The expression of this receptor therefore correlates with the development of the vascular system and with endothelial cell proliferation. (See Joukov et al., EMBO J. 15:290-298, 1996). Vector: In one embodiment a nucleic acid molecule as introduced into a host cell, thereby producing a transformed host cell. A vector may include nucleic acid sequences that permit it to replicate in the host cell, such as an origin of replication. A vector may also include one or more selectable marker genes and other genetic elements known in the art. In one embodiment the term “vector” includes viral vectors, such as adenoviruses, adeno-associated viruses, vaccinia, and retroviral vectors. In one embodiment the term vector includes bacterial vectors. Unless otherwise explained, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The singular terms “a,” “an,” and “the” include plural referents unless context clearly indicates otherwise. Similarly, the word “or” is intended to include “and” unless the context clearly indicates otherwise. It is further to be understood that all base sizes or amino acid sizes, and all molecular weight or molecular mass values given for nucleic acids or polypeptides are approximate, and are provided for description. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of this disclosure, suitable methods and materials are described below. The term “comprises” means “includes.” All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including explanations of terms, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting. Diagnosis A method of diagnosing vascular function in a subject is disclosed herein. Specifically, the method is of use in diagnosing decreased vascular function. In several embodiments, the method includes assaying endothelial progenitor cells. The assay can determine endothelial cell (or endothelial precursor cell) function, endothelial cell activity, or can determine the number of circulating endothelial cells. The method can be used, for example, to predict future cardiovascular risk. Specifically, the method can be used to predict risk for myocardial infarction, intermittent claudication, bowel ischemia, retinal ischemia, transient ischemic attacks (TIAs), ischemic strokes, restenosis after angioplasty, transplant atherosclerosis, unstable angina, sudden death, and other conditions associated with cardiovascular dysfunction. In one specific, non-limiting example, the enumeration of endothelial progenitor cells is of use in predicting cardiovascular risk for myocardial ischemia and/or infarction. Cardiovascular risk indicates the potential for a future cardiovascular event, such as myocardial infarction, intermittent claudication, bowel ischemia, retinal ischemia, transient ischemic attacks (TIAs), ischemic strokes, restenosis after angioplasty, transplant atherosclerosis, unstable angina, sudden death, and other conditions associated with cardiovascular dysfunction. Factors involved in cardiovascular risk include, but are not limited to, serum cholesterol, hypertension, diabetes, sex, and age. In another specific, non-limiting example, the enumeration of endothelial progenitor cells is of use in diagnosing artherosclerosis. Thus, the method includes measuring the number of circulating endothelial cell precursors to determine the risk for developing a cardiovascular condition such as, but not limited to, atherosclerosis. The methods disclosed herein include assaying the number of endothelial progenitor cells. A decrease in the number of endothelial progenitor cells as compared to a control indicates decreased vascular function, for example, increased future cardiovascular risk. In one specific, non-limiting example, an assessment of the risk of a subject to develop vascular disease, or an assessment of vascular function is made by determining the number of circulating endothelial progenitor cells, using methods such as the ones disclosed below. In one embodiment, assaying the number of endothelial progenitor cells includes isolating the buffy coat from a blood sample of the subject and culturing the buffy coat on a solid support coated with a substrate, including, but not limited to fibronectin, vitronectin, or collagen. In one specific, non-limiting example, the solid substrate, such as a polymer suitable for tissue culture, is coated with fibronectin. The culture period can be from about 24 hours to about 72 hours, such as but not limited to, for about 36 hours or about 48 hours. The non-adherent cells are isolated from the culture and again cultured on a solid support coated with a substrate. The substrate includes, but is not limited to, fibronectin, vitronectin, or collagen. The substrate can be the same as used for the culture of the buffy coat, or can be different. In one example, the substrate is fibronectin for both the culture of the buffy coat and the culture of the non-adherent cells. Solid surfaces suitable for tissue culture are known in the art, and include, but are not limited to, polystyrene, glass, and polypropylene. The number of colonies produced on the solid support is then enumerated. For example, enumeration can take place at 4 to 10 days following culture of the non-adherent cells. In one specific, non-limiting example, the number of colonies are counted at about seven days following the plating of the non-adherent cells. In one embodiment, a lower number of colonies on the solid support as compared to a control indicates decreased vascular function or increased cardiovascular risk. In one specific, non-limiting example, the control is a standard value. In another specific, non-limiting example, the control is the number of colonies obtained after culturing a similar number of cells from the buffy coat of a subject known not to be affected by a specific disease or disorder. In yet another example, the control is the number of colonies obtained from culturing a similar number of cells from the buffy coat of the same subject, taken at a different time, such as an earlier time point. In another embodiment, the number of circulating endothelial progenitor cells in a subject is evaluated by measuring the number of circulating cells in a sample, such as a blood sample, from the subject. For example, the number of VEGFR2+CD31hi cells is assessed. Alternatively, the number of endothelial progenitor cells expressing AC133 is assessed. One of skill in the art can readily determine the number of these cells. Suitable methods include, but are not limited to, fluorescence activated cell sorting and immunohistochemical staining of blood cells. Methods of determining the presence or absence of a cell surface marker, such as a VEGF receptor, e.g. VEGFR2, are well known in the art. Typically, labeled antibodies specifically directed to the marker are used to identify the cell population. The antibodies can be conjugated to other compounds including, but not limited to, enzymes, magnetic beads, colloidal magnetic beads, haptens, fluorochromes, metal compounds, radioactive compounds or drugs. The enzymes that can be conjugated to the antibodies include, but are not limited to, alkaline phosphatase, peroxidase, urease and β-galactosidase. The fluorochromes that can be conjugated to the antibodies include, but are not limited to, fluorescein isothiocyanate, tetramethylrhodamine isothiocyanate, phycoerythrin, allophycocyanins and Texas Red. For additional fluorochromes that can be conjugated to antibodies see Haugland, R. P., Molecular Probes: Handbook of Fluorescent Probes and Research Chemicals, 1992-1994. The metal compounds that can be conjugated to the antibodies include, but are not limited to, ferritin, colloidal gold, and particularly, colloidal superparamagnetic beads. The haptens that can be conjugated to the antibodies include, but are not limited to, biotin, digoxigenin, oxazalone, and nitrophenol. The radioactive compounds that can be conjugated or incorporated into the antibodies are known to the art, and include but are not limited to technetium 99 m (99Tc), 125I and amino acids comprising any radionuclides, including, but not limited to, 14C, 3H and 35S. Fluorescence activated cell sorting (FACS) can be used to sort cells that express VEGFR2, by contacting the cells with an appropriately labeled antibody. In one embodiment, additional antibodies and FACS sorting can further be used to produce substantially purified populations of CD31 expressing (CD31hi) cells. A FACS employs a plurality of color channels, low angle and obtuse light-scattering detection channels, and impedance channels, among other more sophisticated levels of detection, to separate or sort cells. Any FACS technique may be employed as long as it is not detrimental to the viability of the desired cells. (For exemplary methods of FACS see U.S. Pat. No. 5,061,620, herein incorporated by reference). Similarly, FACS can be used to substantially purify VEGFR2 expressing cells, or VEGFR2+CD31hi cells. However, other techniques of differing efficacy may be employed to purify and isolate desired populations of cells. The separation techniques employed should maximize the retention of viability of the fraction of the cells to be collected. The particular technique employed will, of course, depend upon the efficiency of separation, cytotoxicity of the method, the ease and speed of separation, and what equipment and/or technical skill is required. Separation procedures may include magnetic separation, using antibody-coated magnetic beads, affinity chromatography, cytotoxic agents, either joined to a monoclonal antibody or used in conjunction with complement, and “panning,” which utilizes a monoclonal antibody attached to a solid matrix, or another convenient technique. Antibodies attached to magnetic beads and other solid matrices, such as agarose beads, polystyrene beads, hollow fiber membranes and plastic petri dishes, allow for direct separation. Cells that are bound by the antibody can be removed from the cell suspension by simply physically separating the solid support from the cell suspension. The exact conditions and duration of incubation of the cells with the solid phase-linked antibodies will depend upon several factors specific to the system employed. The selection of appropriate conditions, however, is well within the skill in the art. The unbound cells then can be eluted or washed away with physiologic buffer after sufficient time has been allowed for the cells expressing a marker of interest (e.g. VEGFR2 or CD31) to bind to the solid-phase linked antibodies. The bound cells are then separated from the solid phase by any appropriate method, depending mainly upon the nature of the solid phase and the antibody employed. Antibodies may be conjugated to biotin, which then can be removed with avidin or streptavidin bound to a support, or fluorochromes, which can be used with a fluorescence activated cell sorter (FACS), to enable cell separation (see above). In one specific, non-limiting example, the VEGFR2+CD31hi cells initially may be separated from other cells by the cell-surface expression of CD31. In one specific, non-limiting example, CD31hi cells are positively selected by magnetic bead separation, wherein magnetic beads are coated with CD31 reactive monoclonal antibody. The CD31hi cells are then removed from the magnetic beads. Release of the CD31hi cells from the magnetic beads can be effected by culture release or other methods. Purity of the isolated CD31hi cells is then checked with a flow cytometer, such as a FACSCAN™ flow cytometer (Becton Dickinson, San Jose, Calif.), if so desired. In one embodiment, further purification steps are performed, such as FACS sorting the population of cells released from the magnetic beads, such as the cells expressing VEGFR2. In one embodiment, magnetic bead separation is used to first separate a population of cells that do not express more than one lineage specific markers, for example, CD31 or VEGFR2. In addition, panning can be used to separate cells that do not express one or more lineage specific markers. Panning methods are well known in the art (e.g., see Small et al., J Immunol Methods 167(1-2):103-7, 1994). In yet a further embodiment, a function parameter of endothelial cells or endothelial progenitor cells is assessed. Specific, non-limiting examples of these parameters are uptake of acetylated LDL or production of nitric oxide (NO) in response to VEGF stimulation. In yet another embodiment, a method is provided for diagnosing decreased vascular function or increased risk for cardiovascular disease in a subject that includes determining the number of senescent circulating endothelial progenitor cells in the subject. An increase in the number of senescent circulating endothelial progenitor cells as compared to a control indicates that the subject has decreased vascular function or is at increased risk for the development of a cardiovascular disease. In one specific, non-limiting example, the control is a standard value. In another specific, non-limiting example, the control is the number of senescent endothelial cells in a subject known not to be affected by a specific disease or disorder. In yet another example, the control is the number of senescent cells from same subject, taken at a different time, such as, but not limited to, an earlier time point when the subject is known to have adequate vascular function. Methods of isolating endothelial progenitor cells are disclosed herein. Once these cells are isolated, senescence can be measured by any means known to one of skill in the art. For example, endogenous cellular β-galactosidase activity can measured as a marker of cellular senescence (Dimri et al., Proc. Natl. Acad. Sci. U.S.A. 92:9363-9367, 1995). Alternatively, cell proliferation can be measured using standard assays such as bromodeoxyuridine (BrdU) or 3H-thymidine labeling of cells. In these assays, proliferation of the endothelial progenitor cells results in incorporation of the label. Drug Screening A method is disclosed herein for screening agents that can be used to treat cardiovascular disease, or that affect endothelial cell function. The method includes treating a subject with the agent, and assaying for the number of circulating endothelial precursor cells or for a function of endothelial cells or endothelial cell precursors. An increase in the number of endothelial progenitor cells, as compared to a control, indicates that the agent is of use in treating cardiovascular disease or increasing vascular function. In one specific, non-limiting example, the number of senescent endothelial progenitor cells is assessed. The animal can be any subject, including both human and non-human subjects. In several non-limiting examples, the animal is a primate (human, chimpanzee, macaque, etc.), farm animal (cow, pig, etc.), a domestic animal (cat, dog, etc.), or a rodent (mouse, rat, guinea pig, etc). In one specific, non-limiting example, the subject is a human subject. In one specific, non-limiting example, the method includes assaying the number of endothelial progenitor cells. An increase in the number of circulating endothelial progenitor cells as compared to a control indicates that the agent is effective for treating a cardiovascular disease, or for increasing endothelial cell function. Suitable controls include an animal not treated with an agent, or a standard value. Suitable controls also include the number of endothelial progenitor cells in the animal prior to treatment with the agent. In several embodiments, the agent is of use in the treatment of myocardial infarction, intermittent claudication, bowel ischemia, retinal ischemia, transient ischemic attacks (TIAs), ischemic strokes, restenosis after angioplasty, transplant atherosclerosis, unstable angina, sudden death, and other conditions associated with cardiovascular dysfunction. Assaying the number of endothelial progenitor cells includes, for example, isolating the buffy coat from a blood sample of the treated animal and culturing the buffy coat on a solid support coated with a substrate, such as, but not limited to, fibronectin, vitronectin, or collagen. In one specific, non-limiting example, the solid substrate, such as a polymer suitable for tissue culture, is coated with fibronectin. The non-adherent cells are isolated and cultured on a solid support coated with a substrate, such as, but not limited to, fibronectin. The number of colonies produced on the solid support is then enumerated. In one embodiment, a higher number of colonies on the solid support as compared to a control indicates that the agent is effectively increasing endothelial cell function. Thus, a higher number of colonies indicates that the agent is of use in treatment of a cardiovascular disease, and/or for increasing vascular function (see above). In another embodiment, the number of endothelial progenitor cells in a subject is evaluated by measuring the number of circulating cells in a sample, such as a blood sample, from the subject. For example, the number of VEGFR2+CD31hi cells is assessed. Alternatively, the number of endothelial progenitor cells expressing AC133 is assessed. Methods for enumerating these cells are described above. In another specific, non-limiting example, the method includes treating a subject with the agent, and assaying for the number of senescent endothelial precursor cells. A decrease in the number of senescent endothelial progenitor cells, as compared to a control, indicates that the agent is of use in treating cardiovascular disease or increasing vascular function. Methods for determining the number of senescent endothelial cells are disclosed herein. Examples of agents of interest include, but are not limited to, chemical compounds; growth factors; peptidomimetics; antibodies; synthetic ligands that endothelial cells or endothelial progenitor cells, cytolines, small molecules, and receptor ligands (e.g. agonists of a receptor, such as but not limited to, VEGFR2). The determination and isolation of ligand/compositions is well described in the art. See, e.g., Lerner, Trends Neuro Sci. 17:142-146, 1994. The test compound may also be a combinatorial library for screening a plurality of compounds. Compounds identified in the method of the invention can be further evaluated, detected, cloned, sequenced, and the like, either in solution of after binding to a solid support, by any method usually applied to the detection of a specific DNA sequence, such as PCR, oligomer restriction (Saiki et al., Bio/Technology 3:1008-1012, 1985), allele-specific oligonucleotide (ASO) probe analysis (Conner et al., Proc. Natl. Acad. Sci. U.S.A. 80:278, 1983), oligonucleotide ligation assays (OLAs) (Landegren et al., Science 241:1077, 1988), and the like. Molecular techniques for DNA analysis have been reviewed (Landegren et al., Science 242:229-237, 1988). Methods of Treatment Methods are disclosed herein for improving vascular function in a subject. The methods include administering to the subject a therapeutically effective amount of endothelial precursor cells, to improve vascular function. In one embodiment, the subject has atherosclerosis. In other embodiments, the subject has had a myocardial infarction, or has intermittent claudication, bowel ischemia, retinal ischemia, transient ischemic attacks (TIAs), ischemic strokes, restenosis after angioplasty, transplant atherosclerosis, unstable angina, or another condition associated with cardiovascular dysfunction. A therapeutically effective amount of an endothelial progenitor cell can determined by various methods, including generating an empirical dose-response curve, predicting potency and efficacy of using modeling, and other methods used in the biological sciences. In general, a therapeutically effective amount of an endothelial progenitor cell is an amount sufficient to prevent, treat, reduce, eliminate and/or ameliorate a symptom and/or the underlying causes of the disease or disorder being treated, such as any condition associated with cardiovascular dysfunction. In one embodiment, a therapeutically effective amount is an amount sufficient to increase blood flow. The therapeutically effective amount of endothelial progenitor cells will be dependent on the subject being treated (e.g. the species or size of the subject), the type of cardiovascular dysfunction suffered by the subject, and the location of administration of the cells (e.g. intravenously, locally, etc). In one embodiment, a therapeutically effective amount of cells is an amount of cells sufficient to treat a subject suffering from a myocardial injury. In specific, non-limiting examples, a therapeutically effective amount of endothelial progenitor cells is more than about 100 cells, more than about 1000 cells, more than about 10,000 cells, more than about 100,000 cells, more than about 250,000 cells, more than about 1,000,000 cells, or between about 250,000 cells and about 1,000,000 cells. In one example, greater than 2×106/kg of endothelial progenitor cells are administered to the subject. In another embodiment, 2×106/kg-5×106/kg endothelial progenitor cells are administered. Without being bound by theory, these doses of endothelial cells are applicable in both autologous and allogeneic settings (Sezer et al., J. Clin. Onc. 18:3319-3320, 2000; Mavroudis et al., Blood 88:3223-3229, 1996). Accordingly, it is anticipated that the administration of compositions comprising an equivalent or greater number of endothelial progenitor cells, either alone or in combination with other stern/progenitor cells, should result in increased vascular function and/or decreased cardiovascular risk. Specific assays for determining the therapeutically effective amount of endothelial progenitor cells are provided herein. The methods have equal application in medical and veterinary settings. In a further embodiment, other agents such as growth factors or cytokines are administered in conjunction with endothelial progenitor cells. For example, a therapeutically effective amount of vascular endothelial growth factor, angiopoeitin, or fibroblast growth factor is administered in conjunction with a therapeutically effective amount of endothelial progenitor cells. These agents can be administered before, after, or simultaneously with the endothelial progenitor cells. One or multiple doses can be administered. Thus a therapeutically effective amount of endothelial progenitor cells is administered to a subject requiring treatment, such a subject with impaired vascular function. A therapeutically effective amount of endothelial progenitor cells is the amount sufficient to improve vascular function. The composition can be supplemented with growth factors or with other lineage-uncommitted cells. Precise, effective quantities can be readily determined by those who are skilled in the art and will depend, of course, upon the exact condition being treated by the particular therapy being employed. One or multiple doses can be administered. Administration can be systemic or local, and can be by any route, such as intramuscular, subcutaneous, intravascular, intraperitoneal, intranasal, or oral administration. Administration can be by injection. Specific, non-limiting examples of administration by injection include administration by subcutaneous injection, intramuscular injection, or intravenous injection. If administration is intravenous, an injectible liquid suspension of endothelial progenitor cells can be prepared and administered by a continuous drip or as a bolus. One specific, non-limiting example of local administration is intra-cardiac injection. For intra-cardiac injection, the endothelial progenitor cells are in an injectible liquid suspension preparation or in a biocompatible medium which is injectible in liquid form and becomes semi-solid at the site of damaged myocardium. A conventional intra-cardiac syringe or a controllable endoscopic delivery device can be used so long as the needle lumen or bore is of sufficient diameter (e.g. 30 gauge or larger) that shear forces will not damage the endothelial progenitor cells. In one specific, non-limiting example, a therapeutically effective amount of endothelial progenitor cells is administered to a subject with impaired vascular function. The endothelial progenitor cells are administered in conjunction with a therapeutically effective amount of a mobilization agent, such as, but not limited to, a therapeutically effective amount of granulocyte macrophage colony stimulating factor (GM-CSF), AMD-3100, or granulocyte colony stimulating factor (G-CSF). In one embodiment, endothelial progenitor cells are administered in conjunction with a mobilizing agent, such as but not limited to, G-CSF or GM-CSF. Administration can be by any route, such as, but not limited to, intracardiac injection (e. g. see Selier et al., Circulation 104(17):2012-7, 2001). The invention is illustrated by the following non-limiting Examples. EXAMPLES Example 1 Methods Study Subjects: Forty-five healthy male subjects >21 years of age (mean 50.3±1.7), with or without conventional cardiovascular risk factors, were studied. Patients were solicited from the community through the NIH Patient Recruitment and Public Liaison Office by placement of a general announcement for volunteers with or without cardiovascular risk factors who were free of ischemic symptoms or a known history of cardiovascular disease. The total risk factor burden was calculated by employing the Framingham risk factor score that has been previously used for predicting future risk of coronary artery disease in individuals free of disease, based on the measurement of risk factors including age, gender, systolic blood pressure, cigarette smoking, glucose intolerance, left ventricular hypertrophy, as well as total cholesterol, low density lipoprotein (LDL) and high density lipoprotein (HDL) levels (Wilson et al., Am J Cardiol 59:91G-94G, 1987). Subjects with known or symptomatic cardiovascular disease were excluded from this study because of the confounding effects of ischemia and corresponding neovascularization on endothelial progenitor cell activity. Similarly, women were excluded from this study because of the potential confounding effects of follicular and uterine wall angiogenesis that occurs during the menstrual cycle. (asuda et al., Circulation 100:475, 1999; Masuda et al., Circulation 100:691-692, 1999.) To avoid other conditions in which adult neovascularization might be present, patients with cancer, proliferative retinopathy, hyperthyroidism, or chronic disease were also excluded. All enrolled subjects underwent detailed cardiovascular risk assessment after signing informed consent and the study was approved by the National Heart, Lung, and Blood Institutional Review Board. No medications, including vitamins, were taken for at least one week prior to the study. Statins and angiotensin converting enzyme (ACE) inhibitors were discontinued for two months after appropriate tapering, and other anti-hypertensive medications were discontinued for at least two weeks with appropriate blood pressure monitoring. Diabetics continued their regular glucose control medications. Endothelial progenitor cell isolation and colony forming assay: A 20 ml sample of venous blood was used for endothelial progenitor cell isolation. Samples were initially diluted with phosphate buffered saline (PBS) and peripheral blood mononuclear cells (PBMCs) were isolated by density gradient centrifugation using Ficoll-Paque™ PLUS (Amersham Phannacia Biotech AB, Uppsala, Sweden). All isolations occurred within four hours of obtaining the sample. Recovered cells were washed twice with PBS and once in growth media consisting of Medium 199 (GIBCO BRL® Life Technologies) supplemented with 20% FBS, penicillin (100 U/ml) and streptomycin (100 μg/ml). Isolated cells were subsequently re-suspended in growth media and plated on dishes coated with human fibronectin (BIOCOAT® Becton Dickinson Labware, Bedford, Mass.) and incubated at 37° C. in humidified 5% CO2. To eliminate the contamination of the assay with mature circulating endothelial cells, an initial pre-plating step was performed using 5 million PBMCs per well of a 6-well plate. After 48 hours, the non-adherent cells were collected and 1×106 cells were then re-plated onto fibronectin-coated 24-well plates for final colony number assessment. Growth media was changed every three days, and after seven days the numbers of endothelial progenitor cell colonies were counted. An endothelial progenitor cell colony consisted of multiple thin, flat cells emanating from a central cluster of rounded cells. A central cluster alone without associated emerging cells was not counted as positive. Colonies were counted manually in a minimum of four separate wells by observers unaware of the clinical profile. Confirmation of endothelial lineage in selected subjects (n=10) was performed as previously described (Asahara et al., Science 275:964-967, 1997; Ito et al., Cancer Res 59:5875-5877, 1999). Briefly, indirect immunostaining was performed using endothelial specific antibodies directed against the Vascular Endothelial Growth Factor Receptor kinase insert domain receptor (KDR, Flk-1, vascular endothelial growth factor-2) and CD31 (DAKO). In addition, confirmation of the cell type was performed using uptake of DiI-acetylated low density lipoprotein (DiI-Ac-LDL) and co-staining with BS-1 Lectin. Further confirmation of EPC lineage was sought using flow cytometry by incubation of peripheral blood samples with monoclonal antibodies directed against KDR and the early stem and progenitor cell marker, AC133 (Miltenyi Biotech). To assess reproducibility, colony counts were measured twice from the same subjects (n=10) from two separate blood samples, drawn at least one week apart and read independently by two observers blinded to the cardiovascular risk profile of the subject. The interobserver correlation for measurement of progenitor colonies was 0.92 while the intra-class correlation obtained by a single observer reading the same patient, sampled on two separate occasions separated by at least one week, was 0.97. For measurement of cellular senescence, a subset of 16 age-matched patients who were divided into high and low Framingham risk groups (mean 7.3+/−2.3 versus 1.5+/−2.1; p<0.01) was recruited from the original 45 subjects. Endothelial progenitor cell cultures derived from these individuals were maintained for seven days with fresh media supplied every three days. Senescence associated β-galactosidase (SA-β-Gal) activity was measured as previously described in Dimri et al., Proc. Natl. Acad. Sci. U.S.A. 92:9363-9367, 1995. Briefly, cells were fixed with 4% formaldehyde and incubated overnight in X-Gal solution (1 mg/ml) at 37° C. without CO2. Only isolated cells away from central colonies were analyzed and only those cells with distinct blue cytoplasmic color were counted as positive. The percentage of positive cells was determined by counting four random fields containing approximately 100-200 cells. Assessment of endothelium-dependent and -independent function: Brachial reactivity testing was performed in the morning after an overnight fast. Imaging of the brachial artery, proximal to the antecubital fossa was performed using high-resolution ultrasound (12.5 MHz linear-array transducer ATL HDI 5000, Advanced Technology Laboratories, Inc. Bothell Wash.), as previously reported. (Prasad et al., J Am Coll Cardiol 38:1089-1095, 2001; Corretti et al., J Am Coll Cardiol 39:257-265, 2002.) Endothelium-dependent flow-mediated vasodilation (flow mediated brachial reactivity) was assessed by measuring the maximum increase in diameter of the brachial artery during reactive hyperemia created by a cuff inflated at 225 mmHg for five minutes on the upper arm, proximal to the measurement site. After rapid cuff deflation, flow velocity was measured for the first 15 seconds, and the artery lumen was imaged continually for the next 120 seconds of hyperemia. Baseline measurements included brachial artery diameter and flow velocity measured by pulsewave-Doppler at approximately 70° to the vessel. Following a rest period of 15 minutes, repeat baseline measurements (diameter and flow velocity) were recorded, followed by 0.4 mg sublingual nitroglycerin (nitroglycerin) spray to assess endothelium-independent vasodilation. Three minutes later, diameter and flow velocity measurements were recorded. Studies were performed by a single experienced operator (G.Z.) and images were digitized and recorded on VHS videotape for subsequent analysis. Prior to patient enrollment in this study, an eight-week reproducibility study was performed of the entire procedure of flow-mediated and nitroglycerin induced brachial reactivity with a single observer and seven patients. Brachial artery diameter measurements at rest (3.77 and 3.72, r=0.99), with flow mediated dilation (4.02 and 4.0, r=0.97) and with nitroglycerin (4.23 and 4.09, r=0.88) were reproducible. Flow-mediated vasodilation was similar at baseline and at eight week follow up (12.7+/−0.8% and 11.9+/−0.8%, P=0.7). Furthermore, interobserver variability of the ultrasound analysis (acquired by a single operator) was also measured and was found to have an r value of 0.99. The brachial artery vasodilator response was calculated as: % vasodilation=[post-ischemia or nitroglycerin diameter−baseline diameter]×100 baseline diameter Statistical analysis: Measurement data are expressed as mean±SEM. Means of subjects with high versus low cardiovascular risk were compared by 2-tailed unpaired Student's t-test. The chi-square test was used for comparisons of categorical variables. Univariate correlations were performed using the Spearman's correlation coefficient. To identify predictors of change in endothelial progenitor cell colony counts in a multivariate setting, multiple linear regression was used (General Linear Model Procedure of SAS) on the regressors: age, race, body mass index, cigarette smoking, hypertension, diabetes, cholesterol and glucose levels. In addition, the flow mediated brachial reactivity and nitroglycerin responses were also entered as covariates. A similar analysis was repeated for determinants of flow mediated brachial reactivity. Example 2 Endothelial Progenitor Cell Colony Formation and Individual Risk Factors Recent studies have defined a cell population termed endothelial progenitor cells that can be isolated from circulating mononuclear cells (Asahara et al., Science 275:964-967, 1997; Lin et al., J Clin Invest 105:71-77, 2000; Peichev et al., Blood 95:952-958, 2000), bone marrow (Reyes et al., J Clin Invest 109:337-346, 2002) and cord blood (Murohara et al., J Clin Invest 105:1527-1536, 2000). As disclosed herein, tests have been conducted to determine that endothelial progenitor cells contribute to ongoing endothelial repair and maintenance of endothelial function. Endothelial progenitor cell activity in a group of healthy adult men has been measured. These individuals had no symptoms associated with atherosclerosis or of active ischemia and therefore seemed unlikely to have significant levels of ongoing neovascularization. The data described below shows that in these individuals, there is a strong association between depressed endothelial progenitor cell levels and impairment in endothelial function. In addition, individuals with high cardiovascular risk not only have fewer endothelial progenitor cells, but their endothelial progenitor cells also appear biologically older. Peripheral blood mononuclear cells plated on fibronectin coated dishes formed distinct colonies that were easily visualized (FIG. 1). Endothelial progenitor cells isolated in this fashion exhibit many endothelial characteristics including staining positive for CD31, Tie-2 and Flk-1 (Asahara et al., Science 275:964-967, 1997; Ito et al., Cancer Res 59:5875-5877, 1999). The level of circulating endothelial progenitor cells was assessed, and correlated with the presence or absence of known conventional cardiovascular risk factors. As noted in FIG. 2A, endothelial progenitor cell colony forming units were significantly reduced in patients with elevated serum cholesterol level, hypertension or diabetes (P=<0.05). A negative correlation between the patient's age and circulating endothelial progenitor cells was observed. However this relationship was not statistically significant. When, in this small group of relatively healthy volunteers, the individual risk factors of cholesterol, hypertension and diabetes were adjusted for age, only hypercholesterolemia remained significant (P=0.004, P=0.08 and P=0.07 respectively). To determine whether a cumulative risk factor profile influenced endothelial progenitor cell counts, the Framingham risk factor score was calculated for each patient. A significant correlation between the calculated risk score and endothelial progenitor cell counts (r=−0.39, p=0.008) was found, with higher scores associated with diminished endothelial progenitor cell counts (FIG. 2B). Example 3 Endothelial Progenitor Cell Colony Counts and Endothelium-dependent and -Independent Function Because the vascular endothelium integrates the injury from established and as yet unknown risk factors, the relationship between endothelial progenitor cell colony counts and flow mediated brachial reactivity, a composite measure of endothelial integrity, was assessed. As noted in FIG. 3A, there was a strong correlation between endothelial progenitor cell colony count and flow mediated brachial reactivity (r=0.59, P<0.001). When the measured flow mediated brachial reactivity was divided into tertiles (FIG. 3B), subjects with the highest flow mediated brachial reactivity had endothelial progenitor cell colony counts approximately 3-fold higher than those in the lowest tertile (24.5±3.6 versus 7.8±1.5, P<0.001). In order to determine whether the relationship between endothelial progenitor cells and flow mediated brachial reactivity was strictly determined by endothelium-dependent function, the response of each subject to nitroglycerin was determined. These studies demonstrated a correlation between endothelial progenitor cell counts and the response to nitroglycerin (r=0.40, P=0.007). To assess whether the observed relationship between flow mediated brachial reactivity and endothelial progenitor cell counts were independent of vascular smooth muscle function, the ratio of flow mediated brachial reactivity/nitroglycerin was subsequently determined for each individual. This analysis normalizes endothelium-dependent responses for smooth muscle function in each patient. As demonstrated in FIG. 3C, patients in the tertile with the lowest flow mediated brachial reactivity/nitroglycerin ratio had reduced endothelial progenitor cell counts compared to those in the tertile with the highest flow mediated brachial reactivity/nitroglycerin ratio (8.1±1.2 versus 21.5±3.7, P=0.01). Finally, a multivariate regression analysis was performed to determine whether the number of endothelial progenitor cell colonies were associated with age, race, body mass index, cigarette smoking, hypertension, diabetes, total cholesterol, glucose levels, brachial flow mediated brachial reactivity or nitroglycerin responses. This analysis demonstrated that flow mediated brachial reactivity was an independent predictor of endothelial progenitor cell colony number (P<0.001). A reciprocal analysis that divided subjects into tertiles of measured endothelial progenitor cell activity demonstrated a striking relationship between endothelial progenitor cell levels and flow mediated brachial reactivity (FIG. 5, Table 1). Example 4 Endothelial Progenitor Cells are Important Biological Determinants of Flow Mediated Brachial Reactivity If endothelial progenitor cells constitute an important aspect of ongoing vascular repair, it was reasoned that elevated levels of these cells might preserve flow mediated brachial reactivity even in the presence of ongoing vascular injury or dysfunction. Similarly, it was reasoned that in the setting of low levels of endothelial progenitor cells, flow mediated brachial reactivity might be impaired even in the absence of conventional risk factors. To test this hypothesis, subjects were divided into four subsets based on their Framingham score and endothelial progenitor cell colony counts. As noted in FIG. 4, those individuals with high endothelial progenitor cell counts (>13, mean 23) had preserved flow mediated brachial reactivity irrespective of whether or not they had a high or low conventional risk factor score. Similarly, those with low endothelial progenitor cell counts (<13, mean 7) had depressed flow mediated brachial reactivity, independent of whether or not their risk factor score was high or low. From these observations, it appears that endothelial progenitor cell activity is a better predictor of flow mediated brachial reactivity then the presence or absence of conventional risk factors. A formal statistical analysis was performed to confirm these conclusions. When assessed alone, Framingham risk score significantly correlated with observed flow mediated brachial reactivity (P=0.016). However, in a multivariate analysis of flow mediated brachial reactivity using both Framingham risk score and endothelial progenitor cells as regressors, cumulative risk score lost its significance (P=0.27), while endothelial progenitor counts were strongly significant (P=0.003) over and above the effects of the Framingham risk score. Example 5 Risk Factor Profile and Endothelial Progenitor Cell Senescence The decreased levels of circulating endothelial progenitor cells observed in individuals with elevated risk factors might occur through multiple mechanisms. Without being bound by theory, one possibility is that risk factors could somehow directly influence bone marrow mobilization or biological half-life of endothelial progenitor cells. Again, without being bound by theory, an alternative explanation is that with continuous endothelial damage or dysfunction there is an eventual exhaustion of the supply of endothelial progenitor cells. It is important to note that unlike multi-potential stem cells, progenitor cells do not share the almost infinite capacity for self-renewal. If the latter hypothesis was correct, endothelial progenitor cells derived from patient with high cardiovascular risk might be qualitatively different then endothelial progenitor cells derived from low risk patients. In particular, if endothelial progenitor cells from high risk individuals had undergone use-dependent depletion, those cells remaining in circulation might demonstrate in vitro characteristics of clonal exhaustion and/or accelerated aging. To further assess this possibility, endogenous cellular β-galactosidase activity was measured, a widely used marker of cellular senescence (Dimri et al., Proc. Natl. Acad. Sci. U.S.A. 92:9363-9367, 1995) in a subset of our patients (n=16) selected because they had either high or low cumulative cardiovascular risk (Framingham risk 7.3+/−2.3 versus 1.5+/−2.1; ??p<0.01) but similar chronological age (high risk group mean age 49.1+/−5.9 versus low risk 54.6+/−9.3; p=0.85. Endothelial progenitor cells were grown from these subjects for seven days in culture and then assayed for the percentage of cells exhibiting a senescent phenotype. A significant difference in the observed level of cellular senescence that averaged 27+/−9% in low risk individuals compared to 72+/−15% in aged matched high risk individuals (P<0.001) was noted. Endothelial damage ultimately represents a balance between the magnitude of injury and the capacity for repair. A variety of evidence suggests that cardiovascular risk factors induce endothelial injury and that impaired endothelial function represents a functional integration of this ongoing injury. As demonstrated herein, there is a strong correlation between levels of circulating endothelial progenitor cells and total cardiovascular risk. Levels of circulating endothelial progenitor cells were also highly correlated with endothelium-dependent flow mediated brachial reactivity. This observation suggests that individuals with multiple risk factors would develop impaired endothelial dysfunction when their intrinsic ability to repair the vascular endothelium was impaired (i.e. low endothelial progenitor cell levels). Analysis of the subgroup with multiple risk factors confirmed that flow mediated brachial reactivity was depressed only in those subjects with low endothelial progenitor cell counts, while a high risk factor score with high endothelial progenitor cell activity had preserved endothelial function (FIG. 4). These results are particularly significant given the growing realization that endothelial dysfunction conveys significant prognostic implications (Suwaidi et al., Circulation 101:948-954, 2000; Schächinger et al., Circulation 101:1899-1906, 2000; Perticone et al., Circulation 104:191-196, 2001; Gokce et al., Circulation 105:1567-1572, 2002; Halcox et al., Circulation 2002; 106:653-658). Similarly, as demonstrated herein, even in the absence of conventional risk factors, low levels of endothelial progenitor cells were predictive of impaired flow mediated brachial reactivity. Without being bound by theory, one explanation for the observations of this latter subgroup is that impaired flow mediated brachial reactivity results from currently unknown and hence non-conventional risk factors influencing the vessel wall. Alternatively, impaired flow mediated brachial reactivity in this group might have resulted from a primary defect in endothelial progenitor cell levels. Indeed, although Framingham risk score was significantly correlated with flow mediated brachial reactivity, in a multivariate analysis of flow mediated brachial reactivity using both risk factor and endothelial progenitor cell as regressors, only endothelial progenitor cell levels remained a significant determinant of endothelial function. Statin therapy increases the levels of circulating endothelial progenitor cells in both animal models as well as in patients with coronary artery disease (Llevadot et al., J Clin Invest 108:399-405, 2001; Dimmeler et al., J of Clin Invest 108:391-397, 2001; Vasa et al., Circulation 103:2885-2890, 2001). Thus, as described herein, lipid lowering agents, or other risk factor modifications, directly affect endothelial progenitor cell kinetics. Without being bound by theory, continuous endothelial damage or dysfunction there is an eventual depletion or exhaustion of a presumed finite supply of endothelial progenitor cells. Such depletion is not simply a reflection of chronological age, since as noted in FIG. 2A, although older subjects tended to have fewer endothelial progenitor cells, this relationship was not statistically significant. The level and duration of risk factors induced injury and dysfunction, and not biological age, is the primary determinant for the differences observed. In the studies described herein, progenitor cells derived from high risk patients are both fewer in number and appear to undergo senescence at a more rapid rate then similar derived cells from low risk patients. Most of the emphasis in preventing cardiovascular disease has been aimed at reducing risk factor-induced endothelial damage or dysfunction, while comparatively little emphasis has been placed on understanding or manipulating the intrinsic vascular repair mechanisms. As described in this work, the endothelial progenitor cells are important in this ongoing repair process, as there is an association between circulating endothelial progenitor cells and both cardiovascular risk and function. Administration of endothelial cells could be used to prevent or treat loss of vascular function. It will be apparent that the precise details of the methods or compositions described may be varied or modified without departing from the spirit of the described invention. We claim all such modifications and variations that fall within the scope and spirit of the claims below.
<SOH> BACKGROUND <EOH>Cardiovascular disease is a major health risk throughout the industrialized world. Atherosclerosis, the most prevalent of cardiovascular diseases, is the principal cause of heart attack, stroke, and gangrene of the extremities. It is also the principal cause of death in the United States. Atherosclerosis is a complex disease involving many cell types and molecular factors (for review, see Ross, Nature 362:801-809, 1993). The process is believed to occur as a response to insults to the endothelial cell layer that lines the wall of the artery. The process includes the formation of fibrofatty and fibrous lesions or plaques, preceded and accompanied by inflammation. The advanced lesions of atherosclerosis may occlude an artery, and result from an excessive inflammatory-fibroproliferative response to numerous different forms of insult. For example, shear stresses are thought to be responsible for the frequent occurrence of atherosclerotic plaques in regions of the circulatory system where turbulent blood flow occurs, such as branch points and irregular structures. The first event that is observed in the formation of an atherosclerotic plaque occurs when blood-borne monocytes adhere to the vascular endothelial layer and transmigrate through to the sub-endothelial space. Adjacent endothelial cells at the same time produce oxidized low density lipoprotein (LDL). These oxidized LDL's are then taken up in large amounts by the monocytes through scavenger receptors expressed on their surfaces. In contrast to the regulated pathway by which native LDL (nLDL) is taken up by nLDL specific receptors, the scavenger pathway of uptake is not regulated by the monocytes. The lipid-filled monocytes are termed “foam cells,” and are the major constituent of the fatly streak. Interactions between foam cells and the endothelial and SMCs which surround them lead to a state of chronic local inflammation which can eventually lead to smooth muscle cell proliferation and migration, and the formation of a fibrous plaque. Such plaques occlude the blood vessel concerned and restrict the flow of blood, resulting in ischemia. Ischemia is characterized by a lack of oxygen supply in tissues of organs due to inadequate perfusion. The most common cause of ischemia in the heart is atherosclerotic disease of epicardial coronary arteries. By reducing the lumen of these vessels, atherosclerosis causes an absolute decrease in myocardial perfusion in the basal state or limits appropriate increases in perfusion when the demand for flow is augmented. The principal surgical approaches to the treatment of ischemic atherosclerosis are bypass grafting, endarterectomy, and percutaneous translumenal angioplasty (PCTA). The latter approach often fails due to restenosis, in which the occlusions recur and often become even worse. This is estimated to occur at an extraordinarily high (30-50%) rate. It appears that much of the restenosis is due to further inflammation, smooth muscle accumulation, and thrombosis. Thus, there remains a need for methods to diagnose and/or treat atherosclerosis.
<SOH> SUMMARY <EOH>Methods for assessing the number of circulating endothelial progenitor cells are disclosed herein. Enumeration of the number of circulating endothelial progenitor cells can be used to detect alterations in vascular function, and can be used to identify agents that affect vascular function. These methods are of use in diagnosing and treating a variety of vascular disorders, including, but not limited to atherosclerosis. In one embodiment, a method is disclosed herein for diagnosing decreased vascular function in a subject. The method includes assaying the number of endothelial progenitor cells, for example from a blood sample from a subject. A decrease in the number of endothelial progenitor cells in the sample as compared to a control indicates decreased vascular function. In another embodiment, a method is also disclosed for detecting increased vascular function in a subject. The method includes assaying the number of endothelial progenitor cells, for example from a blood sample from a subject. An increase in the number of endothelial progenitor cells in the sample as compared to a control indicates increased vascular function. In yet another embodiment, a method for diagnosing future cardiovascular risk, such as the development of atherosclerosis, is disclosed. The method includes assaying the number of endothelial progenitor cells. A decrease in the number of endothelial progenitor cells in the sample as compared to a control indicates increased cardiovascular risk. A method is disclosed to screen for agents that affect vascular function. The method includes administering a therapeutically effective amount of the agent to a subject, and assessing the number of endothelial progenitor cells in a sample from the subject. An increased number of endothelial progenitor cells in the sample as compared to a control indicates that the agent affects vascular function. A method is also disclosed for screening for agents of use in treating cardiovascular disease. The method includes administering a therapeutically effective amount of the agent to a subject, and assessing the number of endothelial progenitor cells in a sample from the subject. An increased number of endothelial progenitor cells in the sample as compared to a control indicates that the agent is of use for the treatment of the cardiovascular disease. Also disclosed is a method for treating a subject with decreased vascular function. The method includes administering a therapeutically effective amount of endothelial progenitor cells to the subject. In one embodiment, the subject has atherosclerosis. A method is disclosed for diagnosing increased cardiovascular risk or decreased vascular function in a subject. The method includes assaying a number of senescent endothelial progenitor cells in a blood sample from the subject, wherein a increase in the number of senescent endothelial progenitor cells in the sample as compared to a control indicates increased cardiovascular risk or decreased vascular function. In addition, a method is disclosed for screening for an agent of use in treating a cardiovascular disease. The method includes administering a therapeutically effective amount of the agent to a subject, and assessing the number of senescent endothelial progenitor cells in a sample from the subject. A decreased number of endothelial progenitor cells in the sample as compared to a control indicates that the agent is of use in treating the cardiovascular disease. The foregoing and other features and advantages will become more apparent from the following detailed description of several embodiments, which proceeds with reference to the accompanying figures.
20050511
20100504
20060316
95404.0
A61K4800
0
KAUSHAL, SUMESH
METHOD FOR DIAGNOSIS AND TREATMENT OF VASCULAR DISEASE
UNDISCOUNTED
0
ACCEPTED
A61K
2,005
10,534,632
ACCEPTED
Imaging system for vehicle
An imaging system for a vehicle includes a camera module positionable at the vehicle and a control. The camera module includes a plastic housing that houses an image sensor, which is operable to capture images of a scene occurring exteriorly of the vehicle. The control is operable to process images captured by the image sensor. The portions of the housing may be laser welded or sonic welded together to substantially seal the image sensor and associated components within the plastic housing. The housing may include a ventilation portion that is at least partially permeable to water vapor to allow water vapor to pass therethrough while substantially precluding passage of water droplets and/or other contaminants. The housing may be movable at the vehicle between a stored position and an operational position, where the image sensor may be directed toward the exterior scene.
1: An imaging system for a vehicle, said imaging system comprising: a camera module positionable at the vehicle, said camera module comprising a plastic housing and an imaging sensor, said plastic housing including a first portion and a second portion, said first portion and said second portion being one of laser welded and sonic welded together to substantially seal said image sensor and associated components within said plastic housing; and a control operable to process images captured by said image sensor. 2-3. (canceled) 4: The imaging system of claim 1, wherein said first portion comprises a connector portion and includes a connector at an end thereof and said second portion comprises a camera portion and includes a transparent cover portion for receiving an image therethrough. 5: The imaging system of claim 4, wherein said transparent cover is one of laser welded and sonic welded to said camera portion. 6: The imaging system of claim 1, wherein said camera module is positioned in a movable housing that is movable relative to an exterior portion of the vehicle to move said image sensor between a stored position generally within the portion of the vehicle and an operational position where said image sensor is positioned to have a field of view exteriorly of the vehicle. 7: The imaging system of claim 6, wherein said movable housing comprises a transparent panel, said transparent panel being positioned at least partially across an opening of said housing and generally in the field of view of said image sensor. 8: The imaging system of claim 7, wherein said movable housing comprises a panel cleaning device positionable at the exterior portion of the vehicle and configured to engage an exterior surface of said transparent panel to clean said transparent panel as said housing moves said image sensor between said stored position and said operational position. 9: The imaging system of claim 7, wherein said housing is configured to receive an illumination source, said illumination source being directable toward the exterior scene when said housing moves said image sensor to said operational position. 10-11. (canceled) 12: The imaging system of claim 1 including at least one illumination source, said control being operable to selectively activate said at least one illumination source in response to a detected ambient light level. 13-14. (canceled) 15: The imaging system of claim 1, wherein said control is operable to selectively switch said image sensor from a color mode to a black and white mode. 16: The imaging system of claim 1, wherein said housing includes a ventilation portion, said ventilation portion being at least partially permeable to water vapor to allow water vapor to pass therethrough while substantially precluding passage of at least one of water droplets and contaminants. 17-30. (canceled) 31: An imaging system of a vehicle, said imaging system comprising: an imaging device operable to capture images of a scene occurring exteriorly of the vehicle; a holding device for movably holding said imaging device, said holding device comprising a housing, a transparent panel and a panel cleaning device, said housing being movably mountable at an exterior portion of a vehicle, said imaging device being positioned within said housing, said transparent panel being positioned at least partially across an opening of said housing and generally in the field of view of said imaging device, said housing being movable relative to the exterior portion of the vehicle to move said imaging device between a stored position, where said imaging device is positioned generally within the portion of the vehicle, and an operational position, where said imaging device is positioned to have a field of view exteriorly of the vehicle, said panel cleaning device being positionable at the exterior portion of the vehicle and configured to engage an exterior surface of said transparent panel to clean said transparent panel as said housing moves said imaging device between said stored position and said operational position; and a control operable to process images captured by said imaging device. 32-33. (canceled) 34: The imaging system of claim 31, wherein said housing moves said imaging device to said operational position in response to engagement of a reverse gear of the vehicle. 35: The imaging system of claim 31 including a spraying device operable to spray fluid onto said transparent panel. 36: The imaging system of claim 31 including an illumination source that is selectively operable to illuminate the exterior scene. 37: The imaging system of claim 36, wherein said housing is configured to receive said illumination source, said illumination source being directable toward the exterior scene when said housing moves said imaging device to said operational position. 38-39. (canceled) 40: The imaging system of claim 37, wherein said control is operable to selectively activate said illumination source and said imaging device when said imaging device is moved to said stored position to determine if moisture is present on said transparent panel. 41: The imaging system of claim 36, wherein said control is operable to selectively activate said illumination source in response to at least one of (a) said imaging device being in said operational position and (b) a detected ambient light level. 42-46. (canceled) 47: The imaging system of claim 31, wherein said housing is movable to selectively position said imaging device in first and second operational positions. 48: The imaging system of claim 47, wherein said control is operable to determine a distance to at least one object in response to processing of images captured by said imaging device when in said first and second operational positions. 49: The imaging system of claim 47, wherein said control is operable to selectively move said housing to position said imaging device at said first operational position in response to the vehicle making an initial approach to a target zone and to position said imaging device at said second operational position in response to the vehicle moving further into the target zone, said imaging device being directed more downward when in said second operational position relative to said first operational position. 50-65. (canceled)
CROSS REFERENCE TO RELATED APPLICATIONS The present application claims priority of U.S. provisional applications, Ser. No. 60/426,239, filed Nov. 14, 2002 by Bingle for CAMERA MODULE FOR VEHICLE (DON01 P-1031); Ser. No. 60/477,416, filed Jun. 10, 2003 by Camilleri for IMAGING SYSTEM FOR VEHICLE (DON01 P-1097); and Ser. No. 60/492,544, filed Aug. 5, 2003 by Whitehead et al. for CAMERA HOUSING FOR VEHICLE IMAGING SYSTEM (DON01 P-1108), which are all hereby incorporated herein by reference in their entireties. FIELD OF THE INVENTION The present invention relates to an imaging system for a vehicle and, more particularly, to a camera which may be mounted at an exterior portion of a vehicle for providing an image of a scene exteriorly of the vehicle. The present invention also relates to an imaging system for a vehicle which provides color imaging and a low light imaging capability. BACKGROUND OF THE INVENTION The advent of low cost, reliable imaging devices, based on a variety of silicon technologies, and in particular CMOS technology, combined with an improved cost/performance ratio for displays capable of meeting automotive specifications, and an increasing application rate of video monitor displays for automotive navigation systems or as part of the driver interface to a wide variety of vehicle systems, has lead to an increasing use of cameras or imaging sensors designed to give the driver a view of those areas around the vehicle which are not in the normal direct field of view of the driver, typically referred to as “blind spots”. These areas include the region close to the front of the vehicle, typically obscured by the forward structure of the vehicle, the region along the passenger side of the vehicle, the region along the driver's side of the vehicle rearward of the driver, and the area or region immediately rearward of the vehicle which cannot be seen directly or indirectly through the rear view mirror system. The camera or imaging sensor may capture an image of the rearward (or sideward or other blind spot area) field of view, and the image may be displayed to the driver of the vehicle to assist the driver in backing up or reversing or otherwise driving or maneuvering the vehicle. The use of electronic cameras in these applications significantly increases the driver's knowledge of the space immediately surrounding the vehicle, which may be of importance prior to and during low speed maneuvers, and thus contributes to the safe completion of such maneuvers. It is thus known to provide a camera or imaging sensor on a vehicle for providing an image of a scene occurring exteriorly or interiorly of the vehicle to a driver of the vehicle. Such a camera may be positioned within a protective housing, which may be closed about the camera or sensor and secured together via fasteners or screws or the like. For example, a metallic protective housing may be provided, such as a die cast housing of aluminum or zinc or the like. In particular, for camera sensors mounted on the exterior of a vehicle, protection against environmental effects, such as rain, snow, road splash and/or the like, and physical protection, such as against road debris, dirt, dust, and/or the like, is important. Thus, for example, in known exterior camera sensor mounts, a butyl seal, such as a hot dispensed butyl seal, or an O-ring or other sealing member or material or the like, has been provided between the parts of the housing to assist in sealing the housing to prevent water or other contaminants from entering the housing and damaging the camera or sensor positioned therein. However, such housings typically do not provide a substantially water tight seal, and water droplets thus may enter the housing. Furthermore, any excessive vibration of the camera sensor, due to its placement (such as at the exterior of the vehicle), may lead to an undesirable instability of the image displayed to the driver of the vehicle. Also, such cameras or sensors are costly to manufacture and to implement on the vehicles. Such vehicle vision systems often position a camera or imaging sensor at an exterior portion of a vehicle to capture an image of a scene occurring exteriorly of the vehicle. The cameras, particularly the cameras for rearward vision systems, are thus typically placed or mounted in a location that tends to get a high dirt buildup on the camera and/or lens of the camera, with no easy way of cleaning the camera and/or lens. In order to reduce the dirt or moisture buildup on the lenses of such cameras, it has been proposed to use hydrophilic or hydrophobic coatings on the lenses. However, the use of such a hydrophilic or hydrophobic coating on the lens is not typically effective due to the lack of air flow across the lens. It has also been proposed to use heating devices or elements to reduce moisture on the lenses. However, the use of a heated lens in such applications, while reducing condensation and misting on the lens, may promote the forming of a film on the lens due to contamination that may be present in the moisture or water. Also, the appearance of such cameras on the rearward portion of vehicles is often a problem for styling of the vehicle. Typically, based on consumer preference and at least a perceived improved ability to extract information from the image, it is desired to present a color image to the driver that is representative of the exterior scene as perceived by normal human vision. It is also desirable that such imaging devices or systems be useful in all conditions, and particularly in all lighting conditions. However, it is often difficult to provide a color imaging sensor which is capable of providing a clear image in low light conditions. This is because conventional imaging systems typically have difficulty resolving scene information from background noise in low light conditions. Silicon-based cameras may be responsive to light in the visible and near infrared portions of the spectrum. It is known to filter out the infrared portion of the energy available to the camera in order to maintain an appropriate color balance. When this is done, the camera sensitivity may be less than if the near infrared and infrared light was received and used by the camera. Depending on the imaging technology used, the minimum sensitivities currently economically available for automotive cameras are typically in the range of 1 to 2 lux and may maintain a reasonable image quality at light levels at or above such levels. However, the conditions on a dark cloudy night where moonlight is obscured, and/or in rural situations in which there is no source of artificial lighting, may result in a scene illumination as low as about 0.01 lux. While the technology continues to improve the low light sensitivity of silicon based cameras, it is not expected that 0.01 lux capability will become available in the foreseeable future. Other technologies may be capable of such sensitivity, but are not sufficiently cost effective for general application in the automotive industry. Therefore, there is a need in the art for a camera housing that overcomes the shortcomings of the prior art, and a need in the art for an imaging system that may provide clear, satisfactory images during all driving or lighting conditions, and thus overcomes the shortcomings of the prior art imaging systems. SUMMARY OF THE INVENTION The present invention is intended to provide a camera module which includes a camera or image sensor and a circuit board positioned within a housing, which may be laser welded or sonic welded or the like to substantially seal the camera and circuit board within the housing. The housing, preferably molded of a plastic material, may include a plastic molded connector extending therefrom, such that the camera housing and connector are configured as a single unitary module. The camera module may include a heating element for heating a transparent cover at the lens (or for heating the lens itself) of the camera to assist in defogging or defrosting the transparent cover in cold weather conditions. The transparent cover may have a transparent conductive coating (such as an indium tin oxide (ITO) coating or doped tin oxide or a metal grid or the like), preferably on its inner surface, such that contact of a power terminal (connected to or in communication with or powered by a battery or other power source of the vehicle) and a ground terminal of the heating elements at the conductive coating causes heating of the coating to defrost or defog the cover. The heating elements or terminals may be actuated in response to a control or thermostat, which functions to activate and deactivate the heating element at predetermined temperatures sensed by a temperature sensor at or in the camera module or elsewhere at, in or on the vehicle. The present invention thus provides a camera module that maintains the camera or imaging sensor and is substantially impervious to environmental elements, such as rain, snow, dirt, dust, road splash, road debris and the like. The present invention also provides at least partial, and preferably substantial, reduced vibration affects of the camera or image sensor. According to an aspect of the present invention, a substantially sealed camera module for an imaging system of a vehicle includes a plastic housing, which preferably includes first and second portions. The first and second portions are preferably laser welded or sonic welded together to substantially seal the camera or sensor and associated components within the plastic housing. The laser welded or sonic welded plastic housing provides a substantially hermetic seal to prevent water intrusion or the like into the housing. Alternately, and less preferably, the first and second portions may be adhesively sealed or joined. The camera module may be incorporated into an imaging system that includes the sensor and a control for processing images captured by the imaging sensor. The camera module may be positioned within a movable housing that is movable relative to the vehicle to move the imaging sensor between an in use or operational position, where the imaging sensor is directed toward the exterior scene, and a storage position, where the housing and the imaging sensor are positioned within a portion of the vehicle. According to another aspect of the present invention, a vented camera module for a vehicle includes a plastic housing which is configured to receive a camera or sensor therein. The housing of the vented camera module includes a semi-permeable ventilation area, such as a Gore-Tex assembly or area or patch or the like, which is at least partially permeable to water vapor and/or is porous enough to allow transfer of water vapor into and out from the housing, while substantially precluding entry of water droplets, dirt or the like into the housing. According to another aspect of the present invention, a camera module for a vehicle includes a housing and a transparent cover at a portion of the housing. The transparent cover provides a transparent wall of the housing for the lens and sensor or camera to receive an image therethrough. The cover may be heated to defrost or defog the cover in cold weather conditions or the like. The cover includes a surface (such as an inner surface within the housing) which has a conductive coating, such as a coating of indium tin oxide (ITO), doped tin oxide or the like. The module includes a pair of heater terminals or elements which contact the coating, whereby heating of the cover or coating on the cover (such as the inner surface of the cover) is accomplished by generating a flow of electricity or electrons or current across the coating on the cover via the heater terminals or elements. In one form, one of the heater terminals may be energized or charged with electricity and the other terminal may be grounded to the vehicle, such that the electrical current travels from the energized or powered terminal across the conductive coating to the grounded terminal, thereby heating the conductive coating and, thus, the transparent cover. Preferably, the heater terminals are spaced apart at generally opposite sides or portions of the transparent cover. Actuation of the heater terminals may defrost or defog the transparent cover and/or may heat the module housing and interior compartment of the camera module to dry out any moisture within the housing or compartment. In applications where the module includes a ventilation area, such as a vented semi-permeable membrane, such as a Gore-Tex assembly or the like, heating of the compartment may be especially suited for driving moisture out of the compartment or module through the ventilation area to limit or substantially preclude moisture condensing within the module. Optionally, the heater terminals may be actuated or energized in response to a control, which is operable to energize the heater terminals or elements in response to a thermostat and/or temperature sensor positioned at or within the camera module or elsewhere at, in or on the vehicle. Optionally, desiccant material, such as silica gel or the like, may be included in the housing to absorb moisture which may be present within the housing. According to yet another aspect of the present invention, a camera module for a vehicle comprises a housing, a transparent cover at a portion of the housing, an image sensor, at least one heating element and a control. The image sensor is positioned within the housing and is operable to receive an image of a scene exteriorly of the housing through the transparent cover. The heating element is operable to heat the transparent cover. The control is operable to activate the heating element in response to a temperature sensor. The heating element is activatable to heat the transparent cover to reduce fog and/or ice on the transparent cover. The present invention also provides a camera housing that is movably positioned at an exterior portion of a vehicle such that the camera may be moved from a stored position to an in-use or exterior or operational position. The camera housing may include a transparent window or panel and may further include a window wiper that functions to wipe dirt and/or moisture or the like from the window or panel as the housing moves the camera between the stored position and the operational position. According to an aspect of the present invention, a holding device for movably holding an imaging device of a vehicle includes a housing, a transparent panel and a panel cleaning device. The imaging device is operable to capture an image of a scene occurring exteriorly of the vehicle. The housing is movably mountable at an exterior portion of the vehicle and is configured to receive an imaging device therein. The housing is movable relative to the exterior portion of the vehicle to move the imaging device between a stored position, where the imaging device is positioned generally within the portion of the vehicle, and an operational position, where the imaging device is positioned to have a field of view exteriorly of the vehicle. The transparent panel is positioned at least partially across an opening of the housing and generally in the field of view of the imaging device. The panel cleaning device is positionable at the exterior portion of the vehicle and configured to engage the transparent panel to clean the transparent panel as the housing moves the imaging device between the stored position and the operational position. According to another aspect of the present invention, an imaging system for a vehicle includes an imaging device operable to capture an image of a scene occurring exteriorly of a vehicle, a control operable to process the image captured by the imaging device, and a camera housing device. The housing device includes a housing portion defining a compartment, a transparent panel substantially closing an opening of the compartment, and a panel cleaning device. The housing device is movably mountable on an exterior portion of the vehicle. The imaging device is positioned within the compartment and directed toward the transparent panel. The housing device is movable between a stored position, where the imaging device and the transparent panel are positioned at least substantially within the exterior portion of the vehicle, and an operational position, where the imaging device is directed exteriorly of the vehicle and has a field of view directed through the transparent panel and toward the exterior scene. The panel cleaning device is positionable at the exterior portion of the vehicle and configured to engage the transparent panel to clean the transparent panel as the housing device moves between the stored position and the operational position. The imaging system may include a display operable to display the image captured by the imaging device. The housing device may be pivotably mountable at the exterior portion of the vehicle, or the housing device may be slidably or otherwise movably mountable at the exterior portion of the vehicle. An outer panel of the housing device may define an exterior cover portion at the exterior portion of the vehicle when the housing device is moved or pivoted to the stored position. Optionally, the imaging system may comprise a color imaging sensor operable to capture color images of the exterior scene and an infrared imaging sensor operable to capture infrared images of the exterior scene. The control may selectively activate one of the color imaging sensor and the infrared imaging sensor in response to the ambient light intensity present in the exterior scene. Optionally, the imaging system may include an illumination source positioned within the compartment and directed toward the exterior scene when the housing device is moved to the operational position. The transparent panel and the compartment are positioned generally within the exterior portion of the vehicle when the housing device is moved to the stored position. Optionally, the control may be operable to selectively activate the illumination source and the imaging device when the housing device is moved to the stored position to determine if moisture is present on the transparent panel. The housing device may include a heater element that is selectively operable to heat the transparent panel to reduce moisture present on the transparent panel. Optionally, the housing device may be movable to selectively position the imaging device in first and second operational positions. The control may be operable to determine a distance to at least one object in the exterior scene in response to processing of images captured by the imaging device when the imaging device is in the first and second operational positions. For example, the control may be operable to selectively move the housing device to position the imaging device at the first operational position in response to the vehicle making an initial approach to a target zone and to position the imaging device at the second operational position in response to the vehicle moving further into the target zone. The imaging device may be directed more downward when in the second operational position relative to the first operational position. According to another aspect of the present invention, an imaging system of a vehicle includes an imaging device, a holding device and a control. The imaging device is operable to capture images of a scene occurring exteriorly of the vehicle. The holding device is pivotally mountable at a portion of a vehicle and includes a housing having an exterior panel and a transparent panel. The imaging device is positioned within the housing. The transparent-panel is positioned at least partially across an opening of the housing and generally in the field of view of the imaging device. The holding device is pivotable relative to the portion of the vehicle to move the imaging device between a stored position, where the imaging device is positioned generally within the portion of the vehicle, and an operational position, where the imaging device is positioned to have a field of view exteriorly of the vehicle. The exterior panel is generally aligned with an exterior surface of the portion of the vehicle and the transparent panel is generally within the portion of the vehicle when the imaging device is in the stored position. The control is operable to process images captured by the imaging device. The present invention also provides a vehicular imaging system or image capture system which is operable to capture an image of an exterior scene and to display the images at a display of the vehicle. The imaging system is operable to control illumination sources operable to illuminate the exterior scene and/or to control the color processing of the captured images and/or to control the color/monochromatic status or mode of the image capture device or camera of the system, in order to provide or display an optimum color or black and white image at the display which has optimum color representation of the scene or has optimum illumination or visibility or clarity or contrast ratio in the image displayed. For example, the imaging system may selectively activate visible or infrared or near infrared illumination sources or light emitting diodes (LEDs) in response to a detected ambient light level dropping or decreasing or lowering to a threshold level. The imaging system may also or otherwise selectively switch the imaging sensor from a color mode to a black and white mode in response to the reduced ambient light level. Optionally, the imaging system may apply an infrared contribution correction to the detected levels for each color (such as red, green, blue) detected by the imaging sensor to adjust the color balance of the imaging sensor for better color rendition in the captured images. Optionally, the imaging system may provide visible illumination to the exterior scene and may limit or block infrared and near infrared light present in the illuminated scene to reduce processing requirements to obtain the appropriate color balance in the captured images. Therefore, the present invention provides a camera module for a vehicle which may be substantially hermetically sealed to limit or substantially preclude water intrusion or the like into the housing of the module, or which may be vented to allow for water vapor to enter or exit the module. The camera housing may also include a heating element which is operable to defrost or defog the transparent cover of the module and/or to heat the compartment of the camera housing to limit or substantially preclude condensation from forming within the module. The heating element may be activated and deactivated at predetermined temperatures in response to a temperature sensor and/or thermostat. The transparent cover of the housing may include a conductive coating on a surface thereof, such that applying an electrical current or flow through or across the coating on the surface of the transparent cover functions to heat the surface of the cover to defrost or defog the transparent cover. The present invention thus provides an environmentally resilient, protected, economical camera module which may be mounted to a vehicle and connected or plugged into a wiring connector of the vehicle. The present invention thus also provides a camera housing device that is movable or adjustable to move a camera or imaging sensor between an operational position and a stored position. The camera thus may be positioned in a stored position within an exterior portion of the vehicle when not in use. The exterior panel of the camera housing device may provide an exterior cover at the exterior portion of the vehicle to protect the camera and lens from the elements when they are not in use. The housing device may include a transparent panel that substantially encloses the camera and lens within the housing. The housing device may also include a panel cleaning device that may clean the transparent panel to limit or substantially preclude dirt buildup or debris on the panel that may adversely effect the performance of the camera and thus of the imaging system. The present invention also provides an imaging system that is capable of providing a color image during daytime conditions, and that may provide a black and white image, with or without additional infrared or near infrared illumination provided to the scene, during darkened or nighttime conditions. The imaging system may correct the color image to account for infrared and near infrared illumination that may be present in the exterior scene, in order to provide an image with proper or desired color balance. The present invention thus may provide optimal images to the driver of the vehicle during substantially all types of lighting conditions. These and other objects, purposes, advantages and features of the present invention will become apparent upon review of the following specification in conjunction with the drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a rear perspective view of a vehicle having an imaging system thereon in accordance with the present invention; FIG. 2 is a plan view of the vehicle of FIG. 1; FIG. 3 is a perspective view of a camera module in accordance with the present invention; FIG. 4 is a side elevation of the camera module of FIG. 3; FIG. 5 is another side elevation of the camera module of FIGS. 3 and 4; FIG. 6 is an end elevation of the camera module of FIGS. 3-5; FIG. 7 is a sectional view of the camera module taken along the line VII-VII in FIG. 6; FIG. 8 is an opposite end elevation of FIG. 6 of the camera module of FIGS. 3-7; FIG. 9 is a sectional view of the camera module taken along the line IX-IX in FIG. 5; FIG. 10 is a sectional view of the camera module taken along the line X-X in FIG. 8; FIG. 11 is another sectional view of the camera module taken along the line XI-XI in FIG. 8; FIG. 12A is a side elevation of a camera housing portion of the camera module of the present invention; FIG. 12B is an end elevation of the camera housing portion of FIG. 12A; FIG. 12C is an opposite end elevation of FIG. 12B of the camera housing portion of FIGS. 12A and 12B; FIG. 12D is a sectional view of the camera housing portion taken along the line D-D in FIG. 12C; FIG. 13A is a top plan view of a circuit board useful with the camera module of the present invention; FIG. 13B is a side elevation of the circuit board of FIG. 13A; FIG. 14A is another plan view of the circuit board of FIGS. 13A and 13B, with the circuit board folded over itself; FIG. 14B is a side elevation of the circuit board of FIG. 14A; FIG. 15A is a side elevation of a connector portion of the camera module of the present invention; FIG. 15B is an end elevation of the connector portion of FIG. 15A; FIG. 15C is a sectional view of the connector portion taken along the line C-C in FIG. 15B; FIG. 15D is another sectional view of the connector portion taken along the line D-D in FIG. 15B; FIG. 15E is an opposite end elevation of FIG. 15B of the connector portion of FIGS. 15A-D; FIGS. 16A-D are various views of one side or portion of a metallic protective shield for the camera module of the present invention; FIG. 16E is a sectional view of the protective shield taken along the line E-E in FIG. 16D; FIGS. 17A and 17B are side elevations of an alternate embodiment of another camera module and/or components thereof in accordance with the present invention, with the connector portion being angled; FIG. 17C is a perspective view of the connector portion of the camera module of FIGS. 17A and 17B; FIG. 17D is a sectional view of the camera module taken along the line D-D in FIG. 17B; FIG. 17E is a sectional view of the camera module taken along the line E-E in FIG. 17A; FIG. 18 is a rear perspective view of a vehicle with a camera housing device in accordance with the present invention positioned thereon and positioned in its in-use or operational position; FIG. 19 is a side elevation and sectional view of a camera housing device in accordance with the present invention, with the camera housing device positioned so the camera is in its stored position; FIG. 20 is a side elevation and sectional view similar to FIG. 19, with the camera housing device positioned so the camera is in its operational position; FIG. 21 is a side elevation and sectional view of another camera housing device in accordance with the present invention, with an illumination source positioned within the camera housing device and movable with the housing device and camera; FIG. 22 is a side elevation and sectional view of another camera housing device in accordance with the present invention, with the camera housing device being slidable to move the camera between its stored position and operational position, and with the camera housing device shown in the stored position; FIG. 23 is a side elevation and sectional view of the camera housing device of FIG. 22, with the camera housing device shown in the extended or operational position; FIG. 24 is a schematic of an image capture device in accordance with the present invention; FIG. 25 is a block diagram of an imaging system in accordance with the present invention; and FIG. 26 is a perspective view of an imaging system module in accordance with the present invention, having auxiliary illumination sources. DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring now to the drawings and the illustrative embodiments depicted therein, an image capture system or imaging or vision system 7 is positioned at a vehicle 8, such as at a rearward exterior portion 8a of the vehicle 8, and is operable to capture an image of a scene occurring interiorly or exteriorly of the vehicle, such as rearwardly of the vehicle, and to display the image at a display or display system 9a of the vehicle which is viewable by a driver or occupant of the vehicle (FIGS. 1 and 2). Imaging system 7 includes a camera module 10, which is mountable on, at or in the vehicle to receive an image of a scene occurring exteriorly or interiorly of the vehicle, and a control 9b that is operable to process images captured by an image sensor 18 of camera module 10. Camera module 10 includes a plastic camera housing 11 and a metallic protective shield or casing 16 (FIGS. 3-12). Camera housing 11 includes a camera housing portion 12 and a connector portion 14, which mate or join together and are preferably laser welded or sonic welded together to substantially seal the housing 11 to substantially limit or prevent water intrusion or other contaminants from entering the housing, as discussed below. Housing 11 of camera module 10 substantially encases a camera or image sensor or sensing device 18 (FIGS. 7, 9-11, 13A, 13B, 14A and 14B), which is operable to capture an image of the scene occurring exteriorly or interiorly of the vehicle, depending on the particular application of camera module 10. Housing 11 also includes a cover portion 20 at an end of camera housing portion 12. Cover portion 20 provides a transparent cover plate 22 which allows the image of the scene exteriorly or interiorly of the vehicle to pass therethrough and into housing 11 to camera 18, and which may be heated to defrost or defog the cover, as discussed below. Camera module 10 may include the protective shield 16, which substantially encases camera housing portion 12 and a portion of connector portion 14, thereby substantially limiting or reducing electronic noise going into or out of the camera module and/or protecting the plastic housing 11 from damage due to impact or the like with various items or debris that may be encountered at the exterior of the vehicle. Camera module 10 provides a camera or image capture device 18 for capturing an image of a scene occurring exteriorly or interiorly of a vehicle. The captured image may be communicated to a display or display system 9a which is operable to display the image to a driver of the vehicle. The camera or imaging sensor 18 useful with the present invention may comprise an imaging array sensor, such as a CMOS sensor or a CCD sensor or the like, such as disclosed in commonly assigned U.S. Pat. Nos. 5,550,677; 5,670,935; 5,796,094; and 6,097,023, and U.S. patent application, Ser. No. 09/441,341, filed Nov. 16, 1999 by Schofield et al. for VEHICLE HEADLIGHT CONTROL USING IMAGING SENSOR (Attorney Docket DON01 P-770), which are hereby incorporated herein by reference. Camera module 10 and imaging sensor 18 may be implemented and operated in connection with various vehicular vision systems, and/or may be operable utilizing the principles of such other vehicular systems, such as a vehicle headlamp control system, such as the type disclosed in U.S. Pat. Nos. 5,796,094; 6,097,023; 6,320,176; and 6,559,435, and U.S. patent application, Ser. Nos. 09/441,341, filed Nov. 16, 1999 by Schofield et al. for VEHICLE HEADLIGHT CONTROL USING IMAGING SENSOR (Attorney Docket DON01 P-770); and Ser. No. 10/427,146, filed Apr. 30, 2003 by Schofield et al. for VEHICLE HEADLIGHT CONTROL USING IMAGING SENSOR (Attorney Docket DON01 P-1091), which are all hereby incorporated herein by reference, a rain sensor, such as the types disclosed in commonly assigned U.S. Pat. Nos. 6,353,392; 6,313,454; and/or 6,320,176, which are hereby incorporated herein by reference, a vehicle vision system, such as a forwardly, sidewardly or rearwardly directed vehicle vision system utilizing principles disclosed in U.S. Pat. Nos. 5,550,677; 5,670,935; 5,760,962; 5,877,897; 5,949,331; 6,222,447; 6,302,545; 6,396,397; 6,498,620; 6,523,964; 6,611,202; and 6,201,642, and/or in U.S. patent application, Ser. Nos. 09/199,907, filed Nov. 25,1998 by Bos et al. for WIDE ANGLE IMAGE CAPTURE SYSTEM FOR VEHICLE (Attorney Docket DON01 P-676); Ser. No. 10/372,873, filed Feb. 24, 2003 by Schofield et al. for VEHICLE IMAGE CAPTURE SYSTEM (Attorney Docket DON01 P-1077); Ser. No. 10/011,517, filed Nov. 5, 2001 by Bos et al. for INTERIOR REARVIEW MIRROR SYSTEM INCLUDING A FORWARD FACING VIDEO DEVICE (Attorney Docket DON01 P-934); Ser. No. 10/324,679, filed Dec. 20, 2002 by Schofield et al. for VEHICULAR VISION SYSTEM (Attorney Docket DON01 P-1059); Ser. No. 10/047,901, filed Jan. 14, 2002 by Bos et al. for VEHICLE IMAGING SYSTEM WITH ACCESSORY CONTROL (Attorney Docket DON08 P-949); Ser. No. 10/643,602, filed Aug. 19, 2003 by Schofield et al. for VISION SYSTEM FOR A VEHICLE INCLUDING IMAGING PROCESSOR (Attorney Docket DON01 P-1087); and Ser. No. 10/010,862, filed Dec. 6, 2001 by Bos for PLASTIC LENS SYSTEM FOR VEHICLE IMAGING SYSTEM (Attorney Docket DON01 P-954), which are all hereby incorporated herein by reference, a trailer hitching aid or tow check system, such as the type disclosed in U.S. patent application, Ser. No. 10/418,486, filed Apr. 18, 2003 by McMahon et al. for VEHICLE IMAGING SYSTEM (Attorney Docket DON01 P-1070), which is hereby incorporated herein by reference, a reverse or sideward imaging system, such as for a lane change assistance system or lane departure warning system, such as the type disclosed in U.S. patent application, Ser. No. 10/427,051, filed Apr. 30, 2003 by Pawlicki et al. for OBJECT DETECTION SYSTEM FOR VEHICLE (Attorney Docket DON01 P-1075), which is hereby incorporated herein by reference, a traffic sign recognition system, a system for determining a distance to a leading or trailing vehicle or object, such as a system utilizing the principles disclosed in U.S. Pat. No. 6,396,397, which is hereby incorporated herein by reference, and/or the like. Typically, cameras are best suited for uniform lighting conditions, and typically have a dynamic range of approximately 60 to 70 dB. The lighting extremes which are encountered in automotive applications create challenges for these cameras. For example, a single frame captured by the camera may include sunlight reflecting off concrete pavement and a dark shadow cast by the vehicle or other object. In such a situation, standard dynamic range cameras are limited in their ability to display usable images in both portions of the frame. Either the light area may be washed out, or the shadowed area may be black or darkened. Optionally, and preferably, camera 18 may comprise an extended dynamic range camera, which may have a dynamic range of greater than approximately 100 dB, and preferably approximately 100 to 120 dB. The linear dynamic range of the camera or sensor may be extended to above 100 dB by programming a non-linear response curve that generally matches the response of the human eye. By providing such an extended dynamic range camera, the camera module may provide an image which is readable and not washed out or darkened in both the highly lighted areas and the dark areas of each frame of the image captured by the camera. Such a camera thus may provide an image to the display or display system which is readable in both the light and dark regions of each frame. In a preferred embodiment, the extended dynamic range camera may provide a dynamic range of approximately 62 dB in a linear mode and approximately 110 dB in a non-linear mode. The camera or sensor may have a sensitivity of approximately 5 V/lux.s (if the sensor comprises a monochrome sensor) or approximately 2.7 V/lux.s (if the sensor comprises a color sensor), and may be operable at a frame rate of approximately 30 frames per second. For example, the camera or sensor may comprise a LM9618 Monochrome CMOS Image Sensor or a LM9628 Color CMOS Image Sensor, both of which are commercially available from National Semiconductor. Other suitable cameras or sensors may otherwise be implemented with the camera module, without affecting the scope of the present invention. Although shown at a rear portion of a vehicle, camera 18 and camera module 10 may be positioned at any suitable location on the vehicle, such as within a rear panel or portion of the vehicle, a side panel or portion of the vehicle, a license plate mounting area of the vehicle, an exterior mirror assembly of the vehicle, an interior rearview mirror assembly of the vehicle or any other location where the camera may be positioned and oriented to provide the desired view of the scene occurring exteriorly or interiorly of the vehicle. The camera module of the present invention is particularly suited for use as an exterior camera module. However, the camera module may be positioned at an interior portion of the vehicle, such as at or in an interior rearview mirror assembly or accessory module at or near an interior rearview mirror assembly, to provide an image of an interior scene or of an exterior scene through a window or windshield of the vehicle, without affecting the scope of the present invention. The image captured by the camera may be displayed at a display screen or the like positioned within the cabin of the vehicle, such as at an interior rearview mirror assembly (such as disclosed in U.S. patent application, Ser. No. 09/793,002, filed Feb. 26, 2001 by Schofield et al. for VIDEO MIRROR SYSTEMS INCORPORATING AN ACCESSORY MODULE (Attorney Docket DON01 P-869), which is hereby incorporated herein by reference), or elsewhere at or within the vehicle cabin, such as by using the principles disclosed in U.S. Pat. Nos. 5,550,677; 5,670,935; 5,796,094; 6,097,023 and 6,201,642, and/or in U.S. patent application, Ser. No. 09/199,907, filed Nov. 25, 1998 by Bos et al. for WIDE ANGLE IMAGE CAPTURE SYSTEM FOR VEHICLE (Attorney Docket DON01 P-676), which are hereby incorporated herein by reference. As best shown in FIGS. 7 and 9-12, camera housing portion 12 includes a generally cylindrical portion 12a extending outwardly from a base portion 12b. Camera portion 12 comprises a molded plastic component and may include a pair of heater terminals or elements 30a, 30b insert molded within and/or along the walls of cylindrical portion 12a, as discussed below. Cylindrical portion 12a receives a lens or optic system 24 therein, which functions to focus the image onto camera or sensor 18, which is positioned at a circuit board 26 mounted within the base portion 12b of camera housing portion 12. Lens system 24 is positioned within cylindrical portion 12a of camera portion 12 so as to receive light from the exterior or interior scene through cover 22 at end 12c of camera portion 12. Lens system 24 is mounted to, such as via threaded engagement with, camera cover or housing 28, which functions to substantially cover or encase camera or sensor 18 to substantially prevent or limit incident light from being received by camera 18 and interfering with the image received by camera 18 through cover 22 and lens system 24. The lens system 24 may be any small lens or lens system which may focus an image of the scene exteriorly of the camera module onto the camera or image sensor 18, such as, for example, the types disclosed in U.S. Pat. No. 6,201,642; and/or in U.S. patent application, Ser. No. 10/010,862, filed Dec. 6, 2001 by Bos for PLASTIC LENS SYSTEM FOR VEHICLE IMAGING SYSTEM (Attorney Docket DON01 P-954), which are hereby incorporated herein by reference. The lens system 24 may provide a wide-angle field of view, such as approximately 120 degrees or more. Cover portion 20 is mounted at an outer end 12c of camera housing portion 12 opposite from base portion 12b, as shown in FIGS. 7 and 9-11. Cover portion 20 includes an outer circumferential ring or cover retainer 20a, which engages an outer surface of transparent cover 22 and functions to retain transparent cover 22 in position at the end 12c of the cylindrical portion 12a of camera receiving portion 12. Preferably, circumferential ring 20a is laser welded or sonic welded or otherwise joined or bonded to outer end 12c of cylindrical portion 12a of camera receiving portion 12, as discussed below. The laser or sonic welding of the seam substantially seals and secures cover portion 20 onto camera receiving portion 12, and may limit or substantially preclude any water intrusion or contaminant intrusion into the camera receiving portion at the outer end 12c. Preferably, an inner surface 22a of transparent cover 22 includes a transparent conductive coating for heating the cover, as also discussed below. In the illustrated embodiment, base portion 12b is generally square and defines a generally square mating edge 12e around the base portion 12b for mating and securing to a corresponding edge 14g of connector portion 14, as discussed below. Base portion 12b receives circuit board 26 and camera 18 therein, while a camera housing or shield 28 and lens or lens system 24 extend into cylindrical portion 12a of camera portion 12 to receive the image through transparent cover 22. Connector portion 14 of housing 11 is a molded plastic component and includes a connector terminal or connector 14a, such as a multi-pin snap-on connector or the like, extending from a base portion 14b. Base portion 14b is formed (such as in a square shape as shown in the illustrated embodiment) to substantially and uniformly mate or connect to base portion 12b of camera housing 12, as can be seen with reference to FIGS. 7 and 9-11. The base portions 12b and 14b mate together and define a pocket or space for receiving and securing circuit board 26 therein. Base portions 14b and 12b may be laser welded or sonic welded together at their mating joint or connection 13. Laser or sonic welding of the joint melts the plastic edges or seams together to substantially hermetically seal housing 11 to prevent water intrusion or other contaminant intrusion into housing 11 of camera module 10. Optionally, and less desirably, the base portions may be otherwise joined or substantially sealed together (such as via suitable adhesives and/or sealants). The module may optionally include a vented portion or semi-permeable membrane to vent the module, as discussed below. The base portions 12b and 14b may further include mounting tabs or flanges 12d, 14f, which extend outwardly from base portion 12b, 14b. Mounting tabs 12d, 14f are generally aligned with one another when the base portions are secured together and include an aperture therethrough for mounting the camera module 10 at or to the vehicle via suitable fasteners or the like (not shown). Although shown as having generally square-shaped mating portions, connector portion 14 and camera portion 12 may have other shaped mating portions or surfaces, without affecting the scope of the present invention. Multi-pin connector 14a extends from base portion 14b and includes a plurality of pins or terminals 14c for electrically connecting camera module 10 with a connector (not shown) of the vehicle. For example, one end 14d of terminals 14c may connect to circuit board 26, while the other end 14e of terminals 14c connects to the corresponding connector of the vehicle. The corresponding connector may partially receive the ends 14e of pins or terminals 14c at multi-pin connector 14a and may snap together with multi-pin connector 14a via a snap connection or the like. As best shown in FIGS. 15A, 15C and 15D, ends 14d of terminals 14c protrude or extend from connector portion 14, such that the ends 14d may be received within corresponding openings or apertures 26c in circuit board 26 when housing portion 11 is assembled, as discussed below. As shown in FIGS. 3-11, connector portion 14 may provide a generally straight multi-pin connector extending longitudinally from the base portion of the housing 11. However, other shapes of connectors, such as angled connectors or bent connectors or the like, such as a 90 degree angle connector portion 14′ of a camera module 10′ (FIGS. 17A-E), discussed below, may be implemented, depending on the particular application of the camera module, without affecting the scope of the present invention. Optionally, camera module 10 may comprise a substantially hermetically sealed module, such that water intrusion into the module is limited or substantially precluded. Base portion 12b of camera housing portion 12 and base portion 14b of connector portion 14 are correspondingly formed so as to substantially mate or join together at their mating seam 13, whereby the portions may be laser welded or sonic welded together or otherwise joined, while cover portion 20 is also laser welded or sonic welded or otherwise secured and substantially sealed at the opposite end 12c of camera portion 12, in order to substantially seal the camera housing. Laser or sonic welding techniques are preferred so as to join the materials at a state where they are able to re-flow, either via heat, vibration or other means, such that the materials re-flow and cross-link and become a unitary part. Such joining results in a substantially hermetically sealed camera module. Additionally, the pores in the plastic as well as any voids around the insert molded pins and stampings may be sealed with a Loctite material or other suitable sealing material, to further limit or substantially preclude entry of water droplets and/or water vapor into the housing of the substantially sealed module. Optionally, or alternately, the camera module of the present invention may comprise a vented module, which allows for water vapor to enter and/or exit the housing, while substantially precluding water droplets and the like from entering the housing. The camera portion 12 or connector portion 14 may include a semi-permeable ventilation portion or membrane 15 (FIG. 10), which preferably comprises a material or membrane which is at least partially permeable to water vapor and/or is porous enough to allow for ventilation of water vapor, but does not allow water droplets to pass therethrough, such that water vapor may enter and exit the housing 11, while water droplets and the like are kept outside the housing 11. For example, the ventilation portion 15 may comprise a Gore-Tex material or the like. In such applications where the module comprises a vented module and includes a ventilation portion, it is not necessary that the seams of the housing be laser welded or sonic welded, since the substantially hermetic sealing of the seams of the module would not be critical when the module is vented. Optionally, desiccant material, such as silica gel or the like, may be included in the housing to absorb moisture which may be present within the housing. Camera housing portion 12 also includes a pair of heating terminals 30a, 30b which extend from within base portion 12b to outer end 12c substantially along/or within the walls of cylindrical portion 12a. Preferably, the terminals 30a, 30b are insert molded within the cylindrical wall of camera portion 12a. As shown in FIGS. 7 and 12D, the ends 30c of terminal portions 30a, 30b extend downward into base portion 12b of camera receiving portion 12, for connection to circuit board 26, as discussed below. The opposite ends 30d of terminals 30a, 30b extend radially inward at outer end 12c of cylindrical portion 12a and may provide arcuate or semicircular contacts at inner surface 22a of transparent cover 22 (FIGS. 7, 12B and 12C). A power or positive terminal 30a may be insert molded along and at least partially within the cylindrical portion 12a and positioned generally along an interior portion of the cylindrical portion 12a, while a ground or negative terminal 30b is insert molded along and partially within cylindrical portion 12a and positioned along an exterior wall or surface of the cylindrical portion 12a (as can be seen in FIGS. 7 and 12D). The exteriorly positioned ground terminal 30b may contact the metallic protective shield 16, discussed below, to ground the shield to the heating device and/or camera module. Heating device 30 functions to heat inner surface 22a of transparent cover 22, in order to defrost or defog the cover 22. Heating device 30 may also function to heat the inside or interior compartment of housing 11, in order to maintain the temperature within the housing above a threshold temperature to further limit or substantially preclude moisture from condensing within the camera housing. This is especially useful when implemented in a vented module having a semi-permeable membrane or portion, whereby the heater may generate heat to dry out and drive out any moisture within the camera body compartment. The heated camera module thus may substantially preclude moisture from condensing within the module, since the water vapor would otherwise condense on the coldest surface available within the module. The power heater terminal 30a may be connected to or in communication with the vehicle battery or other power source and may be energizable to provide electrical current to inner surface 22a of transparent cover 22, while the ground terminal 30b provides a ground connection for the heating device. Energization of terminal 30a thus causes electrical current or electrons to flow across the inner surface 22a of cover 22 to ground terminal 30b. Preferably, inner surface 22a of transparent cover 22 includes a transparent conductive coating or layer, such as an indium tin oxide (ITO) coating or a doped tin oxide coating or the like, such as the types of layers or coatings used in electro-optic or electrochromic mirror technology and as disclosed in U.S. Pat. Nos. 5,140,455; 5,151,816; 6,178,034; 6,154,306; 6,002,544; 5,567,360; 5,525,264; 5,610,756; 5,406,414; 5,253,109; 5,076,673; 5,073,012; 5,117,346; 5,724,187; 5,668,663; 5,910,854; 5,142,407 and 4,712,879, which are hereby incorporated herein by reference. Preferably, the conductive coating or layer provides a resistance of less than approximately 80 ohms per square, and more preferably less than approximately 20 ohms per square. The conductive coating generates heat as electrons or electricity flow from contact 30d of power terminal 30a across surface 22a to contact 30d of ground terminal 30b. The contacts 30d are spaced apart at generally opposite sides of the transparent cover 22 and provide for generally uniform and thorough heating of inner surface 22a when electricity is applied to heating terminal 30a As can be seen in FIGS. 12B and 12C, contacts 30d of terminals 30a, 30b are preferably semicircular or half moon shaped contacts to extend substantially across each side of the cover 22, without interfering with the central region of the cover through which the scene may be viewed by the camera and lens. Preferably, circuit board 26 of camera module 10 also includes a heater circuit for controlling the heater device 30 and heater terminals 30a, 30b in response to a temperature sensor (not shown). The heater circuit may be operable to actuate the heater device 30, such as via energizing heater terminal 30a, when the temperature at, within or near the camera module (or elsewhere at, in or on the vehicle) drops to a threshold temperature. The control or circuit is also operable to deactivate the heating device at a second predetermined threshold temperature. The heating device thus is operable via a thermostatic circuit which may activate and deactivate the heating device to heat the transparent cover 22 and/or the interior compartment of the housing when the temperature is detected to be low enough to warrant such activation. Such a thermostatic circuit may be operable to activate the heater elements when it is most desirable to heat the transparent cover and/or the interior of the housing and, thus, may limit or substantially preclude fogging or freezing of cover 22 and/or moisture condensing within the housing, while limiting or substantially precluding operation of the heating device in circumstances or situations when heat is not required on the transparent cover or in the housing. As best shown in FIGS. 13A, 13B, 14A and 14B, circuit board 26 includes a camera mounting circuit board 26a, which is connected to a connector receiving circuit board 26b via a multi-wire ribbon wire 27 or the like. Camera mounting circuit board 26a is mounted or secured to the base portion 12b of camera portion 12, while connector circuit board 26b is mounted or secured to the base portion 14b of connector portion 14. Camera or image sensor 18 is mounted at a surface of camera circuit board 26a, and is substantially encased at circuit board 26a by camera cover 28 and lens 24 (FIGS. 7 and 9-11). As shown in FIGS. 7, 13A and 14A, camera circuit board 26a includes a pair of apertures 26c for receiving ends 30c of heating terminals 30a, 30b. Likewise, connector circuit board 26b includes a plurality of openings or apertures 26d for receiving ends 14d of connector terminals 14c therethrough (FIGS. 7, 10, 11 and 13A). The ends of the pins or terminals may be soldered in place in their respective openings. As shown in FIGS. 9, 11 and 14B, circuit board 26 is folded at ribbon wire 27, such that circuit board 26a generally overlaps circuit board 26b when they are positioned within the base portions 12b, 14b of the camera housing. The circuit board 26 may thus fold to an open position after the separate boards 26a, 26b are secured within their respective base portions of the housing to facilitate soldering of the connector terminals or heater terminals at the respective circuit boards. After all of the connections are made, the housing may be folded to its closed position and laser welded or sonic welded together or otherwise joined or bonded together to substantially seal the circuit board within the housing. Optionally, the exterior surface 22b of cover 22 (which may be exposed to the atmosphere exterior of the camera module) may be coated with an anti-wetting property such as via a hydrophilic coating (or stack of coatings), such as is disclosed in U.S. Pat. Nos. 6,193,378; 5,854,708; 6,071,606; and 6,013,372, the entire disclosures of which are hereby incorporated by reference herein. Also, or otherwise, the exterior or outermost surface 22b of cover 22 may optionally be coated with an anti-wetting property such as via a hydrophobic coating (or stack of coatings), such as is disclosed in U.S. Pat. No. 5,724,187, the entire disclosure of which is hereby incorporated by reference herein. Such hydrophobic property on the outermost surface of the cover can be achieved by a variety of means, such as by use of organic and inorganic coatings utilizing a silicone moeity (for example, a urethane incorporating silicone moeities) or by utilizing diamond-like carbon coatings. For example, long-term stable water-repellent and oil-repellent ultra-hydrophobic coatings, such as described in PCT Application Nos. WO0192179 and WO0162682, the entire disclosures of which are hereby incorporated by reference herein, can be disposed on the exterior surface of the cover. Such ultra-hydrophobic layers comprise a nano structured surface covered with a hydrophobic agent which is supplied by an underlying replenishment layer (such as is described in Classen et al., “Towards a True ‘Non-Clean’ Property: Highly Durable Ultra-Hydrophobic Coating for Optical Applications”, ECC 2002 “Smart Coatings” Proceedings, 2002, 181-190, the entire disclosure of which is hereby incorporated by reference herein). In the illustrated embodiment, camera module 10 includes a protective shield or casing 16 which partially encases the plastic housing 11 and functions to limit or reduce electronic noise which may enter or exit camera module 10 and may protect the plastic housing from damage from impact of various items or debris which the camera module may encounter at the exterior portion of the vehicle. The protective shield or casing 16 includes a pair of casing portions 16a (one of which is shown in FIGS. 16A-16E). Each of the casing portions 16a partially encases about half of the plastic housing 11 of camera module 10 and partially overlaps the other of the casing portion 16a, to substantially encase the plastic housing within protective shield 16. Each of the portions 16a includes a slot 16b for receiving the mounting tabs 12d, 14f therethrough for mounting the camera module at the desired location at the vehicle. Each casing portion 16a includes overlapping portions 16c which overlap an edge of the other casing portion 16a to assemble the casing 16 around the plastic housing. The casing portions 16a may be welded, crimped, adhered, banded, or otherwise joined or secured together about the plastic housing 11, in order to encase the housing 11. Preferably, protective shield 16 comprises a metallic shield and contacts ground terminal 30b of heating device 30 at the exterior surface of the cylindrical portion 12a of camera receiving portion 12 and, thus, may be grounded to the heating device and/or the camera module or unit via the ground terminal 30b, as can be seen with reference to FIG. 7. Protective shield 16 may comprise a stamped metal shielding or may be formed by vacuum metalizing a shield layer over the plastic housing 11, or may comprise a foil or the like, without affecting the scope of the present invention. With reference to FIGS. 17A-17E, a camera module 10′ is shown which includes a connector portion 14′ of a housing 11′ which provides for a 90 degree bend in the connector pins or terminals 14c′ to accommodate different mounts or connections to a connector of the vehicle. Other bends or shapes of the molded connector portion may be implemented without affecting the scope of the present invention. The other components of camera module 10′ are substantially similar to the respective components of camera module 10, discussed above, such that a detailed discussion of those components will not be repeated herein. The common components are shown in FIGS. 17A-17E with the same reference numbers as assigned to the respective components of camera module 10 of FIGS. 1-16. Therefore, the present invention provides a sealed camera module which may provide a substantially watertight and substantially hermetically sealed housing about a camera or image sensor of the camera module. The housing components may be laser welded or sonic welded together which substantially seals the plastic housing and substantially precludes water intrusion or the like into the housing at the seams or mating portions of the housing. Because the plastic housing of the camera module of the present invention may be laser welded or sonic welded together to substantially seal the housing, the housing may provide an economical and rugged, environmentally resilient and protective housing for the camera or sensor and circuit board. The unitary housing and connector also makes it easy to install and connect the camera module to a vehicle connector. Alternately, the camera module of the present invention may comprise a vented camera module, where the housing includes a semi-permeable ventilation or venting portion, such as a Gore-Tex assembly, area or patch or the like, which allows for ventilation of water vapor into and out from the housing, while substantially precluding entry of water droplets or dirt or other contaminants or the like into the housing. The plastic vented module of the present invention thus may also provide an economical and rugged, environmentally resilient and protective housing for the camera or sensor and circuit board. Additionally, the camera module of the present invention may include a heating device which functions to heat a transparent conductive coating on a transparent cover of the housing, so as to provide heat to the cover to defrost or defog the cover. The heater elements may be insert molded within the plastic housing of the camera module and may plug into a circuit board received within the housing as the camera module is assembled. Preferably, the heating device may be operable in response to a temperature sensor, such that the heating device may be activated when the temperature drops to a threshold temperature and then deactivated after the temperature has been elevated to a second higher threshold temperature. The heating device is thus automatically operable in low temperature levels when it may be desirable to activate the heating device. The heating device may be activated to defrost or defog the transparent cover of the camera module and/or to heat the interior chamber of the camera module to limit or substantially preclude moisture condensing therein. Heating the interior compartment of the camera module may dry out any moisture within the module and may limit or substantially preclude condensation from forming within the module. In applications where the camera module comprises a vented camera module, the heat generated within the vented camera module may also drive out water vapor through the semi-permeable ventilation area to further limit or substantially preclude water vapor from condensing within the camera module. Referring now to FIGS. 18-20, a camera housing device 110 may house or contain a camera or imaging device 116 and protect the camera from exposure to the elements in applications where the camera may be positioned at a vehicle 8 (FIG. 18) for viewing an area or scene exterior of the vehicle. The camera housing device 110 may be positioned at least partially within an opening 8b at an exterior portion 8a of a vehicle 8 (such as a rearward portion or side portion or elsewhere on the vehicle). The housing device 110 defines a compartment or cavity 114 for receiving camera or imaging device 116 therein and is operable or movable to move the camera or imaging device 116 between a stored position (FIG. 19) and an operational or extended or in-use position (FIG. 20). The camera 116 and compartment 114 are positioned generally inwardly of an outer panel or flap 118 of housing device 110 at the exterior portion 8a of the vehicle 8 when the housing device and camera are in the stored position. As shown in FIG. 19, the outer panel or flap 118 is positioned generally along the exterior portion 8a of the vehicle a and serves as a cover or flap over the opening 8b when housing device 110 is in its stored position. Imaging device 116 may be operable in conjunction with a vision or imaging system of the vehicle, such as a reverse or backup aid system, such as a rearwardly directed vehicle vision system utilizing principles disclosed in U.S. Pat. Nos. 5,550,677; 5,760,962; 5,670,935; 5,760,962; 5,877,897; 5,949,331; 6,222,447; 6,302,545; 6,396,397; 6,498,620; 6,523,964; 6,611,202; and/or 6,201,642, and/or in U.S. patent applications, Ser. No. 09/199,907, filed Nov. 25, 1998 by Bos et al. for WIDE ANGLE IMAGE CAPTURE SYSTEM FOR VEHICLE (Attorney Docket DON01 P-676); Ser. No. 10/372,873, filed Feb. 24, 2003 by Schofield et al. for VEHICLE IMAGE CAPTURE SYSTEM (Attorney Docket DON01 P-1077); Ser. No. 10/011,517, filed Nov. 5, 2001 by Bos et al. for INTERIOR REARVIEW MIRROR SYSTEM INCLUDING A FORWARD FACING VIDEO DEVICE (Attorney Docket DON01 P-934); Ser. No. 10/324,679, filed Dec. 20, 2002 by Schofield et al. for VEHICULAR VISION SYSTEM (Attorney Docket DON01 P-1059); Ser. No. 10/047,901, filed Jan. 14, 2002 by Bos et al. for VEHICLE IMAGING SYSTEM WITH ACCESSORY CONTROL (Attorney Docket DON08 P-949); and Ser. No. 10/643,602, filed Aug. 19, 2003 by Schofield et al. for VISION SYSTEM FOR A VEHICLE INCLUDING IMAGING PROCESSOR (Attorney Docket DON01 P-1087); and Ser. No. 10/010,862, filed Dec. 6, 2001 by Bos for PLASTIC LENS SYSTEM FOR VEHICLE IMAGING SYSTEM (Attorney Docket DON01 P-954), which are hereby incorporated herein by reference, a trailer hitching aid or tow check system, such as the type disclosed in U.S. patent application, Ser. No. 10/418,486, filed Apr. 18, 2003 by McMahon et al. for VEHICLE IMAGING SYSTEM (Attorney Docket DON01 P-1070), which is hereby incorporated herein by reference, or an imaging system that may utilize aspects of other imaging or vision systems, such as the types disclosed in U.S. patent applications, Ser. No. 10/054,633, filed Jan. 22, 2002 by Lynam et al. for VEHICULAR LIGHTING SYSTEM (Attorney Docket DON01 P-962); and Ser. No. 09/793,002, filed Feb. 26, 2001, entitled VIDEO MIRROR SYSTEMS INCORPORATING AN ACCESSORY MODULE (Attorney Docket DON01 P-869), which are hereby incorporated herein by reference. The imaging system includes a control or control system or device that is operable to process images captured by the imaging device 116 and a display 115 (FIG. 1) for displaying the captured images to a driver or occupant of the vehicle. The display may be positioned at an interior portion of the vehicle, such as at an interior rearview mirror assembly of the vehicle or accessory module of the vehicle or the like. The display may comprise a video display screen at a mirror assembly, such as the type disclosed in U.S. provisional applications, Ser. No. 60/439,626, filed Jan. 13, 2003 by Hutzel et al. for MIRROR WITH VIDEO DISPLAY SCREEN (Attorney Docket DON01 P-1061); Ser. No. 60/489,812, filed Jul. 24, 2003 by Hutzel et al. for ACCESSORY SYSTEM FOR VEHICLE (Attorney Docket DON01 P-1100); and Ser. No. 60/492,225, filed Aug. 1, 2003 by Hutzel et al. for ACCESSORY SYSTEM FOR VEHICLE (Attorney Docket DON01 P-1107), which are hereby incorporated herein by reference, or may comprise other types of displays or display systems, such as, for example, a display on demand type of display, such as the types disclosed in commonly assigned U.S. Pat. Nos. 5,668,663 and 5,724,187, and U.S. patent application, Ser. Nos. 10/054,633, filed Jan. 22, 2002 by Lynam et al. for VEHICULAR LIGHTING SYSTEM (Attorney Docket DON01 P-962); and Ser. No. 09/793,002, filed Feb. 26, 2001, entitled VIDEO MIRROR SYSTEMS INCORPORATING AN ACCESSORY MODULE (Attorney Docket DON01 P-869), which are hereby incorporated by reference herein, without affecting the scope of the present invention. The control may also be operable to move the camera housing device between the operational and stored positions. The method of actuation of the housing to move the housing and camera may be accomplished by a motor, such as via a gear or screw mechanism, or by vacuum compressed air or by magnetic or electromagnetic means, such as in the form of a solenoid or the like. Optionally, the camera housing device 110 may be movable to the operational position in response to an engagement of the reverse gear of the vehicle, or in response to an actuation of a backup aid or other reverse viewing system of the vehicle. Optionally, the camera housing may be moved to the operational position in response to a user input or the like, without affecting the scope of the present invention. The camera housing thus allows for occasional use of the camera and may store and protect the camera when the camera is not in use. Imaging device or camera 116 may comprise a camera device or other image capturing device, such as a video camera or sensor, such as a CMOS imaging array sensor, a CCD sensor or the like, such as the types disclosed in commonly assigned, U.S. Pat. Nos. 5,550,677; 5,760,962; 6,097,023 and 5,796,094, which are hereby incorporated herein by reference. Such imaging array sensors comprise an array of photo-sensing pixels to sense light present in the field of view of the sensor. The imaging device 116 may comprise a color sensing imaging device, which includes color filters such that the photo-sensing pixels of the imaging device sense particular colors of light from the scene. Optionally, the imaging device may or may not include an infrared filter to filter or attenuate infrared or near infrared light present in the exterior scene. Optionally, the imaging device may provide an infrared sensing capability to provide enhanced performance of the imaging device during nighttime and/or darkened conditions where the visible light intensity is reduced. Optionally, the housing device may include two separate imaging devices, one for sensing color light for daytime lighting conditions and one for sensing infrared light for nighttime or darkened lighting conditions, as discussed below. Alternately, the control may be operable to selectively switch the imaging sensor between a color mode and a monochromatic mode, such as via utilization of principles described below with respect to imaging system 310. The imaging device may have a lens 117 positioned in front of the sensor, and may utilize aspects of an imaging module of the types described above with respect to the camera modules 10, 10′ of FIGS. 1-17. Housing device 110 mounts or attaches the camera 116 generally at the external flap 118, such that the movement of the external flap between its opened position (FIG. 20) and its closed position (FIG. 19) moves the camera between its operational position and its stored position. The reverse aid camera or imaging device 116 is thus mounted behind the flap 118 such that when the camera is not in use it may be retracted into the vehicle exterior portion or body portion 8a, thereby protecting it from the elements, such as dirt or debris or the like, and keeping the lens 117 relatively clean. The outer flap 118 may partially overlap the edges of the opening 8b in exterior portion 8a of vehicle 8 and may be generally aligned with an outer or exterior surface of the exterior portion to provide a generally flush, finished appearance to the exterior portion 8a when the housing device 110 is in the stored or closed position. As shown in FIGS. 19 and 20, the camera 116 may be mounted in a housing or box or container 119 attached to the flap 118, such that the camera 116 is substantially contained or encased within the compartment 114 defined within the housing 119. The housing device 110 may define compartment or cavity 114 within and between an inner wall or flap 120 and external flap 118, and opposite side walls or flaps 122 (only one side wall shown in FIGS. 19 and 20). The housing 119 of camera housing device 110 may be pivotable about a generally horizontal pivot axis or pin 111 at the exterior portion 8a of the vehicle 8. In the illustrated embodiment, housing device 110 includes a pivot arm or extension 111a extending from inner wall 120. The pivot arm 111a pivotally mounts to a pivot pin 111 and may pivotally move or swing the housing 119 between the stored position and the operational position. The pivot pin or axis 111 may be positioned within the exterior portion 8a of the vehicle 8 and generally adjacent to the edge of the opening 8b in the exterior portion 8a. Optionally, the housing device may be positioned at a side portion of the vehicle (such that the housing may pivot about a generally vertical pivot axis or the like) or at a generally horizontal portion of the vehicle (such that the housing may pivot about a generally horizontal pivot axis and may have an outer flap that is generally horizontal when in its closed orientation, with the camera and housing positioned generally above or below the closed flap, depending on the particular application) or elsewhere on or in the vehicle, without affecting the scope of the present invention. Housing 119 may include a clear or transparent glass or plastic window or panel 124 that at least partially closes the compartment 114 and that is positioned generally in front of the camera or imaging device 116 and covers or generally encases the lens 117 of the camera or imaging device 116. The transparent panel 124 may comprise a visible light transmitting panel that may substantially transmit visible light present in the scene to the imaging sensor 116 within housing 119 and behind transparent panel 124. The transparent panel 124 may comprise a substantially clear or transparent panel to provide protection to the lens and imaging sensor within the housing. Optionally, the transparent panel may comprise or provide an optical lens or may have optical qualities or characteristics or properties, whereby the transparent panel may function to serve or augment the lens of the imaging sensor. Optionally, a wiper blade or wiping or cleaning device 126 may be positioned at the opening 8b of the exterior portion 8a of the vehicle 8 and may engage or wipe the outer surface 124a of the transparent panel 124 as the housing device 110 moves between the stored position and the operational position, in order to brush or clean or wipe debris or dirt or the like from the transparent panel 124. The wiper blade or device 126 may be spring loaded or biased (such as via a flexible spring clip 126a or the like) into engagement or contact with the surface 124a of the window or panel 124 such that as the housing device 110 opens and closes, the wiper 126 engages and wipes and cleans the window 124. The transparent panel 124 thus may comprise a curved or arcuate panel such that the wiping device 126 generally uniformly engages the outer surface of the transparent panel as the housing device is opened and closed. However, the transparent panel may comprise other forms (and may be a generally flat panel), whereby the wiping device may engage only a desired portion of the panel or may be biased more toward the panel to maintain engagement of the wiping device with the panel during movement of the housing device. Optionally, a washer jet 128 may also be positioned at or near the opening 8b and may be operable to spray washer fluid or the like toward the panel or window 124 to clear dirt from the panel or window and to limit or prevent scratching of the window by the wiper. Optionally, the housing device 110 may include a heating element that is operable to heat the transparent panel or window 124 to reduce moisture that may be present on the window. For example, window 124 may be heated by conductive strips embedded in the window, or surface mounted conductive strips, or ITO coatings or similar conductive or semi-conductive coatings or the like, such as described above with respect to camera module 10, 10′. The heater thus may heat the window to limit or substantially avoid condensation obscuring the field of view of the camera. Optionally, condensation may be limited by the use of a desiccant substance or by venting the enclosure or the like, without affecting the scope of the present invention. Optionally, the exterior surface 124a of window 124 may be coated with an anti-wetting property such as via a hydrophilic coating (or stack of coatings), such as is disclosed in U.S. Pat. Nos. 6,193,378; 5,854,708; 6,071,606; and 6,013,372, the entire disclosures of which are hereby incorporated by reference herein. Also, or otherwise, the exterior surface 124a of window 124 may optionally be coated with an anti-wetting property such as via a hydrophobic coating (or stack of coatings), such as is disclosed in U.S. Pat. No. 5,724,187, the entire disclosure of which is hereby incorporated by reference herein. Such hydrophobic property on the outermost surface of the window or panel can be achieved by a variety of means, such as by use of organic and inorganic coatings utilizing a silicone moeity (for example, a urethane incorporating silicone moeities) or by utilizing diamond-like carbon coatings. For example, long-term stable water-repellent and oil-repellent ultra-hydrophobic coatings, such as described in PCT Application Nos. WO0192179 and WO0162682, the entire disclosures of which are hereby incorporated by reference herein, can be disposed on the exterior surface of the window. Such ultra-hydrophobic layers comprise a nano structured surface covered with a hydrophobic agent which is supplied by an underlying replenishment layer (such as is described in Classen et al., “Towards a True ‘Non-Clean’ Property: Highly Durable Ultra-Hydrophobic Coating for Optical Applications”, ECC 2002 “Smart Coatings” Proceedings, 2002, 181-190, the entire disclosure of which is hereby incorporated by reference herein). In some applications, it may be advantageous and desirable to add additional illumination to the exterior scene being captured by the camera. Accordingly, a camera housing device 110′ may house or contain an imaging device or camera 116 and an illumination source or auxiliary light 130 (FIG. 21) that is operable to direct illumination toward the field of view of the camera 116. The illumination source 130 may provide visible light, infrared or near infrared light or may be pulsed to provide pulsed infrared or near infrared light. The auxiliary light 130 may be fixedly positioned on the external bezel portion of the camera housing or of the exterior portion of the vehicle, or optionally, and preferably, may be positioned within the housing and as part of the camera housing device or assembly (such as shown in FIG. 21). In this way, the panel 125 in front of the illumination device 130 may also be cleaned by the same operation or wiper 126 that cleans the transparent panel 124′ in front of the camera 116. Under some conditions, the light from the auxiliary illumination source 130 may be reflected, piped or refracted in or along the compartment and/or transparent panel in such a way that it may interfere with the image captured by the camera. Such interference may be avoided by splitting the clear window (as shown in FIG. 21) such that there is a window or panel 124′ in front of the camera and a second window or panel or section 125 in front of the illumination source 130. Optionally, a divider or separating wall or panel or baffle 132 may be positioned between the compartments 114a, 114b that contain the camera 116 and illumination source 130, respectively. In the illustrated embodiment, the camera transparent panel 124′ is substantially flat or planar, while the light transparent panel 125 is curved or arcuate. However, the transparent panels 124′, 125 may be other shapes, without affecting the scope of the present invention. The separate panels and baffle provide a non-continuous path for the light to travel, so that the light will not have an adverse affect on the images being captured, while still providing for the external surface or surfaces of the panel or panels to be cleaned by the same wiper device. Optionally, by splitting the window into two panels 124′, 125, the panel 125 covering the auxiliary light may be colored, such as red, to improve the appearance of the product on the vehicle. The camera housing device 110′ is otherwise substantially similar to camera housing device 110, discussed above, such that a detailed discussion of the camera housing device will not be repeated herein. Optionally, to improve the performance of the camera, the light level or intensity of the light emitted by the auxiliary light may be monitored by a sensor or device or control, and a control circuit may be used to adjust the camera for different light levels. Such a camera adjustment system would enhance the performance of the camera over a wide range of light conditions, and may also be used to control the auxiliary light if desired. Optionally, when the camera housing is in the closed position, the camera and the auxiliary light may be at least occasionally turned on to illuminate the enclosed cavity and to capture an image of the illuminated enclosed cavity and transparent window. The enclosed cavity provides a known image, and the images captured by the camera in this orientation may be used to examine the window for condensation, dirt or other abnormalities. If condensation is detected on the window, a heater or heating mechanism may be activated to dry or evaporate the moisture from the window. The camera thus may be used to control the heaters that are used to remove condensation from the window. Optionally, if heating the window or cleaning the window does not alleviate a detected abnormality (such as if the same abnormality is detected after two or more openings and closings of the housing device), the control may provide an indication to a user of the imaging system that the transparent window may need to be checked or replaced (in case the abnormality detected is a chip or scratch or crack or the like that may adversely effect the performance of the imaging system). Because the camera housing device is adjustable and may move the camera, the camera housing device of the present invention may provide the ability to change the field of view. For example, the camera can be moved to the furthest out or fully extended position for an initial approach to a parking zone or target zone or area. As the vehicle further enters the parking zone, the camera can be adjusted or moved to a more vertical angle (by pivoting or moving the housing device partially toward the closed position) to display the proximity of the bumper to any obstacle in the exterior scene. Such an adjustment of the camera position or orientation may also be combined with a change or adjustment of the lens configuration, such as by using a longer focal length for the initial approach (which may provide a less distorted view or image) and a wider angle configuration for the close range viewing to provide a wider field of view to the driver of the vehicle during the back up or reverse driving or maneuvering of the vehicle. Also, by using the folding adjustment of the camera housing device to adjust the position of the camera, the housing device and camera may be adjustable to provide a different view of the area behind the vehicle. The control of the imaging system may then be operable to process images captured in each of the views and may compare the images to determine distances to objects detected in the exterior scene (such as by utilizing principles disclosed in U.S. Pat. No. 6,396,397; and/or in U.S. patent application, Ser. No. 10/427,051, filed Apr. 30, 2003 by Pawlicki et al. for OBJECT DETECTION SYSTEM FOR VEHICLE (Attorney Docket DON01 P-1075), which are hereby incorporated herein by reference). By electronic comparison of the images captured between two positions of the camera (capturing at least one image in each of the two views), a distance map can be produced. Such a distance map may then be used to provide additional information about the exterior scene to the driver of the vehicle. Optionally, the housing may not be restricted to one camera and may instead house or include two cameras for different imaging situations. For example, a standard color camera could be used for daylight conditions, while an infrared camera may be used for night or darkened conditions. The infrared or night camera may comprise a CMOS camera or the like without color or infrared filtering, such that it may be highly sensitive to infrared light that is present in the visibly darkened scene. The control may selectively activate the appropriate camera or imaging sensor in response to the ambient light level or intensity present at the exterior scene, such as in response to an ambient light sensor or in response to a light detection by one or both of the imaging sensors or the like. When the night camera is operated or used, the control may also activate (such as continuously activate or pulse) an infrared or near infrared illumination source at the exterior portion of the vehicle (such as within the compartment of the housing device, as discussed above). Optionally, a single camera or imaging sensor may be switched between a color mode and a monochromatic mode (such as described below with respect to imaging system 310), and an infrared illumination source may be activated when in the monochromatic mode, to enhance the performance of the camera or imaging sensor in various lighting conditions. Although shown as being positioned at a rearward portion of a vehicle, the camera housing device of the present invention may be positioned elsewhere on the vehicle, such as a forward portion of the vehicle or a sideward portion of the vehicle or a roof portion of the vehicle or the like, without affecting the scope of the present invention. Also, although the camera housing device is shown as being mounted on a nearly vertical body portion of the vehicle, the camera housing device may be mounted or positioned at a nearly horizontal surface (such as may be found in the top of a number plate applique or the like), without affecting the scope of the present invention. In such a horizontal mounting application, the flap of the housing device may drop down to expose the clear window and to move the camera into its operational position. Referring now to FIGS. 22 and 23, a camera housing device 210 holds or contains a camera or imaging device 216 and is movably mounted to an exterior portion 8a of a vehicle. The housing device 210 is movable to move the camera 216 (and associated lens 217) between a stored position (FIG. 22) and an operational position (FIG. 23). Housing device 210 includes a housing portion 219 that defines the cavity or compartment 214 within an outer panel or flap 218, an inner panel 220 and side panels 222 (one side panel is shown in FIGS. 22 and 23). A transparent cover 224 may close a portion of the cavity and may be positioned generally in front of the imaging device, such that imaging device has a field of view through the transparent window or panel and toward the exterior scene, as discussed above. Housing device 210 is generally linearly slidable relative to the exterior portion 8a of the vehicle (such as via a linear motor, an electromagnetic device or solenoid, a pneumatic device and/or the like) to extend outward from the exterior portion of the vehicle when in the operational position, as shown in FIG. 23. The housing device 210 thus may be generally linearly moved outward and inward relative to the vehicle portion 8a Accordingly, the transparent panel 224 may be a substantially flat or planar panel, such that the wiper device 226 (such as a wiper blade or the like on a spring or biasing member or the like 226a) may engage and wipe the surface 224a of the panel 224 as the panel is moved along adjacent to the wiper device 226. Optionally, the housing device 210 may be generally tubular or even generally cylindrical in shape, such that the transparent panel is curved, while the wiper device is correspondingly curved to substantially uniformly engage the curved or tubular transparent panel as the housing device is moved between the stored and operational positions. The wiping motion of the wiper on the transparent window or panel may thus be achieved by making the camera housing device a generally tubular construction that slides in and out in a generally linear motion, whereby the wiper can then clean the transparent window as the housing device moves in and out. The housing device 210 may otherwise be substantially similar to the housing device 110, 110′, discussed above, such that a detailed discussion of the housing device will not be repeated herein. Therefore, the present invention provides a camera housing device that contains a camera and lens of an imaging system at or partially within an exterior portion of a vehicle. The camera housing device is movable or adjustable to move the camera between an operational position and a stored position. The camera thus may be positioned in a stored position within an exterior portion of the vehicle when not in use. The exterior panel of the camera housing may provide an exterior cover at the exterior portion of the vehicle to protect the camera and lens from the elements when they are not in use. The housing device may include a transparent panel that substantially encloses the camera and lens within the housing; The housing device may also include a panel cleaning device that may clean the transparent panel to limit or substantially preclude dirt buildup or debris on the panel that may adversely effect the performance of the camera and thus of the imaging system. Referring now to FIGS. 24-26, an image capture system or imaging or vision system 310 is positioned at an exterior portion of a vehicle, such as at a rearward portion 8a of the vehicle 8 (FIGS. 1 and 2), and is operable to capture an image of a scene occurring exteriorly of the vehicle, such as rearwardly of the vehicle, and to display the image at a display or display system 314 of the vehicle which is viewable by a driver of the vehicle. Image capture system 310 includes an image capture device or camera 316 (such as a camera or camera module of the types described above), which is directed exteriorly of the vehicle and has an exterior field of view which at least partially encompasses a “blind spot” area exteriorly of the vehicle. The images or frames captured by image capture device 316 are displayed at display 314 to assist the driver in viewing the blind spot areas, such as the rearward area immediately behind the vehicle for backing up or otherwise driving or maneuvering the vehicle. The image capture system 310 may include one or more auxiliary illumination sources 318 (FIG. 26), which may be selectively operable to provide illumination within the field of view of the image capture device 316 to enhance the illumination of the exterior scene. The image capture system 310 may also include a control or control system or microcontroller or microprocessor 320 for controlling or adjusting the image capture device and/or the illumination sources in response to the light levels in the general vicinity of the imaging system or in response to the contrast ratio in the captured image. For example, the microcontroller may selectively activate one or more illumination sources or LEDs 318, or may selectively switch the imaging sensor 316 from a color mode to a monochromatic or black and white mode, or may apply an infrared or near infrared contribution correction to the color levels of the pixels of the imaging sensor to adjust the color balance for better color rendition in the captured images, in response to the ambient light levels or contrast ratio, as discussed below. Image capture system 310 may be positioned at the exterior portion of the vehicle and directed generally exteriorly of the vehicle for capturing images of the exterior scene to assist the driver in maneuvering or driving the vehicle. Image capture system 310 may utilize principles of other vehicle vision or imaging systems, such as a forwardly, sidewardly or rearwardly directed vehicle vision system or imaging system or the like utilizing principles of the systems disclosed in U.S. Pat. Nos. 5,550,677; 5,670,935; 5,760,962; 5,796,094; 5,877,897; 5,949,331; 6,097,023; 6,201,642; 6,222,447; 6,302,545; 6,313,454; 6,320,176; 6,353,392; 6,396,397; 6,498,620; 6,523,964; 6,559,435; and 6,611,202, and U.S. patent application, Ser. Nos. 09/441,341, filed Nov. 16, 1999 by Schofield et al. for VEHICLE HEADLIGHT CONTROL USING IMAGING SENSOR (Attorney Docket DON01 P-770); Ser. No. 10/427,146, filed Apr. 30, 2003 by Schofield et al. for VEHICLE HEADLIGHT CONTROL USING IMAGING SENSOR (Attorney Docket DON01 P-1091); Ser. No. 09/199,907, filed Nov. 25, 1998 by Bos et al. for WIDE ANGLE IMAGE CAPTURE SYSTEM FOR VEHICLE (Attorney Docket DON01 P-676); Ser. No. 10/372,873, filed Feb. 24, 2003 by Schofield et al. for VEHICLE IMAGE CAPTURE SYSTEM (Attorney Docket DON01 P-1077); Ser. No. 10/011,517, filed Nov. 5, 2001 by Bos et al. for INTERIOR REARVIEW MIRROR SYSTEM INCLUDING A FORWARD FACING VIDEO DEVICE (Attorney Docket DON01 P-934); Ser. No. 10/324,679, filed Dec. 20, 2002 by Schofield et al. for VEHICULAR VISION SYSTEM (Attorney Docket DON01 P-1059); Ser. No. 10/047,901, filed Jan. 14, 2002 by Bos et al. for VEHICLE IMAGING SYSTEM WITH ACCESSORY CONTROL (Attorney Docket DON08 P-949); Ser. No. 10/643,602, filed Aug. 19, 2003 by Schofield et al. for VISION SYSTEM FOR A VEHICLE INCLUDING IMAGE PROCESSOR (Attorney Docket DON01 P-1087); and Ser. No. 10/010,862, filed Dec. 6, 2001 by Bos for PLASTIC LENS SYSTEM FOR VEHICLE IMAGING SYSTEM (Attorney Docket DON01 P-954), which are hereby incorporated herein by reference. The imaging system may be operable to captures images of the scene immediately rearward of the vehicle to assist the driver of the vehicle in backing up or maneuvering the vehicle in reverse. The back up assist system may be operable in response to the reverse gear of the vehicle being selected. Image capture device or camera or imaging sensor 316 may comprise an imaging array sensor or a pixelated imaging array, such as a multi-pixel array such as a CMOS sensor or a CCD sensor or the like, such as the types disclosed in commonly assigned U.S. Pat. Nos. 5,550,677; 5,670,935; 5,796,094; 6,097,023; and 6,498,620, and U.S. patent applications, Ser. No. 09/441,341, filed Nov. 16, 1999 by Schofield et al. for VEHICLE HEADLIGHT CONTROL USING IMAGING SENSOR (Attorney Docket DON01 P-770); and Ser. No. 09/93,002, filed Feb. 26, 2001 by Schofield et al. for VIDEO MIRROR SYSTEMS INCORPORATING AN ACCESSORY MODULE (Attorney Docket DON01 P-869), which are hereby incorporated herein by reference, or such as an extended dynamic range camera, such as the types described above. For example, the imaging sensor may comprise a CMOS camera, such as the OV7930 single chip CMOS color NTSC camera available from OmniVision Technologies Inc. of Sunnyvale, Calif. Such color cameras may have the performance characteristics identified above and may additionally provide RGB and/or YCrCb video signals. Preferably, the color video camera operates at a minimum illumination (3000 K) of less than about 5 lux at f1.2, more preferably of less than about 3 lux at f1.2, and most preferably less than about of less than about 2 lux at f1.2. Such CMOS imaging sensors typically may have a peak sensitivity in the near infrared range, such as at approximately 850 nm to 900 nm. Such pixelated imaging sensors may include a plurality of pixels, with at least some of the pixels masked or covered with a particular color filter, such that the individual pixels function to capture a particular color, such as red, green and blue colors or the like, such as disclosed in U.S. Pat. Nos. 5,550,677; 5,670,935; 5,796,094; 6,097,023; and 6,498,620, referenced above. For example, the imaging sensor 16 may comprise an individual blue or a green or a red color filter over each pixel element of the CMOS multi-pixel element array. The imaging sensor is thus operable to provide color images to the display. Such RGB filters enable the capture of a color image by the CMOS detector, but necessarily result in a reduced or decreased low light level sensitivity for a color camera compared to a monochromatic or black and white camera. Optionally, and preferably, the imaging sensor may be capable of selectively operating in either a color mode, in which a color image may be displayed on display 314, or a monochromatic or black and white mode, in which a monochromatic or black and white image may be displayed on display 314, such as by utilizing aspects of the imaging sensor disclosed in U.S. Pat. No. 6,498,620, which is hereby incorporated herein by reference. In the illustrated embodiment of FIGS. 26, the image capture device 316 is at least partially contained within an imaging module or camera module 322, which includes imaging sensor or camera 316 and a lens 324 positioned within a housing (such as similar to housing 11 of camera module 10, discussed above) which defines a transparent window 322a (which may comprise an at least substantially transparent glass or polycarbonate or acrylic (or other suitable material) window or panel) at the end of lens 324 (such as described above with respect to camera module 10, 10′). The imaging module 322 may include the circuitry and controls for imaging sensor 316, such as on one or more printed circuit boards 322b (FIG. 26) contained within the housing. The imaging module 322 is shown in FIG. 26 without the housing for purposes of clarity. As shown in FIG. 26, imaging module 322 may be positioned at or adjacent to a plurality of illumination sources 318 to define an imaging system module 323. The illumination sources 318 may be operable to emit or project illumination in the general direction that the imaging sensor 316 and lens 324 are directed. Preferably, the illumination sources project or emit substantially uniform illumination directly behind the vehicle where the vehicle back up lights do not typically provide adequate illumination. The illumination sources may be selected to provide sufficient intensity over the targeted area to maintain the minimum acceptable contrast ratio (such as about 18 dB) in the displayed images. The illumination sources 318 may comprise infrared or near infrared emitting light emitting diodes (LEDs) or the like and thus may emit light or energy in the infrared or near infrared range (such as energy having a wavelength of approximately 750 nm or greater). The infrared illumination may be provided via pulsing the illumination sources or generally continuously activating the illumination sources. An exemplary near-infrared emitting LED to use in conjunction with the imaging system of the present invention is available from Lumex Inc. of Palatine, Ill. under the trade name OED-EL-1L2. This is a T-5 mm, leaded, clear epoxy −60 degree LED that emits essentially no visible light but that has a peak spectral emission of about 940 nm. Forward current through such infrared LEDs is typically less than about 150 mA, more preferably less than about 100 mA, and most preferably less than about 80 mA. Power consumption by such infrared LEDs is typically less than about 350 mW, more preferably less than about 250 mW, and most preferably is less than about 150 mW. Such LEDs can be powered by duty cycling, such as by pulse width modulation or by direct current drive (typically via a load dropping resistor in series with the vehicle ignition supply). Other near-infrared light emitting diodes or the lice can be used, such as LEDs with a peak light emission intensity at about 730 nm, at about 780 nm, at about 875 nm, and at about 880 nm. Spectral output for such near-infrared LEDs is preferably in the 5 mW/sr to about 35 mW/sr range. Such near-infrared light emitting diodes emit little or no visible light. The infrared or near infrared illumination thus may provide improved camera pixel responsivity in low light levels, and the projected infrared or near infrared illumination is not readily visible directly behind the vehicle when the illumination sources are activated. The wavelength of the illumination emitted by the illumination sources may be selected to best balance the camera spectral response and to minimize ambient lighting affects in the captured image. Optionally, auxiliary illumination sources may be selected that emit visible light, as discussed below. Optionally, additional visible light sources (such as visible light emitting LEDs or an incandescent source or a neon source or the like) can illuminate on occasions at night when the driver wants to have visible light illumination of the area immediately exteriorly of the vehicle. Optionally, the auxiliary illumination may be provided via activation of modified back up lights, which may provide visible or infrared or near infrared illumination at the area immediately rearward of the vehicle, such as when the vehicle is shifted to the reverse gear. With reference to FIG. 25, imaging system 310 includes microcontroller 320, which is operable to control imaging sensor 316 and auxiliary illumination sources 318. The microcontroller 320 may receive an input signal from one or more ambient light sensors 326, which are operable to detect the ambient light levels within the exterior scene. The microcontroller may provide an active camera control and may be operable to adjust or control the imaging sensor and/or the illumination sources in response to the ambient light levels present in the exterior scene. Optionally, the microcontroller may process the captured image to determine the contrast ratio in the images. The microcontroller may then adjust or control the imaging sensor and/or the illumination sources in response to the contrast ratio in order to maintain the image display contrast ratio at a minimum acceptable viewing contrast ratio. For example, the microcontroller may activate or increase the illumination output of the illumination sources to increase the contrast ratio in the captured images to a desired or threshold minimum ratio or level, such as approximately 18 dB. The imaging sensor 316 may receive or capture images via imaging lens 324 and a bandpass filter 328, all of which may be positioned behind the transparent window of camera module 322. The images captured by imaging sensor 316 may be received by an image processor 330 and data translator 332, which may process the images or pixel outputs as desired. For example, the image processor 330 and data translator 332 may be operable to process the images to determine if an object is present in the detected image, such as by utilizing the principles disclosed in U.S. patent application, Ser. No. 10/427,051, filed Apr. 30, 2003 (Attorney Docket DON01 P-1075), which is hereby incorporated herein by reference, or may process the captured images to extract other information therefrom, without affecting the scope of the present invention. The data translator 332 may also receive inputs 333 pertaining to vehicle data or vehicle status data or the like. The images captured may be displayed at the display or display system 314, and/or the processed images or information derived or extracted from the processed images may be displayed at the display or display system 314. During normal day time conditions or high ambient light conditions (for example, when the ambient light sensor or sensors 326 detect an ambient light level which is greater than a threshold light level or when the microcontroller determines that the contrast ratio of the captured images is greater than the minimum acceptable viewing contrast ratio), imaging sensor 316 may provide color images which provide a color rendition consistent with the driver's expectations (in other words, consistent with real world colors). The imaging sensor or camera may be switched or set to a color mode when ambient light levels are at or increase to a sufficient level at or above a minimum or threshold level, and thus may capture color images and may provide color images to the display system during such lighting conditions. The camera or system may also include an automatic color balance algorithm which may function to adjust or optimize the colors in the captured image to the visible spectrum of light, as discussed below. As disclosed in U.S. Pat. Nos. 5,550,677; 5,670,935; 5,796,094; 6,097,023; and 6,498,620, and U.S. patent applications, Ser. No. 09/441,341, filed Nov. 16, 1999 by Schofield et al. for VEHICLE HEADLIGHT CONTROL USING IMAGING SENSOR (Attorney Docket DON01 P-770); and Ser. No. 09/793,002, filed Feb. 26, 2001 by Schofield et al. for VIDEO MIRROR SYSTEMS INCORPORATING AN ACCESSORY MODULE (Attorney Docket DON01 P-869), which are hereby incorporated herein by reference, the pixels of the imaging array sensor 316 may be individually operable to measure a particular color or range of color (such as red, green and blue) in the visible spectrum to determine the color image. Any near infrared radiation or infrared radiation that is received by the pixels may add to the measured value of the particular color that the particular pixel senses or accumulates. This results in a shift in the representation in the color of the captured image and may result in an image having unsatisfactory or unrepresentative color. Optionally, and as discussed below, the band pass filter 328 of the imaging system may comprise an infrared or near infrared filter, which may filter out or substantially block light in the infrared and/or near infrared range of the spectrum, such as light having wavelengths in the approximately 750 to 900 nm, and preferably blocking or reducing transmission of some light in the visible region of the electromagnetic spectrum so that band pass filter 328 passes (i.e. is highly transmitting to) visible wavelengths up to about 650 nm or thereabouts, but has reduced transmission above about 650 nm and, in particular, has substantially reduced transmission in the near infrared region. In order to correct the color balance in the captured images, the image capture system of the present invention may subtract fixed values from the particular color values (e.g., red, green, blue) of each pixel, such that the imaging system may provide an infrared or near infrared contribution correction in situations where the infrared or near infrared light present in the scene (such as from solar radiation) may otherwise washout or distort or otherwise adversely affect the color balance of the captured images. The offset or subtracted values may be a generally fixed intensity offset or value or may be based on the ambient light levels detected by the ambient light sensor or by a combination of pixels of the imaging sensor or the like. Optionally, the infrared radiation present in the exterior scene may be measured, such as via an infrared sensor positioned at the lens 324, imaging sensor 316 or window 322a of camera module 322. The measured infrared radiation may be factored into the infrared contribution correction amount to provide an improved and dynamic correction for the pixels. It is further envisioned that the offset for the particular colors (e.g., red, green, blue) may be different between the colors (for example, in certain lighting conditions, there may be more of an offset for one color, such as, for example, red, than the other color or colors, such as green and blue). The imaging system may thus provide a detection of the infrared radiation and may provide a dynamic correction of each pixel color. The imaging system thus may provide a sensor driven offset or correction. The sensor or sensors may comprise an infrared sensor (with a visible light filter) by itself or in combination with a second sensor which senses visible light (with an infrared filter), to determine the infrared level or intensity in the exterior scene. Optionally, some of the pixels of the imaging array sensor 316 may be unmasked or unfiltered, such that they capture or accumulate the entire spectrum of light (or at least substantially the entire spectrum of light) present in the scene. The unmasked pixels thus are dedicated to sensing the visible and infrared light present in the exterior scene and may provide a basis for determining the offset that is to be applied to the color value of the masked pixels. In such an embodiment, the image capture device would not include an infrared filter, or at least not an infrared filter over the entire pixelated array (however, an infrared filter at the pixel level may be provided, such as an infrared filter at each of the individual color pixels, which also include a mask or filter associated with the particular color that the individual pixel is to capture). The imaging sensor 316, which may comprise a CCD or CMOS camera or the like, may thus operate sufficiently well with its factory settings at illumination levels between a few lux and several thousand lux (such as may be present in normal indoor lighting conditions). When the available ambient illumination is below these levels, however, the camera may have a difficult time distinguishing features in the captured image as compared to the background noise of the camera, and thus may not be able to maintain the minimum contrast ratio during such low light levels. To address this deficiency, the auxiliary illumination sources 318 may be selectively activated to project auxiliary illumination throughout the field of view of the camera, in order to provide sufficient illumination levels for the camera to operate properly. The illumination sources may be selectively activated or controlled by the microcontroller in response to the ambient light levels detected by ambient light sensor or sensors 326 or by imaging sensor 316 (such as in response to a detection that the ambient light level has dropped or reduced to a threshold reduced light level), or in response to the contrast ratio in the captured image (such as in response to the contrast ratio being less than a desired or threshold amount, such as approximately 18 dB). Optionally, the auxiliary illumination sources 318 may emit or project or provide visible light to the exterior scene. In such applications where visible light is provided by the auxiliary illumination sources (or where sufficient visible light may be provided by the backup lights or other lights or illumination sources of the vehicle), the band pass filter 328 may comprise an infrared or near infrared filter (or visible light pass filter) and may provide a cutoff or block at approximately 650 nm, such that the near infrared and infrared spectral regions (and preferably a portion of the visible light region of the spectrum) are limited or blocked from the imaging sensor or camera 316. Because greater visible illumination may thus be provided via the illumination sources in low ambient light conditions, while the infrared and near infrared illumination present in the exterior scene may be filtered or substantially blocked, the imaging system may be capable of capturing images during such lighting conditions which may have acceptable color balance, or which may require a reduced amount of processing or color adjustment to achieve the appropriate or acceptable color balance and contrast ratio. The filter pass or cutoff wavelength range may be selected to tailor the filter cutoff wavelength to the particular application (depending on the illumination provided to the exterior scene and the capabilities of the imaging sensor). The imaging system thus may provide improved imaging capabilities in low light conditions, while providing an appropriate color balance and contrast ratio for the images captured in all ambient lighting conditions. In applications where the auxiliary illumination source or sources comprise infrared or near infrared illumination sources or LEDs, the microcontroller may switch the color camera from the color mode (where the camera captures color images and the display displays color images) to a monochromatic or black and white mode (where the camera captures monochromatic images). The microcontroller may switch the imaging sensor to the black and white mode in response to the ambient light level dropping to the threshold level or in response to the illumination sources being activated. Such a monochromatic mode is preferred in reduced visible lighting conditions and/or when the infrared emitting illumination sources are activated because the automatic color balance algorithm of the imaging system functions to optimize the color in the captured image to the visible spectrum, and may not function as well in such infrared or non-visible lighting conditions. Once the infrared or near infrared illumination is introduced by the illumination sources, the color balance control may be insufficient, which may result in a washed out or distorted image. The black and white image provided by the black and white mode may thus be more pleasing for viewing by the driver of the vehicle during such lighting conditions. The image sensor may quickly switch between the color mode and black and white mode and may provide a smooth transition from one mode to the other. With reference to FIG. 25, the following illustrates the sequence of events that may trigger or initiate the low-light mode of the imaging system of the present invention. The microcontroller 320 may read or receive an output from one or more ambient light sensors 326, which may be positioned at or near imaging sensor 316 and which may be operable to detect or sense the ambient light present in the exterior scene. The microcontroller may also determine the contrast ratio of the images being captured by the imaging sensor. When the ambient light levels are determined to be below a low-light mode calibrated value or threshold value (or when the contrast ratio drops below the threshold level), the microcontroller may then initiate new commands to the imaging sensor or camera 316, such as via an I2C serial link or the like. The new register commands may consist of defeating the automatic gain, exposure and color modes of the imaging sensor 316. The exposure may be set to maximum frame integration time and the amplifier gain may, for example, be set to ½ maximum. This combination provides an enhanced or optimal signal to noise ratio for such lighting conditions. The microcontroller may enter the monochromatic or color defeat mode, whereby the microcontroller may select either a single color kill register or a combination of modifying the color matrix registers to negate the color balance of the imaging sensor. The microcontroller may also enable the infrared LEDs via a logic control signal or the like, so that infrared or near infrared illumination is provided to the exterior scene. The low light mode camera settings may then be maintained until one or more of the ambient light sensors returns values or signals to the microcontroller which are above or outside the calibrated or threshold low-light mode range. Once this occurs, the imaging sensor may be set to the color mode and the above mentioned registers may be again updated with new values, and the illumination sources or LEDs may be disabled. The imaging sensor, such as a CMOS camera or the like, may implement the register updates within approximately two frame times (i.e., the time it takes to capture two consecutive frames or images), which may be within approximately 66 ms, depending on the particular imaging sensor used with the imaging system of the present invention. Because the imaging system of the present invention may correct for washout or distortion in the color values to account for infrared and near infrared illumination in the exterior scene, and because the imaging system may switch to a monochromatic mode when conditions darken and/or when the illumination sources are activated, the present invention may obviate the need or desirability of providing an infrared filter at the imaging sensor, since such a filter may filter out some of the infrared or near infrared illumination provided by the illumination sources when the imaging system is in the low light mode. However, it is envisioned that such a band pass filter or infrared filter element may optionally be provided at the imaging sensor to attenuate at least some of the infrared radiation that may be present in the exterior scene. For example, an infrared filter may be provided that is highly transmitting (such as an integrated photopic visible transmission of at least about 75% transmitting, more preferably at least about 80% transmitting, and most preferably at least about 85% transmitting) in the visible light region between about 300 nm and 800 nm (where the eye's photopic response is sensitive), and more preferably in the 400 mn to 700 nm spectral range, and that has a lower or reduced transmissivity or is lowly transmitting in the 800 nm to 1100 nm region (at least) with a spectral transmission in the 750 nm to 1100 nm of less than about 5% transmission preferred, less than about 3% more preferred, and less than about 1% most preferred. Such infrared filter elements typically consist of a transparent substrate (typically glass) coated with a multilayer stack (typically at least three layers, more preferably at least five layers, most preferably at least seven layers, and typically deposited by vacuum deposition such as by sputtering or evaporation) of metal oxides and similar dielectric thin film layers that form a broad band visible band pass filter with a sharp spectral cut off around 700 nm or so. Such infrared filters typically operate by light interference, and preferably act as cold mirrors reflecting away near-infrared radiation while being highly transmitting to visible light. An example of an infrared filter element suitable for use with the imaging system of the present invention is available from Maier Photonics, Inc. of Manchester Center, VT under the part designation “p/n SP730/14s”. This filter element has a 50% cut-off at +/−10 nm at normal incidence, and comprises a 1 mm thick soda-lime glass substrate. Alternately, a WBHM infrared filter element available from. OCLI of Santa Rosa, Calif. can be used (which has an average transmission equal to or greater than 80% from approximately 400 nm to 700 nm and an average transmission less than or equal to 2% from approximately 750 nm to 1100 nm). Also, an infrared filter element from Evaporated Coatings, Inc. of Willow Grove, Pa. comprising a Corning Micro-Sheet Glass 0211 coated with ECI#1010 can be used. This filter element has an average transmission equal to or greater than 85% at 400 nm to 700 nm; a partial transmission of about 80% at 740 nm (+/−10 nm); a partial transmission of about 50% at 750 nm (+/−10 nm); and an average transmission of less than about 3% at 780 nm to 1100 nm. Such infrared filter elements are abrasion resistant per MIL-C-675A, which is hereby incorporated by reference herein. Such infrared filters may be disposed in the camera assembly in front of the CMOS or CCD imaging array sensor (either in front of the camera lens or between the camera lens and the video detector array). However, a problem can arise when a camera equipped with an infrared element as described above is used in conjunction with near infrared light emitting sources such as those also described above. The near infrared cut off of the camera filter may also severely attenuate and/or block the near infrared radiation emitted by the near infrared LEDs (or similar near-infrared emitting sources) such that nighttime illumination may be inadequate to be useful/valued by the driver. In order to avoid such concerns, while still providing such an infrared filter, the infrared filter and illumination sources may be selected such that at least some of the infrared illumination emitted by the illumination sources is not filtered or blocked by the infrared filter. For example, the filter may be selected that may cut out or substantially block radiation having wavelengths above approximately 950 nm, while the illumination source may emit light having wavelengths of approximately 800 nm to 900 nm. Optionally, and as discussed above, the auxiliary illumination sources may be operable to emit or project visible light to provide adequate visible illumination to the exterior scene, whereby the infrared and near infrared light may not be required by the imaging sensor (and thus may be filtered or blocked, such as at a wavelength of approximately 650 nm and above) in order to provide appropriate clarity and color balance in the images captured by the imaging sensor. Optionally, it is further envisioned that the imaging system may function to remove the infrared filter from in front of the imaging sensor when the infrared illumination sources are activated, such as described in U.S. patent application, Ser. No. 09/793,002, filed Feb. 26, 2001 by Schofield et al. for VIDEO MIRROR SYSTEMS INCORPORATING AN ACCESSORY MODULE (Attorney Docket DON01 P-869), which is hereby incorporated herein by reference. For example, at nighttime when ambient lighting is low and the infrared emitting illumination sources are activated, the infrared filter element may be moved out of the field of view of the lens so that the detector or camera can view unattenuated infrared radiation from the infrared emitting illumination sources so that the output image in the video display is discernable by the driver. Various means can be used to remove the infrared filter element from the camera field of view during nighttime. For example, an electromechanical mechanism, preferably operated by the microcontroller in response to a photo sensor or ambient light sensor, can automatically move the infrared filter element, such as by electrical command, out of the line of sight or field of view of the imaging sensor when the ambient lighting conditions are low. Optionally, electro-optic means can be used to prevent color wash out by day while maximizing low light sensitivity by night. For example, an electrochromic infrared filter can be used, such as a filter utilizing the principles disclosed in U.S. Pat. No. 6,426,492, and U.S. patent application, Ser. No. 10/206,558, filed Jul. 26, 2002 by Bos for ELECTRO-OPTIC FILTER FOR VEHICLE IMAGING SYSTEM (Attorney Docket DON01 P-1013), which are hereby incorporated herein by reference. The filter may include a tungsten oxide electrochromic layer that changes from being substantially visible light transmitting and substantially near-infrared transmitting when uncharged (bleached) and transforms to being significantly near-infrared absorbing/reflecting as well as being significantly visible light attenuating when cathodically charged. The degree of near-infrared attenuation and visible light attenuation is proportional to the negative voltage applied to the electrochromic tungsten oxide metal oxide layer, with applied voltages in the 0.1V to about 2.5V range typical. The higher the cathodic voltage applied, the more the near-infrared/visible light attenuation. Optionally, the imaging system of the present invention may additionally include a plurality of infrared shutters which are in the optical path the imaging array sensor, such as disclosed in U.S. Pat. No. 6,498,620, which is hereby incorporated herein by reference. Each infrared shutter has at least one state in which infrared energy is generally not attenuated to the imaging sensor. In another state, the infrared shutter generally blocks infrared radiation from the array. The state of the infrared shutters may be controlled by the microcontroller, which may control the shutters in response to the ambient light levels in the exterior scene, such as detected by the ambient light sensor or sensors. During periods of high image luminance, the infrared shutters may switch to a state in which the shutters block near infrared radiation from the imaging sensor. However, during low image luminance conditions, the infrared shutters may switch to a state in which the shutters allow the near infrared energy to be transmitted to the imaging sensor. The addition of the near infrared radiation at low luminance levels enhances the image luminance sensed by the imaging sensor. The imaging sensor may also be switched to the monochromatic or black and white mode during such low luminance levels. The infrared shutters may be either electrochromic shutters or liquid crystal shutters, both of which are known in the art. Although many aspects of the present invention are particularly suitable for applications having a CMOS type image sensor or camera (due to the high infrared sensitivity of CMOS cameras), other types of cameras or sensors may be implemented, such as CCDs, etc., without affecting the scope of the present invention. Therefore, the present invention provides an imaging system which may provide enhanced imaging during nighttime conditions, while providing optimal color imaging during daytime conditions. The imaging system may determine the ambient light levels at the exterior scene, such as via ambient light sensors or photosensors, which may be associated with the camera or imaging array sensor, or which may be separate ambient light sensors. When the ambient light levels drop below a threshold level, the color mode of the imaging sensor may be turned off, such that the imaging sensor operates in a monochromatic or black and white mode in such low light conditions, thereby providing an enhanced image to the display for viewing by the driver of the vehicle. Also, the illumination sources (which are preferably infrared or near infrared illumination sources or LEDs) may be activated when the ambient light levels are low, so as to provide additional, substantially non-visible light to the exterior scene. Optionally, the illumination sources may be activated to illuminate the targeted area to increase the contrast ratio in the displayed images to a desired amount in response to the contrast ratio falling below a minimum acceptable viewing contrast ratio. Because the imaging sensors may then be operating in a black and white mode, the infrared illumination emitted by the illumination sources will not result in washed out or saturated or distorted color images. Also, because the imaging sensor may have a peak sensitivity in the infrared or near infrared range, and because the illumination sources may be infrared emitting sources, the imaging sensor may be capable of capturing images in very low lighting conditions, whereby the illumination for the imaging sensor is provided by the infrared illumination sources. Optionally, when the imaging sensor is operating in the color mode, the microcontroller may adjust or correct the color balance via an adjustment of the pixel output for each of the color sensing pixels of the pixelated imaging array sensor. The present invention thus may provide a dynamic color balance adjustment function for a vehicular color exterior-viewing camera, such as one viewing rearward of the vehicle or forward of the vehicle or sideways of the vehicle, such as may be achieved by placing the camera module with integrated auxiliary illumination into an exterior rearview mirror assembly with its field of view directed toward and onto a ground surface adjacent the side body of the vehicle (in this regard, and when auxiliary illumination is required, and when the camera-equipped exterior mirror assembly includes a visible light emitting ground illumination/security light, such as are disclosed in U.S. Pat. Nos. 6,276,821; 6,176,602; 5,823,654; 5,669,699; 5,497,306; and 5,371,659, which are hereby incorporated herein by reference, the ground illumination/security light may optionally be selectively actuated to add additional auxiliary illumination in certain circumstances, such as when about to or first starting to drive the vehicle from a parked position). Preferably, such dynamic adjustment of color balance is achieved by determination of the level of near-infrared radiation incident the camera module and by using this determined level (via a closed-loop or an open-loop control algorithm) to adjust the color balance and/or other characteristics (such as selection of the monochrome or black and white mode) of the video camera system employed. Other camera functions, such as iris function or exposure function, may optionally be similarly dynamically adjusted commensurate with a detected ambient near-infrared or other light level at the camera module. The present invention also finds applicability to interior cabin monitoring systems. Changes and modifications to the specifically described embodiments may be carried out without departing from the principles of the present invention, which is intended to be limited only by the scope of appended claims, as interpreted according to the principles of patent law.
<SOH> BACKGROUND OF THE INVENTION <EOH>The advent of low cost, reliable imaging devices, based on a variety of silicon technologies, and in particular CMOS technology, combined with an improved cost/performance ratio for displays capable of meeting automotive specifications, and an increasing application rate of video monitor displays for automotive navigation systems or as part of the driver interface to a wide variety of vehicle systems, has lead to an increasing use of cameras or imaging sensors designed to give the driver a view of those areas around the vehicle which are not in the normal direct field of view of the driver, typically referred to as “blind spots”. These areas include the region close to the front of the vehicle, typically obscured by the forward structure of the vehicle, the region along the passenger side of the vehicle, the region along the driver's side of the vehicle rearward of the driver, and the area or region immediately rearward of the vehicle which cannot be seen directly or indirectly through the rear view mirror system. The camera or imaging sensor may capture an image of the rearward (or sideward or other blind spot area) field of view, and the image may be displayed to the driver of the vehicle to assist the driver in backing up or reversing or otherwise driving or maneuvering the vehicle. The use of electronic cameras in these applications significantly increases the driver's knowledge of the space immediately surrounding the vehicle, which may be of importance prior to and during low speed maneuvers, and thus contributes to the safe completion of such maneuvers. It is thus known to provide a camera or imaging sensor on a vehicle for providing an image of a scene occurring exteriorly or interiorly of the vehicle to a driver of the vehicle. Such a camera may be positioned within a protective housing, which may be closed about the camera or sensor and secured together via fasteners or screws or the like. For example, a metallic protective housing may be provided, such as a die cast housing of aluminum or zinc or the like. In particular, for camera sensors mounted on the exterior of a vehicle, protection against environmental effects, such as rain, snow, road splash and/or the like, and physical protection, such as against road debris, dirt, dust, and/or the like, is important. Thus, for example, in known exterior camera sensor mounts, a butyl seal, such as a hot dispensed butyl seal, or an O-ring or other sealing member or material or the like, has been provided between the parts of the housing to assist in sealing the housing to prevent water or other contaminants from entering the housing and damaging the camera or sensor positioned therein. However, such housings typically do not provide a substantially water tight seal, and water droplets thus may enter the housing. Furthermore, any excessive vibration of the camera sensor, due to its placement (such as at the exterior of the vehicle), may lead to an undesirable instability of the image displayed to the driver of the vehicle. Also, such cameras or sensors are costly to manufacture and to implement on the vehicles. Such vehicle vision systems often position a camera or imaging sensor at an exterior portion of a vehicle to capture an image of a scene occurring exteriorly of the vehicle. The cameras, particularly the cameras for rearward vision systems, are thus typically placed or mounted in a location that tends to get a high dirt buildup on the camera and/or lens of the camera, with no easy way of cleaning the camera and/or lens. In order to reduce the dirt or moisture buildup on the lenses of such cameras, it has been proposed to use hydrophilic or hydrophobic coatings on the lenses. However, the use of such a hydrophilic or hydrophobic coating on the lens is not typically effective due to the lack of air flow across the lens. It has also been proposed to use heating devices or elements to reduce moisture on the lenses. However, the use of a heated lens in such applications, while reducing condensation and misting on the lens, may promote the forming of a film on the lens due to contamination that may be present in the moisture or water. Also, the appearance of such cameras on the rearward portion of vehicles is often a problem for styling of the vehicle. Typically, based on consumer preference and at least a perceived improved ability to extract information from the image, it is desired to present a color image to the driver that is representative of the exterior scene as perceived by normal human vision. It is also desirable that such imaging devices or systems be useful in all conditions, and particularly in all lighting conditions. However, it is often difficult to provide a color imaging sensor which is capable of providing a clear image in low light conditions. This is because conventional imaging systems typically have difficulty resolving scene information from background noise in low light conditions. Silicon-based cameras may be responsive to light in the visible and near infrared portions of the spectrum. It is known to filter out the infrared portion of the energy available to the camera in order to maintain an appropriate color balance. When this is done, the camera sensitivity may be less than if the near infrared and infrared light was received and used by the camera. Depending on the imaging technology used, the minimum sensitivities currently economically available for automotive cameras are typically in the range of 1 to 2 lux and may maintain a reasonable image quality at light levels at or above such levels. However, the conditions on a dark cloudy night where moonlight is obscured, and/or in rural situations in which there is no source of artificial lighting, may result in a scene illumination as low as about 0.01 lux. While the technology continues to improve the low light sensitivity of silicon based cameras, it is not expected that 0.01 lux capability will become available in the foreseeable future. Other technologies may be capable of such sensitivity, but are not sufficiently cost effective for general application in the automotive industry. Therefore, there is a need in the art for a camera housing that overcomes the shortcomings of the prior art, and a need in the art for an imaging system that may provide clear, satisfactory images during all driving or lighting conditions, and thus overcomes the shortcomings of the prior art imaging systems.
<SOH> SUMMARY OF THE INVENTION <EOH>The present invention is intended to provide a camera module which includes a camera or image sensor and a circuit board positioned within a housing, which may be laser welded or sonic welded or the like to substantially seal the camera and circuit board within the housing. The housing, preferably molded of a plastic material, may include a plastic molded connector extending therefrom, such that the camera housing and connector are configured as a single unitary module. The camera module may include a heating element for heating a transparent cover at the lens (or for heating the lens itself) of the camera to assist in defogging or defrosting the transparent cover in cold weather conditions. The transparent cover may have a transparent conductive coating (such as an indium tin oxide (ITO) coating or doped tin oxide or a metal grid or the like), preferably on its inner surface, such that contact of a power terminal (connected to or in communication with or powered by a battery or other power source of the vehicle) and a ground terminal of the heating elements at the conductive coating causes heating of the coating to defrost or defog the cover. The heating elements or terminals may be actuated in response to a control or thermostat, which functions to activate and deactivate the heating element at predetermined temperatures sensed by a temperature sensor at or in the camera module or elsewhere at, in or on the vehicle. The present invention thus provides a camera module that maintains the camera or imaging sensor and is substantially impervious to environmental elements, such as rain, snow, dirt, dust, road splash, road debris and the like. The present invention also provides at least partial, and preferably substantial, reduced vibration affects of the camera or image sensor. According to an aspect of the present invention, a substantially sealed camera module for an imaging system of a vehicle includes a plastic housing, which preferably includes first and second portions. The first and second portions are preferably laser welded or sonic welded together to substantially seal the camera or sensor and associated components within the plastic housing. The laser welded or sonic welded plastic housing provides a substantially hermetic seal to prevent water intrusion or the like into the housing. Alternately, and less preferably, the first and second portions may be adhesively sealed or joined. The camera module may be incorporated into an imaging system that includes the sensor and a control for processing images captured by the imaging sensor. The camera module may be positioned within a movable housing that is movable relative to the vehicle to move the imaging sensor between an in use or operational position, where the imaging sensor is directed toward the exterior scene, and a storage position, where the housing and the imaging sensor are positioned within a portion of the vehicle. According to another aspect of the present invention, a vented camera module for a vehicle includes a plastic housing which is configured to receive a camera or sensor therein. The housing of the vented camera module includes a semi-permeable ventilation area, such as a Gore-Tex assembly or area or patch or the like, which is at least partially permeable to water vapor and/or is porous enough to allow transfer of water vapor into and out from the housing, while substantially precluding entry of water droplets, dirt or the like into the housing. According to another aspect of the present invention, a camera module for a vehicle includes a housing and a transparent cover at a portion of the housing. The transparent cover provides a transparent wall of the housing for the lens and sensor or camera to receive an image therethrough. The cover may be heated to defrost or defog the cover in cold weather conditions or the like. The cover includes a surface (such as an inner surface within the housing) which has a conductive coating, such as a coating of indium tin oxide (ITO), doped tin oxide or the like. The module includes a pair of heater terminals or elements which contact the coating, whereby heating of the cover or coating on the cover (such as the inner surface of the cover) is accomplished by generating a flow of electricity or electrons or current across the coating on the cover via the heater terminals or elements. In one form, one of the heater terminals may be energized or charged with electricity and the other terminal may be grounded to the vehicle, such that the electrical current travels from the energized or powered terminal across the conductive coating to the grounded terminal, thereby heating the conductive coating and, thus, the transparent cover. Preferably, the heater terminals are spaced apart at generally opposite sides or portions of the transparent cover. Actuation of the heater terminals may defrost or defog the transparent cover and/or may heat the module housing and interior compartment of the camera module to dry out any moisture within the housing or compartment. In applications where the module includes a ventilation area, such as a vented semi-permeable membrane, such as a Gore-Tex assembly or the like, heating of the compartment may be especially suited for driving moisture out of the compartment or module through the ventilation area to limit or substantially preclude moisture condensing within the module. Optionally, the heater terminals may be actuated or energized in response to a control, which is operable to energize the heater terminals or elements in response to a thermostat and/or temperature sensor positioned at or within the camera module or elsewhere at, in or on the vehicle. Optionally, desiccant material, such as silica gel or the like, may be included in the housing to absorb moisture which may be present within the housing. According to yet another aspect of the present invention, a camera module for a vehicle comprises a housing, a transparent cover at a portion of the housing, an image sensor, at least one heating element and a control. The image sensor is positioned within the housing and is operable to receive an image of a scene exteriorly of the housing through the transparent cover. The heating element is operable to heat the transparent cover. The control is operable to activate the heating element in response to a temperature sensor. The heating element is activatable to heat the transparent cover to reduce fog and/or ice on the transparent cover. The present invention also provides a camera housing that is movably positioned at an exterior portion of a vehicle such that the camera may be moved from a stored position to an in-use or exterior or operational position. The camera housing may include a transparent window or panel and may further include a window wiper that functions to wipe dirt and/or moisture or the like from the window or panel as the housing moves the camera between the stored position and the operational position. According to an aspect of the present invention, a holding device for movably holding an imaging device of a vehicle includes a housing, a transparent panel and a panel cleaning device. The imaging device is operable to capture an image of a scene occurring exteriorly of the vehicle. The housing is movably mountable at an exterior portion of the vehicle and is configured to receive an imaging device therein. The housing is movable relative to the exterior portion of the vehicle to move the imaging device between a stored position, where the imaging device is positioned generally within the portion of the vehicle, and an operational position, where the imaging device is positioned to have a field of view exteriorly of the vehicle. The transparent panel is positioned at least partially across an opening of the housing and generally in the field of view of the imaging device. The panel cleaning device is positionable at the exterior portion of the vehicle and configured to engage the transparent panel to clean the transparent panel as the housing moves the imaging device between the stored position and the operational position. According to another aspect of the present invention, an imaging system for a vehicle includes an imaging device operable to capture an image of a scene occurring exteriorly of a vehicle, a control operable to process the image captured by the imaging device, and a camera housing device. The housing device includes a housing portion defining a compartment, a transparent panel substantially closing an opening of the compartment, and a panel cleaning device. The housing device is movably mountable on an exterior portion of the vehicle. The imaging device is positioned within the compartment and directed toward the transparent panel. The housing device is movable between a stored position, where the imaging device and the transparent panel are positioned at least substantially within the exterior portion of the vehicle, and an operational position, where the imaging device is directed exteriorly of the vehicle and has a field of view directed through the transparent panel and toward the exterior scene. The panel cleaning device is positionable at the exterior portion of the vehicle and configured to engage the transparent panel to clean the transparent panel as the housing device moves between the stored position and the operational position. The imaging system may include a display operable to display the image captured by the imaging device. The housing device may be pivotably mountable at the exterior portion of the vehicle, or the housing device may be slidably or otherwise movably mountable at the exterior portion of the vehicle. An outer panel of the housing device may define an exterior cover portion at the exterior portion of the vehicle when the housing device is moved or pivoted to the stored position. Optionally, the imaging system may comprise a color imaging sensor operable to capture color images of the exterior scene and an infrared imaging sensor operable to capture infrared images of the exterior scene. The control may selectively activate one of the color imaging sensor and the infrared imaging sensor in response to the ambient light intensity present in the exterior scene. Optionally, the imaging system may include an illumination source positioned within the compartment and directed toward the exterior scene when the housing device is moved to the operational position. The transparent panel and the compartment are positioned generally within the exterior portion of the vehicle when the housing device is moved to the stored position. Optionally, the control may be operable to selectively activate the illumination source and the imaging device when the housing device is moved to the stored position to determine if moisture is present on the transparent panel. The housing device may include a heater element that is selectively operable to heat the transparent panel to reduce moisture present on the transparent panel. Optionally, the housing device may be movable to selectively position the imaging device in first and second operational positions. The control may be operable to determine a distance to at least one object in the exterior scene in response to processing of images captured by the imaging device when the imaging device is in the first and second operational positions. For example, the control may be operable to selectively move the housing device to position the imaging device at the first operational position in response to the vehicle making an initial approach to a target zone and to position the imaging device at the second operational position in response to the vehicle moving further into the target zone. The imaging device may be directed more downward when in the second operational position relative to the first operational position. According to another aspect of the present invention, an imaging system of a vehicle includes an imaging device, a holding device and a control. The imaging device is operable to capture images of a scene occurring exteriorly of the vehicle. The holding device is pivotally mountable at a portion of a vehicle and includes a housing having an exterior panel and a transparent panel. The imaging device is positioned within the housing. The transparent-panel is positioned at least partially across an opening of the housing and generally in the field of view of the imaging device. The holding device is pivotable relative to the portion of the vehicle to move the imaging device between a stored position, where the imaging device is positioned generally within the portion of the vehicle, and an operational position, where the imaging device is positioned to have a field of view exteriorly of the vehicle. The exterior panel is generally aligned with an exterior surface of the portion of the vehicle and the transparent panel is generally within the portion of the vehicle when the imaging device is in the stored position. The control is operable to process images captured by the imaging device. The present invention also provides a vehicular imaging system or image capture system which is operable to capture an image of an exterior scene and to display the images at a display of the vehicle. The imaging system is operable to control illumination sources operable to illuminate the exterior scene and/or to control the color processing of the captured images and/or to control the color/monochromatic status or mode of the image capture device or camera of the system, in order to provide or display an optimum color or black and white image at the display which has optimum color representation of the scene or has optimum illumination or visibility or clarity or contrast ratio in the image displayed. For example, the imaging system may selectively activate visible or infrared or near infrared illumination sources or light emitting diodes (LEDs) in response to a detected ambient light level dropping or decreasing or lowering to a threshold level. The imaging system may also or otherwise selectively switch the imaging sensor from a color mode to a black and white mode in response to the reduced ambient light level. Optionally, the imaging system may apply an infrared contribution correction to the detected levels for each color (such as red, green, blue) detected by the imaging sensor to adjust the color balance of the imaging sensor for better color rendition in the captured images. Optionally, the imaging system may provide visible illumination to the exterior scene and may limit or block infrared and near infrared light present in the illuminated scene to reduce processing requirements to obtain the appropriate color balance in the captured images. Therefore, the present invention provides a camera module for a vehicle which may be substantially hermetically sealed to limit or substantially preclude water intrusion or the like into the housing of the module, or which may be vented to allow for water vapor to enter or exit the module. The camera housing may also include a heating element which is operable to defrost or defog the transparent cover of the module and/or to heat the compartment of the camera housing to limit or substantially preclude condensation from forming within the module. The heating element may be activated and deactivated at predetermined temperatures in response to a temperature sensor and/or thermostat. The transparent cover of the housing may include a conductive coating on a surface thereof, such that applying an electrical current or flow through or across the coating on the surface of the transparent cover functions to heat the surface of the cover to defrost or defog the transparent cover. The present invention thus provides an environmentally resilient, protected, economical camera module which may be mounted to a vehicle and connected or plugged into a wiring connector of the vehicle. The present invention thus also provides a camera housing device that is movable or adjustable to move a camera or imaging sensor between an operational position and a stored position. The camera thus may be positioned in a stored position within an exterior portion of the vehicle when not in use. The exterior panel of the camera housing device may provide an exterior cover at the exterior portion of the vehicle to protect the camera and lens from the elements when they are not in use. The housing device may include a transparent panel that substantially encloses the camera and lens within the housing. The housing device may also include a panel cleaning device that may clean the transparent panel to limit or substantially preclude dirt buildup or debris on the panel that may adversely effect the performance of the camera and thus of the imaging system. The present invention also provides an imaging system that is capable of providing a color image during daytime conditions, and that may provide a black and white image, with or without additional infrared or near infrared illumination provided to the scene, during darkened or nighttime conditions. The imaging system may correct the color image to account for infrared and near infrared illumination that may be present in the exterior scene, in order to provide an image with proper or desired color balance. The present invention thus may provide optimal images to the driver of the vehicle during substantially all types of lighting conditions. These and other objects, purposes, advantages and features of the present invention will become apparent upon review of the following specification in conjunction with the drawings.
20050511
20110621
20060803
70192.0
H04N718
1
SENFI, BEHROOZ M
IMAGING SYSTEM FOR VEHICLE
UNDISCOUNTED
0
ACCEPTED
H04N
2,005
10,534,644
ACCEPTED
Hydrogen gas sensor
A first electrode and a second electrode are provided, and an electrolyte is disposed between the first electrode and the second electrode. The first electrode and the second electrode are made of corresponding different materials in chemical potential for hydrogen gas. The first electrode includes higher chemical potential material and the second electrode includes lower chemical potential material. The first electrode functions as a detecting electrode for hydrogen gas, and the second electrode functions as a standard electrode for the hydrogen gas. The hydrogen gas is detected on an electromotive force generated between the first electrode and the second electrode.
1. A hydrogen gas sensor comprising a first electrode, a second electrode and an electrolyte contacting with said first electrode and said second electrode, wherein said first electrode and said second electrode are made of corresponding different materials in chemical potential for hydrogen gas, and said first electrode is made of higher chemical potential material and said second electrode is made of lower chemical potential material, wherein said hydrogen gas is detected on an electromotive force generated between said first electrode and said second electrode. 2. A hydrogen gas sensor comprising a first electrode, a second electrode and an electrolyte contacting with said first electrode and said second electrode, wherein said first electrode and said second electrode are made of corresponding different materials in absorption-dissociation active degree for hydrogen gas, and said first electrode is made of higher absorption-dissociation material and said second electrode is made of lower absorption-dissociation material, wherein said hydrogen gas is detected on an electromotive force generated between said fast electrode and said second electrode. 3. The hydrogen gas sensor as defined in claim 1, wherein said first electrode includes a first electrode material which exhibits a standard electromotive force of 0.8V or over in the cell of H2(−)|50 mol/m3 H2SO4| sample(+), and said second electrode includes a second electrode material which exhibits a standard electromotive force of less than 0.8V in the same cell construction. 4. The hydrogen gas sensor as defined in claim 3, wherein said first electrode material includes at least one selected from the group consisting of Pt, Pt alloy, Pd and Pd alloy, and said second electrode material includes at least one selected from the group consisting of Ni, Ni alloy, Ti, Ti alloy, Cu, Cu alloy, Fe, Fe alloy, Al, Al alloy and organic conductive material. 5. The hydrogen gas sensor as defined in claim 1, wherein said first electrode and said second electrode are disposed in the same atmosphere, thereby to contact with said hydrogen gas simultaneously. 6. The hydrogen gas sensor as defined in claim 1, wherein said first electrode and said second electrode are shaped in plate and disposed so as to be opposed to one another, and said electrolyte is disposed between said first electrode and said second electrode. 7. The hydrogen gas sensor as defined in claim 1, wherein said first electrode and said second electrode are shaped in rod or line and disposed on an insulating substrate so as to be separated from one another, and said electrolyte is disposed between said first electrode and said second electrode. 8. The hydrogen gas sensor as defined in claim 1, wherein said second electrode is shaped in cylinder so that said first electrode is disposed in said second electrode, and said electrolyte is disposed at least partially in between said first electrode and said second electrode. 9. The hydrogen gas sensor as defined in claim 1, wherein said electrolyte is a solid electrolyte. 10. The hydrogen gas sensor as defined in claim 9, wherein said solid electrolyte is made of a solid electrolyte raw material and a reinforcing material such as glass wool, wherein said solid electrolyte is made through the solidification of said solid electrolyte raw material with said reinforcing material or the infiltration of said reinforcing material into said electrolyte raw material which is processed in porosity or mesh. 11. A hydrogen gas leak alarm system comprising a hydrogen gas sensor as defined in claim 1 and a voltage comparator, wherein an electromotive force variation as a hydrogen gas detecting information from said hydrogen gas sensor is compared with a reference voltage of said voltage comparator, thereby to put out an signal on the comparison of said electromotive force variation and said reference voltage. 12. A hydrogen gas leak controlling system comprising a hydrogen gas sensor as defined in claim 1 and a voltage comparator, wherein an electromotive force variation as a hydrogen gas detecting information from said hydrogen gas sensor is compared with a reference voltage of said voltage comparator, thereby to put out a signal on the comparison of said electromotive force variation and said reference voltage. 13. A hydrogen gas leak information transmitting system comprising a hydrogen gas sensor as defined in claim 1 and a voltage comparator, wherein an electromotive force variation as a hydrogen gas detecting information from said hydrogen gas sensor is compared with a reference voltage of said voltage comparator, thereby to put out a signal on the comparison of said electromotive force variation and said reference voltage. 14. The hydrogen gas leak alarm system as defined in claim 11, wherein said voltage comparator is configured such that a threshold voltage of a Shumitt inverter is defined as said reference voltage, and compared with an input voltage corresponding to said hydrogen gas detecting information, thereby to put out said signal. 15. The hydrogen gas leak controlling system as defined in claim 12, wherein said voltage comparator is configured such that a threshold voltage of a Shumitt inverter is defined as said reference voltage, and compared with an input voltage corresponding to said hydrogen gas detecting information, thereby to put out said signal. 16. The hydrogen gas leak information transmitting system as defined in claim 13, wherein said voltage comparator is configured such that a threshold voltage of a Shumitt inverter is defined as said reference voltage, and compared with an input voltage corresponding to said hydrogen gas detecting information, thereby to put out said signal. 17. A hydrogen gas sensor array comprising a plurality of hydrogen gas sensors as defined in claim 1, wherein said hydrogen gas sensors are arranged on the same substrate. 18. A hydrogen gas analyzer comprising a hydrogen gas sensor as defined in claim 1 and an electric circuit for detecting an electromotive force from said hydrogen gas sensor, wherein hydrogen gas concentration is detected in dependence on the intensity of said electromotive force. 19. A hydrogen gas sensor element comprising a hydrogen gas sensor as defined in claim 1 and a photo sensor for detecting hydrogen gas shielding contamination from external environment through the detection of an optical signal from an external LED, whereby Fail-Safe function for enhancing reliability in hydrogen gas detection is applied to said hydrogen gas sensor element. 20. A Fail-Safe function for enhancing reliability in hydrogen gas detection wherein hydrogen gas shielding contamination from external environment is detected through the detection of an optical signal from an external LED by a photo sensor. 21. The hydrogen gas sensor as defined in claim 2, wherein said first electrode includes a first electrode material which exhibits a standard electromotive force of 0.8V or over in the cell of H2(−)? 50 mol/m3 H2SO4? sample(+), and said second electrode includes a second electrode material which exhibits a standard electromotive force of less than 0.8V in the same cell construction. 22. The hydrogen gas sensor as defined in claim 21, wherein said first electrode material includes at least one selected from the group consisting of Pt, Pt alloy, Pd and Pd alloy, and said second electrode material includes at least one selected from the group consisting of Ni, Ni alloy, Ti, Ti alloy, Cu, Cu allay, Fe, Fe alloy, Al, Al alloy and organic conductive material. 23. The hydrogen gas sensor as defined in claim 2, wherein said first electrode and said second electrode are disposed in the same atmosphere, thereby to contact with said hydrogen gas simultaneously. 24. The hydrogen gas sensor as defined in claim 2, wherein said first electrode and said second electrode are shaped in plate and disposed so as to be opposed to one another, and said electrolyte is disposed between said first electrode and said second electrode. 25. The hydrogen gas sensor as defined in claim 2, wherein said first electrode and said second electrode are shaped in rod or wire and disposed on an insulating substrate so as to be separated from one another, and said electrolyte is disposed between said first electrode and said second electrode. 26. The hydrogen gas sensor as defined in claim 2, wherein said second electrode is shaped in cylinder so that said first electrode is disposed in said second electrode, and said electrolyte is disposed at least partially in between said first electrode and said second electrode. 27. The hydrogen gas sensor as defined in claim 2, wherein said electrolyte is a solid electrolyte. 28. The hydrogen gas sensor as defined in claim 2, wherein said solid electrolyte is made of a solid electrolyte raw material and a reinforcing material such as glass wool, wherein said solid electrolyte is made through the solidification of said sold electrolyte raw material with said reinforcing material or the infiltration of said reinforcing material into said electrolyte raw material which is processed in porosity or mesh. 29. A hydrogen gas leak alarm system comprising a hydrogen gas sensor as defined in claim 2 and a voltage comparator, wherein an electromotive force variation as a hydrogen gas detecting information from said hydrogen gas sensor is compared with a reference voltage of said voltage comparator, thereby to put out a signal on the comparison of said electromotive force variation and said reference voltage. 30. A hydrogen gas leak controlling system comprising a hydrogen gas sensor as defined in claim 2 and a voltage comparator, wherein an electromotive force variation as a hydrogen gas detecting information from said hydrogen gas sensor is compared with a reference voltage of said voltage comparator, thereby to put out a signal on the comparison of said electromotive force variation and said reference voltage. 31. A hydrogen gas leak information transmitting system comprising a hydrogen gas sensor as defined in claim 2 and a voltage comparator, wherein an electromotive force variation as a hydrogen gas detecting information from said hydrogen gas sensor is compared with a reference voltage of said voltage comparator, thereby to put out a signal on the comparison of said electromotive force variation and said reference voltage. 32. The hydrogen gas leak alarm system as defined in claim 29, wherein said voltage comparator is configured such that a threshold voltage of a Shumitt inverter is defined as said reference voltage, and compared with an input voltage corresponding to said hydrogen gas detecting information, thereby to put out said signal. 33. The hydrogen gas leak controlling system as defined in claim 30, wherein such voltage comparator is configured such that a threshold voltage of a Shumitt inverter is defined as said reference voltage, and compared with an input voltage corresponding to said hydrogen gas detecting information, thereby to put out said signal. 34. The hydrogen gas leak information transmitting system as defined in claim 31, wherein such voltage comparator is configured such that a threshold voltage of a Shumitt inverter is defined as said reference voltage, and compared with an input voltage corresponding to said hydrogen gas detecting information, thereby to put out said signal. 35. A hydrogen gas sensor array comprising a plurality of hydrogen gas sensors as defined in claim 2, wherein said hydrogen gas sensors are arranged on the same substrate. 36. A hydrogen gas analyzer comprising a hydrogen gas sensor as defined in claim 2 and an electric circuit for detecting an electromotive force from said hydrogen gas sensor, wherein hydrogen gas concentration is detected in dependence on the intensity of said electromotive force. 37. A hydrogen gas sensor element comprising a hydrogen gas sensor as defined in claim 2 and a photo sensor for detecting hydrogen gas shielding contamination from external environment through the detection of an optical signal from an external environment through the detection of an optical signal from an external LED, whereby Fail-Safe function for enhancing reliability in hydrogen gas detection is applied to said hydrogen gas sensor element.
FIELD OF THE INVENTION This invention relates to a hydrogen gas sensor which is suitable for detecting hydrogen gas leaked in air or analyzing the concentration of the hydrogen gas. BACKGROUND OF THE ART It is desired in a future hydrogen energy utilizing society to establish a convenient hydrogen energy system from which the hazardous nature of hydrogen explosion is removed to develop the safety of the hydrogen energy system. It is required that the hydrogen gas sensor is configured such that the hydrogen gas amount leaked in air can be detected at once and the structure of the hydrogen gas sensor can be simplified, and the reliability of the hydrogen gas sensor can be enhanced. A conventional hydrogen gas sensor is configured on the detecting principle of semiconductor type, ionization type or combustion type, wherein the hydrogen amount is detected indirectly by utilizing the carrier concentration (semiconductor type), the ion concentration (ionization type) or the reaction heat (combustion type, or the hydrogen gas is burned to measure the vapor pressure) which can be defined as an extensive physical value, thereby to be converted into the corresponding electric value. With the conventional hydrogen gas sensor, therefore, it takes longer period of time to detect the hydrogen gas, e.g., by 100 seconds. Particularly, with a hydrogen gas sensor which is to be utilized in a hydrogen leak alarm system, it is required that the hydrogen gas sensor is configured so as to detect the hydrogen gas concentration within a low concentration range below the explosion limit and shorten the period of time in hydrogen detection. With the conventional (semiconductor type, ionization type or combustion type) hydrogen gas sensor, since the hydrogen gas concentration is detected by utilizing the carrier concentration, the ion concentration or the reaction heat as a hydrogen gas detecting signal, the hydrogen detection requires a large detecting area. In this point of view, the detection precision and sensitivity of the hydrogen gas depends on the structure, the shape and the electrode size of the hydrogen gas sensor, so that the reduction in size of the hydrogen gas sensor is restricted. Moreover, the conventional (semiconductor type, ionization type or combustion type) hydrogen gas sensor may suffer from environmental gases. Particularly, when the hydrogen gas sensor is employed in the atmosphere containing gasoline, hydrocarbon and alcohol which contain hydrogen elements, the hydrogen gas sensor may respond to the hydrogen-based gases, thereby to deteriorate the reliability of the hydrogen gas detection. In this point of view, new electrochemical gas sensors have been developed and practically used, in substitution for the above-mentioned conventional hydrogen gas sensors. The new gas sensors can be classified as electromotive force measuring type hydrogen gas sensors and current detecting type hydrogen gas sensors. With the former type hydrogen gas sensors, as disclosed in Patent Publication No. 1 and 2, a hydrogen gas electrode is prepared as a standard electrode which is configured on the hydrogen standard gas pressure, and a detecting electrode is prepared as an operating electrode for measuring the gas to be detected (hydrogen gas), wherein the difference in potential between the hydrogen gas electrode and the detecting electrode is measured as the output of the hydrogen gas sensor corresponding to the hydrogen gas concentration. With the hydrogen electrode, the atomicity hydrogen exists sufficiently on the electrode surface to form the standard potential of the electrode. Under the condition, when hydrogen gas contacts with the detecting electrode to be dissociated into atomicity hydrogen, the detecting electrode exhibits an electric potential in proportion to the amount of the atomicity hydrogen, and the difference in potential between the hydrogen gas electrode and the detecting electrode is detected as the function of the hydrogen gas concentration. In other words, with the new hydrogen gas sensors, since the detecting hydrogen gas pressure is measured in comparison with the standard hydrogen gas pressure, both of electrodes must be disposed independently in the standard hydrogen gas atmosphere and the detecting gas atmosphere, so that another “standard hydrogen gas pressure room must be provided in addition of the detecting gas pressure room. In this point of view, the hydrogen gas sensors are required to be enlarged in size and the use condition and the like of the hydrogen gas sensors are restricted. With the current detecting type hydrogen gas sensors, the current value is classified as an extensive physical value, so that in order to realize a high precise measurement using the hydrogen gas sensors, the areas or the volumes of the hydrogen gas sensors must be enlarged and external power supplies can be provided for the hydrogen gas sensors. [Patent Publication No. 1] Japanese Patent Application Laid-open No. 2003-270200 [Patent Publication No. 2] Japanese Patent Application Examined Publication No. 5-663 DISCLOSURE OF THE INVENTION Problem To Be Solved By the Invention It is an object of the present invention to provide a new electromotive force type hydrogen gas sensor on electrochemical principle wherein the structure of the hydrogen gas sensor is simplified and the hydrogen gas can be detected high precisely at once. Means For Solving the Problem In order to achieve the object, this invention relates to a hydrogen gas sensor comprising a first electrode, a second electrode and an electrolyte contacting with the first electrode and the second electrode, wherein the first electrode and the second electrode are made of corresponding different materials in chemical potential for hydrogen gas, and the first electrode is made of higher chemical potential material and the second electrode is made of lower chemical potential material, wherein the hydrogen gas is detected on an electromotive force generated between the first electrode and the second electrode. In the present invention, the electrodes of the hydrogen gas sensor are configured so as to contain the corresponding different materials in chemical potential from one another, and the first electrode containing the higher chemical potential material is defined as a detecting electrode and the second electrode containing the lower chemical potential material is defined as a standard electrode. Therefore, when the hydrogen gas sensor is disposed in the same atmosphere containing hydrogen gas, the difference in potential between the first electrode and the second electrode of the hydrogen gas sensor is generated because the electrodes are made of the different materials in chemical potential, respectively. As a result, the hydrogen gas under the same atmosphere can be detected from the difference in potential between the electrodes. According to the hydrogen gas sensor of the present invention, since another standard hydrogen gas pressure room is not required different from the conventional electromotive force measuring type hydrogen gas sensor, the structure of the hydrogen gas sensor can be simplified and the size of the hydrogen gas sensor can be reduced, and also, the hydrogen gas can be detected at once. Herein, the difference in potential between the electrodes of the hydrogen gas sensor is originated from the following relative equation {tilde over (μ)}HM−{tilde over (μ)}HH2=({tilde over (μ)}eII−{tilde over (μ)}eI)−F(φeII−φe1)=−FE (1) wherein the reference character “F” means Faraday constant, and the reference character “E” means EMF value, and {tilde over (μ)}HM, {tilde over (μ)}HH2 are electro-chemical potentials are equal to chemical potentials, respectively of atomicity hydrogen for metal and hydrogen gas. Then, since the terminals [I] and [II] are made of the same copper wire, the electro-chemical potentials of electron are represented by the following equation: {tilde over (μ)}eII={tilde over (μ)}eI (2) Herein, the equation (3) showing the relation between the electrostatic potential and the electromotive force E is employed: φeII−φeI=E (3) wherein φI means an electrostatic of the first electrode and φII means an electrostatic of the second electrode. In this way, the hydrogen gas sensor of the present invention derives the electromotive force corresponding to the chemical potential difference originated from the atomicity hydrogen concentration for both of the electrodes, and detects the hydrogen gas concentration on the electromotive force. As mentioned above, in the present invention, the first electrode is configured as the detecting electrode such that the first electrode contains the higher chemical potential material and the second electrode is configured as the standard electrode such that the second electrode contains the lower chemical potential material, so that the electromotive force E is originated mainly from the electrostatic potential of the first electrode. Since the electromotive force E depends only on the kinds of the electrode materials relating to the chemical potential, not on the size and structure of the electrodes, the hydrogen gas sensor can be reduced in size and simplified in structure. Moreover, since the above-mentioned reaction is created as soon as the hydrogen gas contacts with the first electrode as the detecting electrode, the hydrogen gas detection can be carried out at once. Herein, since the hydrogen gas sensor of the present invention has an inherent spontaneous electromotive force under non-hydrogen atmosphere, the hydrogen gas sensor can have the self-diagnosed function relating to the operationality. In the hydrogen gas sensor, the chemical potential can be associated with the absorption-dissociation active degree of hydrogen gas. That is, the hydrogen gas sensor can be configured such that the electrodes can contain the corresponding different materials in hydrogen absorption-dissociation active degree from one another. In this case, if the first electrode is made of a material of higher absorption-dissociation active degree for hydrogen gas and the second electrode is made of a material of lower absorption-dissociation active degree for hydrogen gas, the first electrode can contain the higher chemical potential material and the second electrode can contain the lower chemical potential material. Concretely, the first electrode can contain a first electrode material which can exhibit a standard electromotive force of 0.8V or over in the cell of H2(−)|50 mol/m3 H2SO4|sample(+), and the second electrode can contain a second electrode material of less than 0.8V in the same cell construction. As the first electrode material can be exemplified Pt, Pt alloy, Pd, Pd alloy. The first electrode can be made of the above-exemplified material or a supported material of the above-exemplified material on a given substrate. The first electrode can be formed in any construction within a scope of the present invention only if the first electrode can function as the detecting electrode for hydrogen gas. As the second electrode material can be exemplified Ni, Ni alloy, Ti, Ti alloy, Cu, Cu alloy, Fe, Fe alloy, Al, Al alloy and organic conductive material. The second electrode can be made of the above-exemplified material, but can be formed in any construction within a scope of the present invention only if the second electrode can function as the standard electrode for the hydrogen gas. A hydrogen gas sensor wherein the detecting electrode for hydrogen gas is made of Pd-H is disclosed in Non-patent Publication No. 1. In this case, since hydrogen gas is partially evaporated from the detecting electrode with time in use, the hydrogen gas sensor can not exhibit the inherent effect/function. In contrast, in the present invention, such a hydrogen-containing electrode is not employed, the above-mentioned problem relating to the use of the hydrogen-containing electrode can be ironed out. [Non-patent Publication No. 1] A. Macker et al., ASTM Spec Tech Publ. No. 962 (June 1998), p 90-97 Moreover, the electrolyte may be made of liquid electrolyte or solid electrolyte, but preferably made of the solid electrolyte. In this case, the handling of the hydrogen gas sensor can be simplified, and can be precisely operated within a temperature range of room temperature (0° C.)-120° C. If a micro heater or the like is installed in the hydrogen gas sensor, the hydrogen gas can be detected easily within a low temperature range of 0° C. or below. As the solid electrolyte can be exemplified phosphorous tungstic acid or phosphorous molybdic acid which has good adhesion for the first electrode and the second electrode and is excellent as an electrolyte for the hydrogen gas sensor. The phosphorous tungstic acid and the phosphorous molybdic can be obtained in the form of powder, so that in the fabrication of the solid electrolyte, the powdery phosphorous tungstic acid or phosphorous molybdic acid is pressed and molded in pellet, and then, processed into the solid electrolyte. However, the pellet is too fragile to be employed for the solid electrolyte as it is. In the use, therefore, some glass wool are added as reinforcing material into the powdery phosphorous tungstic acid or phosphorous molybdic acid in a given solvent (such as ion exchanged water), thereby to be solidified to provide the solid electrolyte. Concretely, the solid electrolyte will be made by the following steps: (1) A powdery raw material for the intended solid electrolyte (such as phosphorous tungstic acid) is melted in a given solvent to be liquidized, (2) A reinforcing material is set into a mold for forming the solid electrolyte, (3) The liquidized raw material is flowed into the mold containing the reinforcing material, (4) The liquidized raw material is solidified to form the solid electrolyte as the primitive form of the hydrogen gas sensor. Herein, it may be that the solid electrolyte is melted and the reinforcing material is added to the melted electrolyte, in substitution for the step (2). In one aspect of the present invention, the hydrogen gas sensor is combined with a voltage comparator to form a hydrogen gas leak alarm system, wherein an electromotive force created on the hydrogen gas detection by the hydrogen gas sensor is compared with a reference voltage of the voltage comparator, and if the electromotive force is larger than the reference voltage, a predetermined alarm is raised. In another aspect of the present invention, a plurality of hydrogen gas sensors are prepared, and arranged on the same substrate to form a hydrogen gas sensor array. According to the hydrogen gas sensor array, hydrogen gas leak from a pipe line series can be detected to form the hydrogen gas leak distribution. If the sensors are arranged densely in series, the sensor output voltage can be enhanced by several times. In still another aspect of the present invention, the hydrogen gas sensor is combined with an electric circuit for detecting the electromotive force from the hydrogen gas sensor, thereby to form a hydrogen gas analyzer which detects hydrogen gas concentration on the electromotive force. Effect of the Invention As described above, since the hydrogen gas sensor of the present invention is configured such that the electrodes are made of the corresponding different material in chemical potential for hydrogen gas and the hydrogen gas is detected by the difference in electromotive force between the electrodes corresponding to the difference in the chemical potential therebetween, the hydrogen gas detection can be carried out at once and the detection performance of hydrogen gas under a low hydrogen gas concentration can be enhanced. Moreover, since the chemical potential and the electromotive force are defined as extensive physical values and do not depend on the size of the electrodes, the hydrogen gas sensor of the present invention can be downsized. Also, since the hydrogen gas sensor can be disposed with the electrodes in the same atmosphere, another standard hydrogen gas pressure room is not required. Therefore, the structure of the hydrogen gas sensor can be simplified and the size of the hydrogen gas sensor can be reduced. In addition, the hydrogen gas sensor can have the inherent spontaneous electromotive force under the non-hydrogen atmosphere, the hydrogen gas sensor can have self-diagnosed function of the operationality. BRIEF EXPLANATION OF THE DRAWINGS FIG. 1 is a structural view illustrating a hydrogen gas sensor according to the present invention, FIG. 2 is a graph showing an electromotive force between the electrodes 11 and 12 of the hydrogen gas sensor illustrated in FIG. 1 when the hydrogen gas sensor is disposed in a hydrogen-containing atmosphere, FIG. 3 is a graph showing the relation between the electrostatic potential and the hydrogen gas concentration at the first electrode of the hydrogen gas sensor illustrated in FIG. 1, FIG. 4 are structural views illustrating another hydrogen gas sensor according to the present invention, FIG. 4(a) being a top plan view of the hydrogen gas sensor, FIG. 4(b) being a side view of the hydrogen gas sensor, FIG. 5 is a structural view illustrating still another hydrogen gas sensor according to the present invention, FIG. 6 is a structural view illustrating a further hydrogen gas sensor according to the present invention, FIG. 7 is a structural view illustrating a still further hydrogen gas sensor according to the present invention, FIG. 8 is a view illustrating the state where the hydrogen gas sensor illustrated in FIG. 7 is integrated, FIG. 9 is a structural view illustrating a hydrogen gas sensor array according to the present invention, FIG. 10 is a view illustrating the state where a plurality of hydrogen gas sensors according to FIG. 7 are arranged and connected to one another in series, FIG. 11 is a block diagram of a hydrogen gas leak alarm system utilizing a hydrogen gas sensor according to the present invention, FIG. 12 is a block diagram of a hydrogen gas leak controlling system utilizing a hydrogen gas sensor according to the present invention, FIG. 13 is a block diagram of a hydrogen gas leak information transmitting system utilizing a hydrogen gas sensor according to the present invention, FIG. 14 is a schematic explanatory view of the structure and operation of the voltage comparator in the systems illustrated in FIGS. 11-13, FIG. 15 is a block diagram of a hydrogen gas analyzer utilizing a hydrogen gas sensor according to the present invention, FIG. 16 is a block diagram of the hydrogen gas leak alarm system with Fail-Safe function, and FIG. 17 is a schematic structural view of a hydrogen gas sensor element with Fail-Safe function. PREFERRED EMBODIMENTS FOR CARRYING OUT THE INVENTION Details, other features and advantages of the present invention will be described hereinafter, with reference to “Preferred Embodiments for Carrying out the Invention”. FIG. 1 is a structural view illustrating a hydrogen gas sensor according to the present invention. Like or similar components are designated by the same reference numerals throughout all of the figures. The hydrogen gas sensor 10 illustrated in FIG. 1 includes a plate-like first electrode 11 and a plate-like second electrode 12, and a solid electrolyte 13 disposed between the electrodes. The first electrode 11 functions as a detecting electrode for hydrogen gas, and the electrostatic potential of the first electrode 11 is varied remarkably when the hydrogen gas contacts with the first electrode 11. The second electrode 12 functions as a standard electrode for the hydrogen gas, and the electrostatic potential of the second electrode 12 is not almost varied or if varied, the variable degree is very small when the hydrogen gas contacts with the second electrode 12. The first electrode 11 is made of a first electrode material of higher chemical potential such as Pt, Pt alloy, Pd, Pd alloy which are higher absorption-dissociation active degree materials. The first electrode 11 can be made of the above-exemplified material or a supported material of the above-exemplified material on a given substrate. The first electrode 11 can be formed in any construction within a scope of the present invention only if the first electrode 11 can function as the detecting electrode for hydrogen gas. The second electrode 12 is made of a second electrode material such as Ni, Ni alloy, Ti, Ti alloy, Cu, Cu alloy, Fe, Fe alloy, Al, Al alloy and organic conductive material which are lower absorption-dissociation active degree materials. The second electrode 12 can be made of the above-exemplified material, but can be formed in any construction within a scope of the present invention only if the second electrode 12 can function as the standard electrode for the hydrogen gas. In this embodiment, the first electrode 11 and the second electrode 12 are formed in plate, but may be formed in any shape such as linear shape, cylindrical shape, disc shape or rectangular shape. The solid electrolyte 13 may be made of an electrolyte such as phosphorous tungstic acid which has higher adhesion for the first electrode 11 and the second electrode 12. The solid electrolyte 13 may contain reinforcing material such as glass wool in addition to the electrolyte such as phosphorous tungstic acid. In this case, the strength of the solid electrolyte 13 can be enhanced and the adhesion of the solid electrolyte 13 for the first electrode 11 and the second electrode 12 can be enhanced. FIG. 2 is a graph showing the variation in electromotive force generated between the electrodes 11 and 12 when the hydrogen gas sensor illustrated in FIG. 1 is disposed in a hydrogen-containing atmosphere. In this case, the first electrode 11 is made of Pt and the second electrode 12 is made of Ni. As is apparent in FIG. 2, in the hydrogen gas sensor, the electromotive force is varied (decreased) within several decimal seconds of less than one second as soon as the hydrogen gas sensor, that is, the electrodes contact with the hydrogen gas. Therefore, the hydrogen gas sensor 10 illustrated in hydrogen gas sensor can detect the hydrogen gas at once. FIG. 3 is a graph showing the relation between the electrostatic potential and the hydrogen gas concentration at the first electrode 11 of the hydrogen gas sensor 10 illustrated in FIG. 1. As is apparent from FIG. 3, the electrostatic potential of the first electrode 11 is decreased uniformly with the hydrogen gas concentration. In contrast, the electrostatic potential of the second electrode 12 of the hydrogen gas sensor 10 does not almost depend on the hydrogen gas concentration. Therefore, an electromotive force of the hydrogen gas sensor 10 is varied with the hydrogen gas concentration, and the hydrogen gas concentration can be detected by the variation of the electromotive force. In this case, the electromotive force of the hydrogen gas sensor is decreased with the increase of the hydrogen gas concentration. In this point of view, the hydrogen gas sensor 10 illustrated in FIG. 1 is excellent in the hydrogen gas detection under minute hydrogen gas concentration (several decimal %). When the environmental temperature of the hydrogen gas sensor 10 illustrated in FIG. 1 is varied within a temperature range of 0-120° C., it is confirmed that the hydrogen gas sensor 10 can operate in the hydrogen gas detection within the temperature range. FIG. 4 is a structural view illustrating another hydrogen gas sensor according to the present invention. In the hydrogen gas sensor illustrated in FIG. 4, a wire-like first electrode 11 and a wire-like second electrode 12 are disposed on an insulating substrate 15 so as to be opposed to one another. The electrodes 11 and 12 can be made by means of sputtering and the like. A solid electrolyte 13 is provided between the first electrode 11 and the second electrode 12 on the insulating substrate 15. In this embodiment, the hydrogen gas sensor can exhibit the same effect/function as the hydrogen gas sensor relating to FIG. 1 if the first electrode 11 and the second electrode 12 are made of corresponding different materials in chemical potential. The first electrode 11 functions as a detecting electrode and is made of higher chemical potential material, and the second electrode 12 functions as a standard electrode and is made of lower chemical potential material. Concretely, the first electrode 11 and the second electrode 12 can be made of the same materials as the corresponding electrodes of the hydrogen gas sensor relating to FIG. 1, respectively. FIG. 5 is a structural view illustrating still another hydrogen gas sensor according to the present invention. In the hydrogen gas sensor 10 illustrated in FIG. 5, a first electrode member 11 and a solid electrolyte 13 are disposed in a cylindrical member 12 made of stainless steel or the like. The solid electrolyte 13 is divided substantially at the center by a gas permeable film 16 and reduced in diameter at the rear portion to form the reducing processed portion 13A. In this case, the cylindrical member 12 also functions as the second electrode corresponding to the standard electrode for the hydrogen gas. On the other hand, the first electrode member 11 functions as the detecting electrode for the hydrogen gas and is made of higher chemical potential material such as Pt. In the hydrogen gas sensor 10 illustrated in FIG. 5, an electromotive force between the first electrode member 11 and the cylindrical member 12 is measured via wires 17 connected to the electrode materials, so that the hydrogen gas can be detected on the electromotive force. FIG. 6 is a structural view illustrating a further hydrogen gas sensor according to the present invention. In the hydrogen gas sensor 10 illustrated in FIG. 6, a first electrode 11 and a solid electrolyte 13 are disposed in a tubule 12 such as a needle. In this case, the tubule 12 functions as the second electrode corresponding to the standard electrode for hydrogen gas, and the first electrode member 11 functions as the detecting electrode for the hydrogen gas. The first electrode 11 is made of higher chemical potential material such as Pt and the second electrode member 12 is made of lower chemical potential material such as Ni. In the hydrogen gas sensor 10 illustrated in FIG. 6, an electromotive force between the first electrode 11 and the tubule 12 is measured via wires 17 connected to the electrode materials, so that the hydrogen gas can be detected on the electromotive force. FIG. 7 is a structural view illustrating a still further hydrogen gas sensor according to the present invention. In the hydrogen gas sensor 10 illustrated in FIG. 7, a tapping screw 12 constitutes the second electrode and a solid electrolyte 13 is charged into the tapping screw 12, and a first electrode 11 is inserted into the tapping screw 12. In this case, hydrogen gas can be detected on an electromotive force generated between the first electrode 11 and the second electrode 12. Herein, the first electrode 11 and the second electrode (tapping screw) 12 may be made of the above-mentioned different materials in chemical potential from one another. FIG. 8 is a view illustrating the state where the hydrogen gas sensor illustrated in FIG. 7 is integrated As illustrated in FIG. 5, when the second electrode is made of such a cylindrical member, the second electrode (cylindrical member) may be formed in porosity or mesh in view of the permeability of the hydrogen gas. FIG. 9 is a structural view illustrating a hydrogen gas sensor array according to the present invention. In the hydrogen gas sensor array illustrated in FIG. 9, a plurality of hydrogen gas sensors according to FIG. 4 are arranged on an insulating substrate 14. In this case, since each hydrogen gas sensor can detect hydrogen gas, the array can detect the hydrogen gas depending on the detecting position. Therefore, the array is suitable for hydrogen gas leak in the wide area such as a hydrogen gas station. If the hydrogen gas sensors are arranged in high density, the array can be constituted as a leak detector using each hydrogen gas sensor as a probe. In the array illustrated in FIG. 9, when the hydrogen gas sensors are connected to one another in series as illustrated in FIG. 10, the electromotive forces from the hydrogen gas sensors are added up to provide larger detecting voltage. The hydrogen gas sensor illustrated in FIG. 1, 4-8 or the hydrogen gas sensor array illustrated in FIG. 9, 10 can be installed in a suitable electric circuit, and the detecting voltage is detected via the electric circuit. If the hydrogen gas sensor is installed into the electric circuit, the electromotive force of the hydrogen gas sensor becomes constant under non-hydrogen atmosphere, which is defined as an electrostatic potential between the first electrode and the second electrode. In this case, therefore, if the electromotive force is measured via the electric circuit, the operating reliability of the hydrogen gas sensor can be appropriately confirmed, so that the hydrogen gas sensor can have the self-diagnosed function. FIGS. 11-13 are block diagrams of a hydrogen gas leak alarm system, a hydrogen gas leak controlling system and a hydrogen gas leak transmitting system which utilize hydrogen gas sensors according to the present invention. FIG. 11 is a block diagram of the hydrogen gas leak alarm system utilizing the hydrogen gas sensor of the present invention. The electromotive force variation as a hydrogen gas detecting information from the hydrogen gas sensor 10 is input into an input buffer 21 of high input impedance, converted in impedance and signal level, and input into a voltage comparator 22. In the voltage comparator 22, the input signal is compared with the reference voltage of a standard power supply 23, and the thus obtained compared result is output via an output buffer 24 provided at the next stage, and input into an alarm buzzer or a light-emitting diode panel (not shown), thereby constituting the hydrogen gas leak alarm system. FIG. 12 is a block diagram of the hydrogen gas leak controlling system utilizing the hydrogen gas sensor of the present invention. In the system, when hydrogen gas over a predetermined level is detected by the hydrogen gas sensor, the hydrogen gas leak information is known via a light-emitting diode panel and at the same time, an external relay or magnetic valve is operated. The electromotive force variation as a hydrogen gas detecting information from the hydrogen gas sensor 10 is input into an input buffer 21 of high input impedance, converted in impedance and signal level, and input into a voltage comparator 22. In the voltage comparator 22, the input signal is compared with the reference voltage of a standard power supply 23, and the thus obtained compared result is output via an output buffer 24 provided at the next stage, and input into an alarm buzzer for warning hydrogen gas leak, a light-emitting diode panel (not shown) for displaying the hydrogen gas leak or an Exit Control System for operating an external relay or magnetic valve via a TTL OUT, thereby constituting the hydrogen gas leak alarm system. FIG. 13 is a block diagram of the hydrogen gas leak transmitting system utilizing the hydrogen gas sensor of the present invention. In the system, when hydrogen gas over a predetermined level is detected by the hydrogen gas sensor, the hydrogen gas leak information is transmitted to a local area via a wireless LAN or a BBS by using a computer. The electromotive force variation as a hydrogen gas detecting information from the hydrogen gas sensor 10 is input into an input buffer 21 of high input impedance, converted in impedance and signal level, and input into a voltage comparator 22. In the voltage comparator 22, the input signal is compared with the reference voltage of a standard power supply 23. The thus obtained compared result is output via an output buffer 24 provided at the next stage, converted in signal level (Wave Form), transmitted to a host computer via an RS232C port and the like as a typical serial communication of PC, and transmitted to a local area via a wireless LAN or a BBS. FIG. 14 is a schematic explanatory view of the structure and operation of the voltage comparator in the systems illustrated in FIGS. 11-13. The voltage comparator 22 is a most important component among all of the components of the systems. When a voltage over the reference voltage is output from the input buffer 21 and input into the voltage comparator 22, the output voltage of the voltage comparator 22, which is almost equal to the power supply voltage, is on, and when a voltage below the reference voltage is output from the input buffer 21 and input into the voltage comparator 22, the output voltage of the voltage comparator 22 is off (becomes almost zero) from on. Conventionally, the voltage comparison would be carried out by using an exclusive IC installed in the voltage comparator. In the present invention, in contrast, in order to simplify the electric circuit construction and realize the absolute voltage comparison, a Shumitt inverter (Shumitt circuit) as a digital IC is installed in the voltage comparator. In this case, therefore, the voltage comparator is utilized as an analog voltage comparator by using the threshold voltage of the Shumitt circuit as a reference voltage standard. Generally, the Shumitt inverter is used in a digital circuit for realizing digital functions such as waveform shaping of digital waveform with noise. In this embodiment, the digital functions of the Shumitt inverter are utilized as analog functions in the voltage comparator 22. In this point of view, the difference between the threshold voltages when the voltage comparator is on from off and off from on is utilized to determine the standard voltage in analog. Therefore, the external controlling circuit can not become unstable around the threshold voltage, thereby to be stabilized. Moreover, since the threshold voltage of the Shumitt voltage corresponds to the reference standard voltage of the voltage comparator 22, the construction of the voltage comparator 22 can be simplified without an external standard voltage power supply and the operation of the voltage comparator 22 can be carried out stably and absolutely. FIG. 15 is a block diagram of a hydrogen gas analyzer utilizing a hydrogen gas sensor according to the present invention. In the hydrogen gas analyzer illustrated in FIG. 15, the electromotive force as a hydrogen gas detecting information from the hydrogen gas sensor 10 is converted in impedance level and signal level by an input buffer 21 of higher input impedance, and input into a Data Table Reference circuit 25 provided at the next stage. In the Data Table Reference circuit 25 is input a Data Table 26 relating to the hydrogen gas concentrations and the electromotive forces of the hydrogen gas sensor, which the Data Table 26 is compared with an electromotive force input into the Data Table Reference circuit 25 to display the hydrogen gas concentration corresponding the input electromotive force via a Display Driver 27. FIG. 16 is a block diagram of the hydrogen gas leak alarm system with Fail-Safe function. In this embodiment, the Fail-Safe functions (units 2 and 3) are combined with the hydrogen gas leak alarm system (unit 1) or the like. In the unit 1, the electromotive force variation as a hydrogen gas detecting information from the hydrogen gas sensor 10 is input into an input buffer 21 of high input impedance, converted in impedance and signal level, and input into a voltage comparator 22. In the voltage comparator 22, the input signal is compared with the reference voltage of a standard power supply 23, and the thus obtained compared result is output to a logical operating circuit 34 via an output buffer 24 provided at the next stage. In the unit 2, the Fail-Safe function is applied to the hydrogen gas sensor element, the input buffer and the voltage comparator. A photo sensor 29 is installed in the hydrogen gas sensor element and monitors the contamination of the sensor component of the hydrogen gas sensor element from external environment. An information from the photo sensor 29 is input in an input buffer 30 of high input impedance, converted in impedance and signal level, and input in a voltage comparator 31. In the voltage comparator 31, the input signal is compared with the reference voltage of a standard power supply 32, and the thus obtained compared result is output to a logical operating circuit 34 via an Output Driver 33 provided at the next stage. In the logical operating circuit 34, the compared result relating to the input signal and the reference voltage is calculated, and an alarm buzzer 35 is switched off only when no hydrogen gas leak information is detected from the output buffer 24 and the operation of the photo sensor 29 is normal, that is, both of the output buffer 24 and the photo sensor 29 are stationary states. Except the stationary states of the output buffer 24 and the photo sensor 29, for example, when the hydrogen gas sensor 10 puts out a hydrogen gas detecting signal and/or the photo sensor 29 detects contamination from the external environment, the alarm buzzer 35 is switched on. In the unit 3, the Fail-Safe function is applied to the light-emitting display for warning and the alarm buzzer. The operating conditions of the light-emitting display and the alarm buzzer are visually checked via a switch 37 for visual check or when the hydrogen gas leak alarm system is switched on. FIG. 17 is a schematic structural view of a hydrogen gas sensor element with Fail-Safe function. The Fail-Safe function relating to the hydrogen gas leak alarm system can be applied to the hydrogen gas sensor detecting section by calculating the signal from the hydrogen gas detecting section at the logical operating circuit 34 via the units 2 and 3. The Fail-Safe function can be also applied to the logical operating circuit 34 via another circuit which is provided in parallel with the circuit 34. In FIG. 17, the Fail-Safe function is applied to the hydrogen gas detecting section, and the LED signal from the LED 36 is transmitted via a protective mesh 37 and detected at the photo sensor 29 via a translucent mesh 38. When the translucent mesh 38 is contaminated from external environment and thus, shut down, the signal from the photo sensor 29 is off, so that the photo sensor 29 is shut down against hydrogen gas due to the contamination. Since the hydrogen gas sensor element functions as an active element with spontaneous electromotive force under non-hydrogen gas atmosphere, the operating condition of the sensor element can be monitored by detecting the spontaneous electromotive voltage. Although the present invention was described in detail with reference to the above examples, this invention is not limited to the above disclosure and every kind of variation and modification may be made without departing from the scope of the present invention.
<SOH> BACKGROUND OF THE ART <EOH>It is desired in a future hydrogen energy utilizing society to establish a convenient hydrogen energy system from which the hazardous nature of hydrogen explosion is removed to develop the safety of the hydrogen energy system. It is required that the hydrogen gas sensor is configured such that the hydrogen gas amount leaked in air can be detected at once and the structure of the hydrogen gas sensor can be simplified, and the reliability of the hydrogen gas sensor can be enhanced. A conventional hydrogen gas sensor is configured on the detecting principle of semiconductor type, ionization type or combustion type, wherein the hydrogen amount is detected indirectly by utilizing the carrier concentration (semiconductor type), the ion concentration (ionization type) or the reaction heat (combustion type, or the hydrogen gas is burned to measure the vapor pressure) which can be defined as an extensive physical value, thereby to be converted into the corresponding electric value. With the conventional hydrogen gas sensor, therefore, it takes longer period of time to detect the hydrogen gas, e.g., by 100 seconds. Particularly, with a hydrogen gas sensor which is to be utilized in a hydrogen leak alarm system, it is required that the hydrogen gas sensor is configured so as to detect the hydrogen gas concentration within a low concentration range below the explosion limit and shorten the period of time in hydrogen detection. With the conventional (semiconductor type, ionization type or combustion type) hydrogen gas sensor, since the hydrogen gas concentration is detected by utilizing the carrier concentration, the ion concentration or the reaction heat as a hydrogen gas detecting signal, the hydrogen detection requires a large detecting area. In this point of view, the detection precision and sensitivity of the hydrogen gas depends on the structure, the shape and the electrode size of the hydrogen gas sensor, so that the reduction in size of the hydrogen gas sensor is restricted. Moreover, the conventional (semiconductor type, ionization type or combustion type) hydrogen gas sensor may suffer from environmental gases. Particularly, when the hydrogen gas sensor is employed in the atmosphere containing gasoline, hydrocarbon and alcohol which contain hydrogen elements, the hydrogen gas sensor may respond to the hydrogen-based gases, thereby to deteriorate the reliability of the hydrogen gas detection. In this point of view, new electrochemical gas sensors have been developed and practically used, in substitution for the above-mentioned conventional hydrogen gas sensors. The new gas sensors can be classified as electromotive force measuring type hydrogen gas sensors and current detecting type hydrogen gas sensors. With the former type hydrogen gas sensors, as disclosed in Patent Publication No. 1 and 2, a hydrogen gas electrode is prepared as a standard electrode which is configured on the hydrogen standard gas pressure, and a detecting electrode is prepared as an operating electrode for measuring the gas to be detected (hydrogen gas), wherein the difference in potential between the hydrogen gas electrode and the detecting electrode is measured as the output of the hydrogen gas sensor corresponding to the hydrogen gas concentration. With the hydrogen electrode, the atomicity hydrogen exists sufficiently on the electrode surface to form the standard potential of the electrode. Under the condition, when hydrogen gas contacts with the detecting electrode to be dissociated into atomicity hydrogen, the detecting electrode exhibits an electric potential in proportion to the amount of the atomicity hydrogen, and the difference in potential between the hydrogen gas electrode and the detecting electrode is detected as the function of the hydrogen gas concentration. In other words, with the new hydrogen gas sensors, since the detecting hydrogen gas pressure is measured in comparison with the standard hydrogen gas pressure, both of electrodes must be disposed independently in the standard hydrogen gas atmosphere and the detecting gas atmosphere, so that another “standard hydrogen gas pressure room must be provided in addition of the detecting gas pressure room. In this point of view, the hydrogen gas sensors are required to be enlarged in size and the use condition and the like of the hydrogen gas sensors are restricted. With the current detecting type hydrogen gas sensors, the current value is classified as an extensive physical value, so that in order to realize a high precise measurement using the hydrogen gas sensors, the areas or the volumes of the hydrogen gas sensors must be enlarged and external power supplies can be provided for the hydrogen gas sensors. [Patent Publication No. 1] Japanese Patent Application Laid-open No. 2003-270200 [Patent Publication No. 2] Japanese Patent Application Examined Publication No. 5-663
20060406
20120117
20060824
75934.0
G01N2726
0
OLSEN, KAJ K
HYDROGEN GAS SENSOR
SMALL
0
ACCEPTED
G01N
2,006
10,534,650
ACCEPTED
Benzofuran derivatives, process for their preparation and intermediates thereof
Compound of formula (I) wherein A is selected from pyridin-2-yl or thiazol-2-yl and R1, R2 and R3 are as described in the specification and their use in the treatment or prevention of a disease or medical conditions mediated through glucokinase.
1. A compound of formula (I): wherein: Ring A is pyridin-2-yl or thiazol-2-yl; wherein said pyridin-2-yl or thiazol-2-yl is optionally substituted on carbon by one or more groups selected from R4; one of R1 and R2 is hydrogen and the other is hydrogen or C1-4alkyl; wherein R1 and R2 are optionally substituted on carbon by one or more groups selected from R5; R3 is selected from C1-4alkyl, C1-4alkoxy, carbocyclyl, heterocyclyl, carbocyclyloxy and heterocyclyloxy; wherein R3 is independently optionally substituted on carbon by one or more groups selected from R6; and wherein if said heterocyclyl contains an —NH— moiety that nitrogen is optionally substituted by C1-4alkyl; R4 is selected from halo, carboxy and C1-4alkyl; R5 and R6 are independently selected from halo, C1-4alkyl, C1-4alkoxy, N-(C1-4alkyl)amino, N,N-(C1-4alkyl)2amino, carbocyclyl, heterocyclyl, carbocyclyloxy, heterocyclyloxy and carbocyclylidenyl;. wherein R5 and R6 are independently optionally substituted on carbon by one or more R7; and wherein if said heterocyclyl contains an —NH— moiety that nitrogen is optionally substituted by C1-4alkyl; R7 is selected from halo, carboxy, methyl, ethyl, methoxy, ethoxy, methylamino, ethylamino, dimethylamino, diethylamino and N-methyl-N-ethylamino; or a salt, solvate or pro-drug thereof. 2. A compound according to claim 1 wherein Ring A is unsubstituted or is substituted by carboxy. 3. A compound according to claim 1 wherein one of R1 and R2 is hydrogen and the other is hydrogen or C1-4alkyl. 4. A compound according to claim 1 wherein R3 is selected from C1-4alkoxy; wherein R3 is independently optionally substituted on carbon by one or more groups selected from R6. 5. A compound according to claim 1 wherein R3 is selected from 2-fluorobenzyloxy, 5-methylisoxazol-3-ylmethoxy and 2-thien-3-ylethoxy 6. A compound according to claim 1 selected from: 2-methyl-4-isobutoxy-6-[N-(5-carboxypyridin-2-yl)carbamoyl]benzofuran; 2-methyl-4-(2-fluorophenylmethoxy)-6-[N-(5-carboxypyridin-2-yl)carbamoyl]benzofuran; 2-methyl-4-isobutoxy-6-[N-(5-carboxythiazol-2-yl)carbamoyl]benzofuran; 2-methyl-4-(5-methylisoxazol-3-ylmethoxy)-6-[N-(5-carboxypyridin-2-yl)carbamoyl]benzofuran; 4-(2-fluorophenylmethoxy)-6-[N-(5-carboxypyridin-2-yl)carbamoyl]benzofuran; 4-(5-methylisoxazol-3-ylmethoxy)-6-[N-(5-carboxypyridin-2-yl)carbamoyl]benzofuran; 2-methyl-4-(thien-2-ylethoxy)-6-[N-(5-carboxypyridin-2-yl)carbamoyl]benzofuran; and 2-methyl-4-isobutoxy-6-[N-(thiazol-2-yl)carbamoyl]benzofuran; or a salt, solvate or pro-drug thereof. 7. A pharmaceutical composition comprising a compound according to any one of claims 1 to 6, or a salt, pro-drug or solvate thereof, together with a pharmaceutically acceptable diluent or carrier. 8. A method of treating a disease mediated through glucokinase, comprising administering a compound according to any one of claims 1 to 6. 9. A process for preparing a compound of formula (I): wherein: Ring A is pyridin-2-yl or thiazol-2-yl; wherein said pyridin-2-yl or thiazol-2-yl is optionally substituted on carbon by one or more groups selected from R4; one of R1 and R2 is hydrogen and the other is hydrogen or C1-4alkyl; wherein R1 and R2 are optionally substituted on carbon by one or more groups selected from R5; R3 is selected from C1-4alkyl, C1-4alkoxy, carbocyclyl, heterocyclyl, carbocyclyloxy and heterocyclyloxy; wherein R3 is independently optionally substituted on carbon by one or more groups selected from R6; and wherein if said heterocyclyl contains an —NH— moiety that nitrogen is optionally substituted by C1-4alkyl; R4 is selected from halo, carboxy and C1-4alkyl; R5 and R6 are independently selected from halo, C1-4alkyl, C1-4alkoxy, N-(C1-4alkyl)amino, N,N-(C1-4alkyl)2amino, carbocyclyl, heterocyclyl, carbocyclyloxy, heterocyclyloxy and carbocyclylidenyl; wherein R5 and R6 are independently optionally substituted on carbon by one or more R7; and wherein if said heterocyclyl contains an —NH— moiety that nitrogen is optionally substituted by C1-4alkyl; R7 is selected from halo, carboxy, methyl, ethyl, methoxy, ethoxy, methylamino, ethylamino, dimethylamino, diethylamino and N-methyl-N-ethylamino or a salt, solvate or pro-drug thereof, which process comprises: Process 1): reacting an acid of formula (II): or an activated derivative thereof; with a compound of formula (III); or Process 2) for compounds of formula (I) wherein R4 is carboxy; deprotecting a compound of formula (III): wherein RxC(O)O— is an ester group; and optionally: i) converting a compound of the formula (I) into another compound of the formula (I); ii) removing any protecting groups; iii) forming a salt, solvate or pro-drug thereof, or a combination thereof. 10. A compound of formula (III): wherein: RxC(O)O— is an ester group; Ring A is pyridin-2-yl or thiazol-2-yl; wherein said pyridin-2-yl or thiazol-2-yl is optionally substituted on carbon by one or more groups selected from R4; and one of R1 and R2 is hydrogen and the other is hydrogen or C1-4alkyl; wherein R1 and R2 are optionally substituted on carbon by one or more groups selected from R5; R3 is selected from C1-4alkyl, C1-4alkoxy, carbocyclyl, heterocyclyl, carbocyclyloxy and heterocyclyloxy; wherein R3 is independently optionally substituted on carbon by one or more groups selected from R6; and wherein if said heterocyclyl contains an —NH— moiety that nitrogen is optionally substituted by C1-4alkyl; R4 is selected from halo, carboxy and C1-4alkyl; R5 and R6 are independently selected from halo, C1-4alkyl, C1-4alkoxy, N-(C1-4alkyl)amino, N,N-(C1-4alkyl)2amino, carbocyclyl, heterocyclyl, carbocyclyloxy, heterocyclyloxy and carbocyclylidenyl; wherein R5 and R6 are independently optionally substituted on carbon by one or more R7; and wherein if said heterocyclyl contains an —NH— moiety that nitrogen is optionally substituted by C1-4alkyl; and R7 is selected from halo, carboxy, methyl, ethyl, methoxy, ethoxy, methylamino, ethylamino, dimethylamino, diethylamino and N-methyl-N-ethylamino.
The present invention relates to chemical compounds useful in the treatment or prevention of a disease or medical conditions mediated through glucokinase (GLK), leading to a decreased glucose threshold for insulin secretion. In addition the compounds are predicted to lower blood glucose by increasing hepatic glucose uptake. Such compounds may have utility in the treatment of type 2 diabetes and obesity. The invention also relates to processes for preparing said compounds, pharmaceutical compositions comprising said compounds, and the use of such a compound in the conditions described above. In the pancreatic β-cell and liver parenchymal cells the main plasma membrane glucose transporter is GLUT2. Under physiological glucose concentrations the rate at which GLUT2 transports glucose across the membrane is not rate limiting to the overall rate of glucose uptake in these cells. The rate of glucose uptake is limited by the rate of phosphorylation of glucose to glucose-6-phosphate (G-6-P) which is catalysed by glucokinase (GLK) [1]. GLK has a high (6-10 mM) Km for glucose and is not inhibited by physiological concentrations of G-6-P [1]. GLK expression is limited to a few tissues and cell types, most notably pancreatic β-cells and liver cells (hepatocytes) [1]. In these cells GLK activity is rate limiting for glucose utilisation and therefore regulates the extent of glucose induced insulin secretion and hepatic glycogen synthesis. These processes are critical in the maintenance of whole body glucose homeostasis and both are dysfunctional in diabetes [2]. In one sub-type of diabetes, type 2 maturity-onset diabetes of the young (MODY-2), the diabetes is caused by GLK loss of function mutations [3, 4]. Hyperglycaemia in MODY-2 patients results from defective glucose utilisation in both the pancreas and liver [5]. Defective glucose utilisation in the pancreas of MODY-2 patients results in a raised threshold for glucose stimulated insulin secretion. Conversely, rare activating mutations of GLK reduce this threshold resulting in familial hyperinsulinism [6, 7]. In addition to the reduced GLK activity observed in MODY-2 diabetics, hepatic glucokinase activity is also decreased in type 2 diabetics [8]. Importantly, global or liver selective overexpression of GLK prevents or reverses the development of the diabetic phenotype in both dietary and genetic models of the disease [9-12]. Moreover, acute treatment of type 2 diabetics with fructose improves glucose tolerance through stimulation of hepatic glucose utilisation [13]. This effect is believed to be mediated through a fructose induced increase in cytosolic GLK activity in the hepatocyte by the mechanism described below [13]. Hepatic GLK activity is inhibited through association with GLK regulatory protein (GLKRP). The GLK/GLKRP complex is stabilised by fructose-6-phosphate (F6P) binding to the GLKRP and destabilised by displacement of this sugar phosphate by fructose-1-phosphate (F1P). F1P is generated by fructokinase mediated phosphorylation of dietary fructose. Consequently, GLK/GLKRP complex integrity and hepatic GLK activity is regulated in a nutritionally dependent manner as F6P is elevated in the post-absorptive state whereas F1P predominates in the post-prandial state. In contrast to the hepatocyte, the pancreatic β-cell expresses GLK in the absence of GLKRP. Therefore, β-cell GLK activity is regulated exclusively by the availability of its substrate, glucose. Small molecules may activate GLK either directly or through destabilising the GLK/GLKRP complex. The former class of compounds are predicted to stimulate glucose utilisation in both the liver and the pancreas whereas the latter are predicted to act exclusively in the liver. However, compounds with either profile are predicted to be of therapeutic benefit in treating type 2 diabetes as this disease is characterised by defective glucose utilisation in both tissues. GLK and GLKRP and the KATP channel are expressed in neurones of the hypothalamus, a region of the brain that is important in the regulation of energy balance and the control of food intake [14-18]. These neurones have been shown to express orectic and anorectic neuropeptides [15, 19, 20] and have been assumed to be the glucose-sensing neurones within the hypothalamus that are either inhibited or excited by changes in ambient glucose concentrations [17, 19, 21, 22]. The ability of these neurones to sense changes in glucose levels is defective in a variety of genetic and experimentally induced models of obesity [23-28]. Intracerebroventricular (icv) infusion of glucose analogues, that are competitive inhibitors of glucokinase, stimulate food intake in lean rats [29, 30]. In contrast, icv infusion of glucose suppresses feeding [31]. Thus, small molecule activators of GLK may decrease food intake and weight gain through central effects on GLK. Therefore, GLK activators may be of therapeutic use in treating eating disorders, including obesity, in addition to diabetes. The hypothalamic effects will be additive or synergistic to the effects of the same compounds acting in the liver and/or pancreas in normalising glucose homeostasis, for the treatment of Type 2 diabetes. Thus the GLK/GLKRP system can be described as a potential “diabesity” target (of benefit in both Diabetes and Obesity). In WO 00/58293 and WO 01/44216 (Roche), a series of benzylcarbamoyl compounds are described as glucokinase activators. The mechanism by which such compounds activate GLK is assessed by measuring the direct effect of such compounds in an assay in which GLK activity is linked to NADH production, which in turn is measured optically—see details of the in vitro assay described below. Compounds of the present invention may activate GLK directly or may activate GLK by inhibiting the interaction of GLKRP with GLK. Many compounds of the present invention may show favourable selectivity compared to known GLK activators. International application number: WO03/000267 describes a group of benzoyl amino pyridyl carboxylic acids which are activators of the enzyme glucokinase (GLK), International application number WO03/015774 describes a group of benzoylamino heterocycle compounds as glucokinase activators and International application number WO03/000262 describes a group or vinyl phenyl derivatives as glucokinase activators. According to the present invention there is provided a compound of formula (I): wherein: Ring A is pyridin-2-yl or thiazol-2-yl; wherein said pyridin-2-yl or thiazol-2-yl may be optionally substituted on carbon by one or more groups selected from R4; One of R1 and R2 is hydrogen and the other is hydrogen or C1-4alkyl; wherein R1 and R2 may be substituted on carbon by one or more groups selected from R5; R3 is selected from C1-4alkyl, C1-4alkoxy, carbocyclyl, heterocyclyl, carbocyclyloxy and heterocyclyloxy; wherein R3 may be independently optionally substituted on carbon by one or more groups selected from R6; and wherein if said heterocyclyl contains an —NH— moiety that nitrogen may be optionally substituted by C1-4alkyl; R4 is selected from halo, carboxy and C1-4alkyl; R5 and R6 are independently selected from halo, C1-4alkyl, C1-4alkoxy, N-(C1-4alkyl)amino, N,N-(C1-4alkyl)2amino, carbocyclyl, heterocyclyl, carbocyclyloxy, heterocyclyloxy and carbocyclylidenyl; wherein R5 and R6 may be independently optionally substituted on carbon by one or more R7; and wherein if said heterocyclyl contains an —NH— moiety that nitrogen may be optionally substituted by C1-4alkyl; R7 is selected from halo, carboxy, methyl, ethyl, methoxy, ethoxy, methylamino, ethylamino, dimethylamino, diethylamino and N-methyl-N-ethylamino; or a salt, solvate or pro-drug thereof. Compounds of formula (I) may form salts which are within the ambit of the invention. Pharmaceutically acceptable salts are preferred although other salts may be useful in, for example, isolating or purifying compounds. The term “halo” includes chloro, bromo, fluoro and iodo; preferably chloro, bromo and fluoro; most preferably fluoro. In this specification the term “alkyl” includes both straight and branched chain alkyl groups. For example, “C1-4alkyl” and “C1-6alkyl” includes propyl, isopropyl and t-butyl. A “carbocyclyl” is a saturated, partially saturated or unsaturated, mono or bicyclic carbon ring that contains 3-12 atoms; wherein a —CH2— group can optionally be replaced by a —C(O)—. Preferably “carbocyclyl” is a monocyclic ring containing 5 or 6 atoms or a bicyclic ring containing 9 or 10 atoms. Suitable values for “carbocyclyl” include cyclopropyl, cyclobutyl, 1-oxocyclopentyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, phenyl, naphthyl, tetralinyl, indanyl or 1-oxoindanyl. Particularly “carbocyclyl” is cyclohexyl or phenyl. Most particularly phenyl. A “heterocyclyl” is a saturated, partially saturated or unsaturated, monocyclic or bicyclic ring containing 3-12 atoms of which at least one atom is chosen from nitrogen, sulphur or oxygen, wherein a —CH2— group can optionally be replaced by a —C(O)— or sulphur atoms in a heterocyclic ring may be oxidised to S(O) or S(O)2. A heterocyclyl ring may, unless otherwise specified, be carbon or nitrogen linked, unless linking via nitrogen leads to a quaternary nitrogen. Preferably a “heterocyclyl” is a saturated, partially saturated or unsaturated, monocyclic or bicyclic ring wherein each ring contains 5 or 6 atoms of which 1 to 3 atoms are nitrogen, sulphur or oxygen, which may, unless otherwise specified, be carbon or nitrogen linked, wherein a —CH2— group can optionally be replaced by a —C(O)— or sulphur atoms in a heterocyclic ring may be oxidised to S(O) or S(O)2 groups. More preferably a “heterocyclyl” is a saturated, partially saturated or unsaturated, monocyclic ring wherein each ring contains 5 or 6 atoms of which 1 to 3 atoms are nitrogen, sulphur or oxygen. Further preferably a “heterocyclyl” is a partially saturated or unsaturated monocyclic ring wherein each ring contains 5 or 6 atoms, preferably 5 atoms, of which 1 to 2 atoms are nitrogen, sulphur or oxygen. Examples and suitable values of the term “heterocyclyl” are thiazolidinyl, pyrrolidinyl, pyrrolinyl, 2-pyrrolidonyl, 2,5-dioxopyrrolidinyl, 2-benzoxazolinonyl, 1,1-dioxotetrahydrothienyl, 2,4-dioxoimidazolidinyl, 2-oxo-1,3,4-(4-triazolinyl), 2-oxazolidinonyl, 5,6-dihydrouracilyl, 1,3-benzodioxolyl, 1,2,4-oxadiazolyl, 2-azabicyclo[2.2.1]heptyl, 4-thiazolidonyl, morpholino, 2-oxotetrahydrofuranyl, tetrahydrofuranyl, 2,3-dihydrobenzofuranyl, benzothienyl, isoxazolyl, tetrahydropyranyl, piperidyl, 1-oxo-1,3-dihydroisoindolyl, piperazinyl, thiomorpholino, 1,1-dioxothiomorpholino, tetrahydropyranyl, 1,3-dioxolanyl, homopiperazinyl, thienyl, isoxazolyl, imidazolyl, pyrrolyl, thiazolyl, thiadiazolyl, isothiazolyl, 1,2,4-triazolyl, 1,2,3-triazolyl, pyranyl, indolyl, pyrimidyl, thiazolyl, pyrazinyl, pyridazinyl, pyridyl, 4-pyridonyl, quinolyl and 1-isoquinolonyl. Preferably the term “heterocyclyl” refers to monocyclic heterocyclic rings with 5- or 6-membered systems, such as isoxazolyl, pyrrolidinyl, 2-pyrrolidonyl, 2,5-dioxopyrrolidinyl, morpholino, tetrahydrofuranyl, piperidyl, piperazinyl, thiomorpholino, tetrahydropyranyl, thienyl, imidazolyl, 1,2,4-triazolyl, 1,3,4-triazolyl, indolyl, thiazolyl, thiadiazolyl, pyrazinyl, pyridazinyl and pyridyl. Preferred examples of 5/6 and 6/6 bicyclic ring systems include benzofuranyl, benzimidazolyl, benzthiophenyl, benzthiazolyl, benzisothiazolyl, benzoxazolyl, benzisoxazolyl, pyridoimidazolyl, pyrimidoimidazolyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, phthalazinyl, cinnolinyl and naphthyridinyl. Examples of C1-4alkyl and C1-6alkyl include methyl, ethyl, propyl, isopropyl, sec-butyl and tert-butyl; examples of C1-4alkoxy include methoxy, ethoxy, propoxy and tert-butoxy; examples of N-(C1-4alkyl)amino include methylamino, ethylamino and isopropylamino; examples of N,N-(C1-4alkyl)2amino include dimethylamino, N-methyl-N-ethylamino and N-ethyl-N-isopropylamino; examples of carbocyclylidenyl are cyclopentylidenyl and 2,4-cyclohexadien-1-ylidenyl. It is to be understood that, insofar as certain of the compounds of formula (I) defined below may exist in optically active or racemic forms by virtue of one or more asymmetric carbon atoms, the invention includes in its definition any such optically active or racemic form which possesses the property of stimulating GLK directly or inhibiting the GLK/GLKRP interaction. The synthesis of optically active forms may be carried out by standard techniques of organic chemistry well known in the art, for example by synthesis from optically active starting materials or by resolution of a racemic form. It is also to be understood that certain compounds may exist in tautomeric forms and that the invention also relates to any and all tautomeric forms of the compounds of the invention which activate GLK. Suitable compounds of formula (I) are those wherein any one or more of the following apply. Such values may be used where appropriate with any of the definitions, claims or embodiments defined hereinbefore or hereinafter. Ring A is pyridin-2-yl optionally substituted on carbon by one or more groups selected from R4. Ring A is thiazol-2-yl optionally substituted on carbon by one or more groups selected from R4. Ring A is pyridin-2-yl or thiazol-2-yl; wherein said pyridin-2-yl or thiazol-2-yl may be optionally substituted on carbon by one or more groups selected from R4 wherein: R4 is carboxy. Ring A is unsubstituted or is substituted by carboxy. Ring A is pyridin-2-yl, 5-carboxypyridin-2-yl, thiazol-2-yl or 5-carboxythiazol-2-yl. Ring A is 5-carboxypyridin-2-yl, thiazol-2-yl or 5-carboxythiazol-2-yl. R1 is hydrogen and R2 is C1-4alkyl; wherein R2 may be substituted on carbon by one or more groups selected from R5. R1 is C1-4alkyl and R2 is hydrogen; wherein R1 may be substituted on carbon by one or more groups selected from R5. One of R1 and R2 is hydrogen and the other is hydrogen or C1-4alkyl. R1 is hydrogen or C1-4alkyl and R2 is hydrogen. Both R1 and R2 are hydrogen. R1 is methyl or hydrogen and R2 is hydrogen. R3 is selected from C1-4alkoxy and carbocyclyloxy; wherein R3 may be independently optionally substituted on carbon by one or more groups selected from R6; wherein: R6 is selected from halo, carbocyclyl, heterocyclyl, carbocyclylidenyl; wherein R6 may be optionally substituted on carbon by one or more R7; wherein: R7 is selected from halo and methyl. R3 is selected from C1-4alkoxy; wherein R3 may be independently optionally substituted on carbon by one or more groups selected from R6; wherein: R6 is selected from carbocyclyl and heterocyclyl; wherein R may be optionally substituted on carbon by one or more R7; wherein: R7 is selected from halo and methyl. R3 is selected from methoxy, ethoxy, iso-butoxy, phenoxy and benzocyclopent-1-yloxy; wherein R3 may be independently optionally substituted on carbon by one or more groups selected from R6; wherein: R6 is selected from fluoro, phenyl, isoxazolyl, thienyl and cyclopentlyidenyl; wherein R6 may be optionally substituted on carbon by one or more R7; wherein: R7 is selected from fluoro and methyl. R3 is selected from methoxy, ethoxy and iso-butoxy; wherein R3 may be independently optionally substituted on carbon by one or more groups selected from R6; wherein: R6 is selected from phenyl, isoxazolyl and thienyl; wherein R6 may be optionally substituted on carbon by one or more R7; wherein: R7 is selected from fluoro and methyl. R3 is selected from 2-fluorobenzyloxy, 5-methylisoxazol-3-ylmethoxy, 2-thien-3-ylethoxy, cyclopenylidenylmethoxy, 1-cyclopenylidenylethoxy, phenoxy, benzocyclopent-1-yloxy and 2-phenyl-2,2-difluoroethoxy. R3 is selected from 2-fluorobenzyloxy, 5-methylisoxazol-3-ylmethoxy and 2-thien-3-ylethoxy. Therefore in a further aspect of the invention, there is provided a compound of formula (I) (as depicted above) wherein Ring A is pyridin-2-yl or thiazol-2-yl; wherein said pyridin-2-yl or thiazol-2-yl may be optionally substituted on carbon by one or more groups selected from R4 wherein: R4 is carboxy; R1 is methyl or hydrogen and R2 is hydrogen; and R3 is selected from C1-4-alkoxy; wherein R3 may be independently optionally substituted on carbon by one or more groups selected from R6; wherein: R6 is selected from carbocyclyl and heterocyclyl; preferably phenyl, thienyl or isoxazolyl, wherein R6 may be optionally substituted on carbon by one or more R7; wherein: R7 is selected from halo and methyl; or a salt, solvate or pro-drug thereof. Therefore in a further aspect of the invention, there is provided a compound of formula (I) (as depicted above) wherein Ring A is 5-carboxypyridin-2-yl, thiazol-2-yl or 5-carboxythiazol-2-yl; R1 is methyl or hydrogen and R2 is hydrogen; and R3 is selected from 2-fluorobenzyloxy, 5-methylisoxazol-3-ylmethoxy and 2-thien-3-ylethoxy; or a salt, solvate or pro-drug thereof. In another aspect of the invention, preferred compounds of the invention include: 2-methyl-4-isobutoxy-6-[N-(5-carboxypyridin-2-yl)carbamoyl]benzofuran; 2-methyl4-(2-fluorophenylmethoxy)-6-[N-(5-carboxypyridin-2-yl)carbamoyl]benzofuran; 2-methyl-4-isobutoxy-6-[N-(5-carboxythiazol-2-yl)carbamoyl]benzofuran; 2-methyl-4-(5-methylisoxazol-3-ylmethoxy)-6-[N-(5-carboxypyridin-2-yl)carbamoyl]benzofuran; 4-(2-fluorophenylmethoxy)-6-[N-(5-carboxypyridin-2-yl)carbamoyl]benzofuran; 4-(5-methylisoxazol-3-ylmethoxy)-6-[N-(5-carboxypyridin-2-yl)carbamoyl]benzofuran; 2-methyl-4-(thien-2-ylethoxy)-6-[N-(5-carboxypyridin-2-yl)carbamoyl]benzofuran; and 2-methyl-4-isobutoxy-6-[N-(thiazol-2-yl)carbamoyl]benzofuran or a salt, solvate or pro-drug thereof. The compounds of the invention may be administered in the form of a pro-drug. A pro-drug is a bioprecursor or pharmaceutically acceptable compound being degradable in the body to produce a compound of the invention (such as an ester or amide of a compound of the invention, particularly an in vivo hydrolysable ester). Various forms of prodrugs are known in the art. For examples of such prodrug derivatives, see: a) Design of Prodrugs, edited by H. Bundgaard, (Elsevier, 1985) and Methods in Enzymology, Vol. 42, p. 309-396, edited by K. Widder, et al. (Academic Press, 1985); b) A Textbook of Drug Design and Development, edited by Krogsgaard-Larsen; c) H. Bundgaard, Chapter 5 “Design and Application of Prodrugs”, by H. Bundgaard p. 113-191 (1991); d) H. Bundgaard, Advanced Drug Delivery Reviews, 8, 1-38 (1992); e) H. Bundgaard, et al., Journal of Pharmaceutical Sciences, 77, 285 (1988); and f) N. Kakeya, et al., Chem Pharm Bull, 32, 692 (1984). The contents of the above cited documents are incorporated herein by reference. Examples of pro-drugs are as follows. An in vivo hydrolysable ester of a compound of the invention containing a carboxy or a hydroxy group is, for example, a pharmaceutically-acceptable ester which is hydrolysed in the human or animal body to produce the parent acid or alcohol. Suitable pharmaceutically-acceptable esters for carboxy include C1-C6alkoxymethyl esters for example methoxymethyl, C1-C6alkanoyloxymethyl esters for example pivaloyloxymethyl, phthalidyl esters, C3-C8cycloalkoxycarbonyloxyC1-C6alkyl esters for example 1-cyclohexylcarbonyloxyethyl; 1,3-dioxolen-2-onylmethyl esters, for example 5-methyl-1,3-dioxolen-2-onylmethyl; and C1-6alkoxycarbonyloxyethyl esters. An in vivo hydrolysable ester of a compound of the invention containing a hydroxy group includes inorganic esters such as phosphate esters (including phosphoramidic cyclic esters) and α-acyloxyalkyl ethers and related compounds which as a result of the in vivo hydrolysis of the ester breakdown to give the parent hydroxy group/s. Examples of α-acyloxyalkyl ethers include acetoxymethoxy and 2,2-dimethylpropionyloxy-methoxy. A selection of in vivo hydrolysable ester forming groups for hydroxy include alkanoyl, benzoyl, phenylacetyl and substituted benzoyl and phenylacetyl, alkoxycarbonyl (to give alkyl carbonate esters), dialkylcarbamoyl and N-(dialkylaminoethyl)-N-alkylcarbamoyl (to give carbamates), dialkylaminoacetyl and carboxyacetyl. A suitable pharmaceutically-acceptable salt of a compound of the invention is, for example, an acid-addition salt of a compound of the invention which is sufficiently basic, for example, an acid-addition salt with, for example, an inorganic or organic acid, for example hydrochloric, hydrobromic, sulphuric, phosphoric, trifluoroacetic, citric or maleic acid. In addition a suitable pharmaceutically-acceptable salt of a benzoxazinone derivative of the invention which is sufficiently acidic is an alkali metal salt, for example a sodium or potassium salt, an alkaline earth metal salt, for example a calcium or magnesium salt, an ammonium salt or a salt with an organic base which affords a physiologically-acceptable cation, for example a salt with methylamine, dimethylamine, trimethylamine, piperidine, morpholine or tris-(2-hydroxyethyl)amine. A further feature of the invention is a pharmaceutical composition comprising a compound of formula (I) as defined above, or a salt, solvate or prodrug thereof, together with a pharmaceutically-acceptable diluent or carrier. According to another aspect of the invention there is provided a compound of formula (I) as defined above for use as a medicament. Further according to the invention there is provided a compound of formula (I) for use in the preparation of a medicament for treatment of a disease mediated through GLK, in particular type 2 diabetes. The compound is suitably formulated as a pharmaceutical composition for use in this way. According to another aspect of the present invention there is provided a method of treating GLK mediated diseases, especially type 2 diabetes, by administering an effective amount of a compound of formula (I), or salt, solvate or pro-drug thereof, to a mammal in need of such treatment. Specific disease which may be treated by the compound or composition of the invention include: blood glucose lowering in diabetes mellitus type 2 without a serious risk of hypoglycaemia (and potential to treat type 1), dyslipidemea, obesity, insulin resistance, metabolic syndrome X, impaired glucose tolerance. As discussed above, thus the GLK/GLKRP system can be described as a potential “diabesity” target (of benefit in both diabetes and obesity). Thus, according to another aspect of the invention there if provided the use of a compound of formula (I), or salt, solvate or pro-drug thereof, in the preparation of a medicament for use in the combined treatment or prevention of diabetes and obesity. According to another aspect of the invention there if provided the use of a compound of formula (I), or salt, solvate or pro-drug thereof, in the preparation of a medicament for use in the treatment or prevention of obesity. According to a further aspect of the invention there is provided a method for the combined treatment of obesity and diabetes by administering an effective amount of a compound of formula (I), or salt, solvate or pro-drug thereof, to a mammal in need of such treatment. According to a further aspect of the invention there is provided a method for the treatment of obesity by administering an effective amount of a compound of formula (I), or salt, solvate or pro-drug thereof, to a mammal in need of such treatment. The compositions of the invention may be in a form suitable for oral use (for example as tablets, lozenges, hard or soft capsules, aqueous or oily suspensions, emulsions, dispersible powders or granules, syrups or elixirs), for topical use (for example as creams, ointments, gels, or aqueous or oily solutions or suspensions), for administration by inhalation (for example as a finely divided powder or a liquid aerosol), for administration by insufflation (for example as a finely divided powder) or for parenteral administration (for example as a sterile aqueous or oily solution for intravenous, subcutaneous, intramuscular or intramuscular dosing or as a suppository for rectal dosing). The compositions of the invention may be obtained by conventional procedures using conventional pharmaceutical excipients, well known in the art. Thus, compositions intended for oral use may contain, for example, one or more colouring, sweetening, flavouring and/or preservative agents. Suitable pharmaceutically acceptable excipients for a tablet formulation include, for example, inert diluents such as lactose, sodium carbonate, calcium phosphate or calcium carbonate, granulating and disintegrating agents such as corn starch or algenic acid; binding agents such as starch; lubricating agents such as magnesium stearate, stearic acid or talc; preservative agents such as ethyl or propyl p-hydroxybenzoate, and anti-oxidants, such as ascorbic acid. Tablet formulations may be uncoated or coated either to modify their disintegration and the subsequent absorption of the active ingredient within the gastrointestinal tract, or to improve their stability and/or appearance, in either case, using conventional coating agents and procedures well known in the art. Compositions for oral use may be in the form of hard gelatin capsules in which the active ingredient is mixed with an inert solid diluent, for example, calcium carbonate, calcium phosphate or kaolin, or as soft gelatin capsules in which the active ingredient is mixed with water or an oil such as peanut oil, liquid paraffin, or olive oil. Aqueous suspensions generally contain the active ingredient in finely powdered form together with one or more suspending agents, such as sodium carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose, sodium alginate, polyvinyl-pyrrolidone, gum tragacanth and gum acacia; dispersing or wetting agents such as lecithin or condensation products of an alkylene oxide with fatty acids (for example polyoxethylene stearate), or condensation products of ethylene oxide with long chain aliphatic alcohols, for example heptadecaethyleneoxycetanol, or condensation products of ethylene oxide with partial esters derived from fatty acids and a hexitol such as polyoxyethylene sorbitol monooleate, or condensation products of ethylene oxide with long chain aliphatic alcohols, for example heptadecaethyleneoxycetanol, or condensation products of ethylene oxide with partial esters derived from fatty acids and a hexitol such as polyoxyethylene sorbitol monooleate, or condensation products of ethylene oxide with partial esters derived from fatty acids and hexitol anhydrides, for example polyethylene sorbitan monooleate. The aqueous suspensions may also contain one or more preservatives (such as ethyl or propyl p-hydroxybenzoate, anti-oxidants (such as ascorbic acid), colouring agents, flavouring agents, and/or sweetening agents (such as sucrose, saccharine or aspartame). Oily suspensions may be formulated by suspending the active ingredient in a vegetable oil (such as arachis oil, olive oil, sesame oil or coconut oil) or in a mineral oil (such as liquid paraffin). The oily suspensions may also contain a thickening agent such as beeswax, hard paraffin or cetyl alcohol. Sweetening agents such as those set out above, and flavouring agents may be added to provide a palatable oral preparation. These compositions may be preserved by the addition of an anti-oxidant such as ascorbic acid. Dispersible powders and granules suitable for preparation of an aqueous suspension by the addition of water generally contain the active ingredient together with a dispersing or wetting agent, suspending agent and one or more preservatives. Suitable dispersing or wetting agents and suspending agents are exemplified by those already mentioned above. Additional excipients such as sweetening, flavouring and colouring agents, may also be present. The pharmaceutical compositions of the invention may also be in the form of oil-in-water emulsions. The oily phase may be a vegetable oil, such as olive oil or arachis oil, or a mineral oil, such as for example liquid paraffin or a mixture of any of these. Suitable emulsifying agents may be, for example, naturally-occurring gums such as gum acacia or gum tragacanth, naturally-occurring phosphatides such as soya bean, lecithin, an esters or partial esters derived from fatty acids and hexitol anhydrides (for example sorbitan monooleate) and condensation products of the said partial esters with ethylene oxide such as polyoxyethylene sorbitan monooleate. The emulsions may also contain sweetening, flavouring and preservative agents. Syrups and elixirs may be formulated with sweetening agents such as glycerol, propylene glycol, sorbitol, aspartame or sucrose, and may also contain a demulcent, preservative, flavouring and/or colouring agent. The pharmaceutical compositions may also be in the form of a sterile injectable aqueous or oily suspension, which may be formulated according to known procedures using one or more of the appropriate dispersing or wetting agents and suspending agents, which have been mentioned above. A sterile injectable preparation may also be a sterile injectable solution or suspension in a non-toxic parenterally-acceptable diluent or solvent, for example a solution in 1,3-butanediol. Compositions for administration by inhalation may be in the form of a conventional pressurised aerosol arranged to dispense the active ingredient either as an aerosol containing finely divided solid or liquid droplets. Conventional aerosol propellants such as volatile fluorinated hydrocarbons or hydrocarbons may be used and the aerosol device is conveniently arranged to dispense a metered quantity of active ingredient. For further information on formulation the reader is referred to Chapter 25.2 in Volume 5 of Comprehensive Medicinal Chemistry (Corwin Hansch; Chairman of Editorial Board), Pergamon Press 1990. The amount of active ingredient that is combined with one or more excipients to produce a single dosage form will necessarily vary depending upon the host treated and the particular route of administration. For example, a formulation intended for oral administration to humans will generally contain, for example, from 0.5 mg to 2 g of active agent compounded with an appropriate and convenient amount of excipients which may vary from about 5 to about 98 percent by weight of the total composition. Dosage unit forms will generally contain about 1 mg to about 500 mg of an active ingredient. For further information on Routes of Administration and Dosage Regimes the reader is referred to Chapter 25.3 in Volume 5 of Comprehensive Medicinal Chemistry (Corwin Hansch; Chairman of Editorial Board), Pergamon Press 1990. The size of the dose for therapeutic or prophylactic purposes of a compound of the formula (I) will naturally vary according to the nature and severity of the conditions, the age and sex of the animal or patient and the route of administration, according to well known principles of medicine. In using a compound of the formula (I) for therapeutic or prophylactic purposes it will generally be administered so that a daily dose in the range, for example, 0.5 mg to 75 mg per kg body weight is received, given if required in divided doses. In general lower doses will be administered when a parenteral route is employed. Thus, for example, for intravenous administration, a dose in the range, for example, 0.5 mg to 30 mg per kg body weight will generally be used. Similarly, for administration by inhalation, a dose in the range, for example, 0.5 mg to 25 mg per kg body weight will be used. Oral administration is however preferred. The elevation of GLK activity described herein may be applied as a sole therapy or may involve, in addition to the subject of the present invention, one or more other substances and/or treatments. Such conjoint treatment may be achieved by way of the simultaneous, sequential or separate administration of the individual components of the treatment. Simultaneous treatment may be in a single tablet or in separate tablets. For example in the treatment of diabetes mellitus chemotherapy may include the following main categories of treatment: 1) Insulin and insulin analogues; 2) Insulin secretagogues including sulphonylureas (for example glibenclamide, glipizide) and prandial glucose regulators (for example repaglinide, nateglinide); 3) Insulin sensitising agents including PPARg agonists (for example pioglitazone and rosiglitazone); 4) Agents that suppress hepatic glucose output (for example metformin). 5) Agents designed to reduce the absorption of glucose from the intestine (for example acarbose); 6) Agents designed to treat the complications of prolonged hyperglycaemia; 7) Anti-obesity agents (for example sibutramine and orlistat); 8) Anti-dyslipidaemia agents such as, HMG-CoA reductase inhibitors (statins, e.g. pravastatin); PPARα agonists (fibrates, eg gemfibrozil); bile acid sequestrants (cholestyramine); cholesterol absorption inhibitors (plant stanols, synthetic inhibitors); bile acid absorption inhibitors (IBATi) and nicotinic acid and analogues (niacin and slow release formulations); 9) Antihypertensive agents such as, β blockers (eg atenolol, inderal); ACE inhibitors (eg lisinopril); Calcium antagonists (eg. nifedipine); Angiotensin receptor antagonists (eg candesartan), α antagonists and diuretic agents (eg. furosemide, benzthiazide); 10) Haemostasis modulators such as, antithrombotics, activators of fibrinolysis and antiplatelet agents; thrombin antagonists; factor Xa inhibitors; factor VIIa inhibitors); antiplatelet agents (eg. aspirin, clopidogrel); anticoagulants (heparin and Low molecular weight analogues, hirudin) and warfarin; and 11) Anti-inflammatory agents, such as non-steroidal anti-infammatory drugs (eg. aspirin) and steroidal anti-inflammatory agents (eg. cortisone). According to another aspect of the present invention there is provided individual compounds produced as end products in the Examples set out below and salts, solvates and pro-drugs thereof. Another aspect of the present invention provides a process for preparing a compound of formula (I) or a salt, solvate or pro-drug thereof which process (wherein variable groups are, unless otherwise specified, as defined in formula (I)) comprises: Process 1): Reacting an Acid of Formula (II): or an activated derivative thereof; with a compound of formula (II): or Process 2) For Compounds of Formula (I) wherein R4 is Carboxy; Deprotecting a Compound of Formula (III): wherein RxC(O)O— is an ester group; and thereafter if necessary or desirable: i) converting a compound of the formula (I) into another compound of the formula (I), and or; ii) removing any protecting groups; and/or iii) forming a salt, solvate or pro-drug thereof. Suitable activated acid derivatives include acid halides, for example acid chlorides, and active esters, for example pentafluorophenyl esters. The reaction of these types of compounds with amines is well known in the art. The group RxOC(O)— is an ester. Suitable values for Rx are C1-6alkyl and benzyl, particularly methyl and ethyl. The reactions described above may be performed under standard conditions. The intermediates described above are commercially available, are known in the art or may be prepared by known procedures. Some of the intermediates described herein are novel and are thus provided as a further feature of the invention. For example compounds of formula (III) are provided as a further feature of the invention. During the preparation process, it may be advantageous to use a protecting group. Protecting groups may be removed by any convenient method as described in the literature or known to the skilled chemist as appropriate for the removal of the protecting group in question, such methods being chosen so as to effect removal of the protecting group with minimum disturbance of groups elsewhere in the molecule. Specific examples of protecting groups are given below for the sake of convenience, in which “lower” signifies that the group to which it is applied preferably has 1-4 carbon atoms. It will be understood that these examples are not exhaustive. Where specific examples of methods for the removal of protecting groups are given below these are similarly not exhaustive. The use of protecting groups and methods of deprotection not specifically mentioned is of course within the scope of the invention. A carboxy protecting group may be the residue of an ester-forming aliphatic or araliphatic alcohol or of an ester-forming silanol (the said alcohol or silanol preferably containing 1-20 carbon atoms). Examples of carboxy protecting groups include straight or branched chain C1-12alkyl groups (e.g. isopropyl, t-butyl); lower alkoxy lower alkyl groups (e.g. methoxymethyl, ethoxymethyl, isobutoxymethyl; lower aliphatic acyloxy lower alkyl groups, (e.g. acetoxymethyl, propionyloxymethyl, butyryloxymethyl, pivaloyloxymethyl); lower alkoxycarbonyloxy lower alkyl groups (e.g. 1-methoxycarbonyloxyethyl, 1-ethoxycarbonyloxyethyl); aryl lower alkyl groups (e.g. p-methoxybenzyl, o-nitrobenzyl, p-nitrobenzyl, benzhydryl and phthalidyl); tri(lower alkyl)silyl groups (e.g. trimethylsilyl and t-butyldimethylsilyl); tri(lower alkyl)silyl lower alkyl groups (e.g. trimethylsilylethyl); and C2-6alkenyl groups (e.g. allyl and vinylethyl). Methods particularly appropriate for the removal of carboxyl protecting groups include for example acid-, metal- or enzymically-catalysed hydrolysis. Examples of hydroxy protecting groups include lower alkenyl groups (e.g. allyl); lower alkanoyl groups (e.g. acetyl); lower alkoxycarbonyl groups (e.g. t-butoxycarbonyl); lower alkenyloxycarbonyl groups (e.g. allyloxycarbonyl); aryl lower alkoxycarbonyl groups (e.g. benzoyloxycarbonyl, p-methoxybenzyloxycarbonyl, o-nitrobenzyloxycarbonyl, p-nitrobenzyloxycarbonyl); tri lower alkyl/arylsilyl groups (e.g. trimethylsilyl, t-butyldimethylsilyl, t-butyldiphenylsilyl); aryl lower alkyl groups (e.g. benzyl) groups; and triaryl lower alkyl groups (e.g. triphenylmethyl). Examples of amino protecting groups include formyl, aralkyl groups (e.g. benzyl and substituted benzyl, e.g. p-methoxybenzyl, nitrobenzyl and 2,4-dimethoxybenzyl, and triphenylmethyl); di-p-anisylmethyl and furylmethyl groups; lower alkoxycarbonyl (e.g. t-butoxycarbonyl); lower alkenyloxycarbonyl (e.g. allyloxycarbonyl); aryl lower alkoxycarbonyl groups (e.g. benzyloxycarbonyl, p-methoxybenzyloxycarbonyl, o-nitrobenzyloxycarbonyl, p-nitrobenzyloxycarbonyl; trialkylsilyl (e.g. trimethylsilyl and t-butyldimethylsilyl); alkylidene (e.g. methylidene); benzylidene and substituted benzylidene groups. Methods appropriate for removal of hydroxy and amino protecting groups include, for example, acid-, base, metal- or enzymically-catalysed hydrolysis, or photolytically for groups such as o-nitrobenzyloxycarbonyl, or with fluoride ions for silyl groups. Examples of protecting groups for amide groups include aralkoxymethyl (e.g. benzyloxymethyl and substituted benzyloxymethyl); alkoxymethyl (e.g. methoxymethyl and trimethylsilylethoxymethyl); tri alkyl/arylsilyl (e.g. trimethylsilyl, t-butyldimethylsily, t-butyldiphenylsilyl); tri alkyl/arylsilyloxymethyl (e.g. t-butyldimethylsilyloxymethyl, t-butyldiphenylsilyloxymethyl); 4-alkoxyphenyl (e.g. 4-methoxyphenyl); 2,4-di(alkoxy)phenyl (e.g. 2,4-dimethoxyphenyl); 4-alkoxybenzyl (e.g. 4-methoxybenzyl); 2,4-di(alkoxy)benzyl (e.g. 2,4-di(methoxy)benzyl); and alk-1-enyl (e.g. allyl, but-1-enyl and substituted vinyl e.g. 2-phenylvinyl). Aralkoxymethyl, groups may be introduced onto the amide group by reacting the latter group with the appropriate aralkoxymethyl chloride, and removed by catalytic hydrogenation. Alkoxymethyl, tri alkyl/arylsilyl and tri alkyl/silyloxymethyl groups may be introduced by reacting the amide with the appropriate chloride and removing with acid; or in the case of the silyl containing groups, fluoride ions. The alkoxyphenyl and alkoxybenzyl groups are conveniently introduced by arylation or alkylation with an appropriate halide and removed by oxidation with ceric ammonium nitrate. Finally alk-1-enyl groups may be introduced by reacting the amide with the appropriate aldehyde and removed with acid. BIOLOGICAL Tests: The biological effects of the compounds of formula (I) may be tested in the following way: (1) Enzymatic activity of GLK may be measured by incubating GLK, ATP and glucose. The rate of product formation may be determined by coupling the assay to a G-6-P dehydrogenase, NADP/NADPH system and measuring the increase in optical density at 340 nm (Matschinsky et al 1993). (2) A GLK/GLKRP binding assay for measuring the binding interactions between GLK and GLKRP. The method may be used to identify compounds which modulate GLK by modulating the interaction between GLK and GLKRP. GLKRP and GLK are incubated with an inhibitory concentration of F-6-P, optionally in the presence of test compound, and the extent of interaction between GLK and GLKRP is measured. Compounds which either displace F-6-P or in some other way reduce the GLK/GLKRP interaction will be detected by a decrease in the amount of GLK/GLKRP complex formed. Compounds which promote F-6-P binding or in some other way enhance the GLK/GLKRP interaction will be detected by an increase in the amount of GLK/GLKRP complex formed. A specific example of such a binding assay is described below. GLK/GLKRP Scintillation Proximity Assay Compounds of the invention were found to have an activity of less than 10 μm when tested in the GLK/GLKRP scintillation proximity assay described below. Recombinant human GLK and GLKRP were used to develop a “mix and measure” 96 well SPA (scintillation proximity assay) as described in WO01/20327 (the contents of which are incorporated herein by reference). GLK (Biotinylated) and GLKRP are incubated with streptavidin linked SPA beads (Amersham) in the presence of an inhibitory concentration of radiolabelled [3H]F-6-P (Amersham Custom Synthesis TRQ8689), giving a signal. Compounds which either displace the P-6-P or in some other way disrupt the GLK/GLKRP binding interaction will cause this signal to be lost. Binding assays were performed at room temperature for 2 hours. The reaction mixtures contained 50 mM Tris-HCl (pH 7.5), 2 mM ATP, 5 mM MgCl2, 0.5 mM DTT, recombinant biotinylated GLK (0.1 mg), recombinant GLKRP (0.1 mg), 0.05 mCi [3H] F-6-P (Amersham) to give a final volume of 100 ml. Following incubation, the extent of GLK/GLKRP complex formation was determined by addition of 0.1 mg/well avidin linked SPA beads (Amersham) and scintillation counting on a Packard TopCount NXT. (3) A F-6-P/GLKRP binding assay for measuring the binding interaction between GLKRP and F-6-P. This method may be used to provide further information on the mechanism of action of the compounds. Compounds identified in the GLK/GLKRP binding assay may modulate the interaction of GLK and GLKRP either by displacing F-6-P or by modifying the GLK/GLKRP interaction in some other way. For example, protein-protein interactions are generally known to occur by interactions through multiple binding sites. It is thus possible that a compound which modifies the interaction between GLK and GLKRP could act by binding to one or more of several different binding sites. The F-6-P/GLKRP binding assay identifies only those compounds which modulate the interaction of GLK and GLKRP by displacing F-6-P from its binding site on GLKRP. GLKRP is incubated with test compound and an inhibitory concentration of F-6-P, in the absence of GLK, and the extent of interaction between F-6-P and GLKRP is measured. Compounds which displace the binding of F-6-P to GLKRP may be detected by a change in the amount of GLKRP/F-6-P complex formed. A specific example of such a binding assay is described below. F-6-P/GLKRP Scintillation Proximity Assay Recombinant human GLKRP was used to develop a “mix and measure” 96 well scintillation proximity assay ) as described in WO01/20327 (the contents of which are incorporated herein by reference). FLAG-tagged GLKRP is incubated with protein A coated SPA beads (Amersham) and an anti-FLAG antibody in the presence of an inhibitory concentration of radiolabelled [3H]F-6-P. A signal is generated. Compounds which displace the F-6-P will cause this signal to be lost. A combination of this assay and the GLK/GLKRP binding assay will allow the observer to identify compounds which disrupt the GLK/GLKRP binding interaction by displacing F-6-P. Binding assays were performed at room temperature for 2 hours. The reaction mixtures contained 50 mM Tris-HCl (pH 7.5), 2 mM ATP, 5 mM MgCl2, 0.5 mM DTT, recombinant FLAG tagged GLKRP (0.1 mg), Anti-Flag M2 Antibody (0.2 mg) (IBI Kodak), 0.5 mCi [3H]F-6-P (Amersham) to give a final volume of 100 ml. Following incubation, the extent of F-6-P/GLKRP complex formation was determined by addition of 0.1 mg/well protein A linked SPA beads (Amersham) and scintillation counting on a Packard TopCount NXT. Production of Recombinant GLK and GLKRP: Preparation of mRNA Human liver total mRNA was prepared by polytron homogenisation in 4M guanidine isothiocyanate, 2.5 mM citrate, 0.5% Sarkosyl, 100 mM b-mercaptoethanol, followed by centrifugation through 5.7M CsCl, 25 mM sodium acetate at 135,000 g (max) as described in Sambrook J, Fritsch E F & Maniatis T, 1989. Poly A+ mRNA was prepared directly using a FastTrack™ mRNA isolation kit (Invitrogen). PCR Amplification of GLK and GLKRP cDNA Sequences Human GLK and GLKRP cDNA was obtained by PCR from human hepatic mRNA using established techniques described in Sambrook, Fritsch & Maniatis, 1989. PCR primers were designed according to the GLK and GLKRP cDNA sequences shown in Tanizawa et al 1991 and Bonthron, D. T. et al 1994 (later corrected in Warner, J. P. 1995). Cloning in Bluescript II Vectors GLK and GLKRP cDNA was cloned in E. coli using pBluescript II, (Short et al 1998) a recombinant cloning vector system similar to that employed by Yanisch-Perron C et al (1985), comprising a colEI-based replicon bearing a polylinker DNA fragment containing multiple unique restriction sites, flanked by bacteriophage T3 and T7 promoter sequences; a filamentous phage origin of replication and an ampicillin drug resistance marker gene. Transformations E. Coli transformations were generally carried out by electroporation. 400 ml cultures of strains DH5a or BL21(DE3) were grown in L-broth to an OD 600 of 0.5 and harvested by centrifugation at 2,000 g. The cells were washed twice in ice-cold deionised water, resuspended in 1 ml 10% glycerol and stored in aliquots at −70° C. Ligation mixes were desalted using Millipore V series™ membranes (0.0025 mm) pore size). 40 ml of cells were incubated with 1 ml of ligation mix or plasmid DNA on ice for 10 minutes in 0.2 cm electroporation cuvettes, and then pulsed using a Gene Pulser™ apparatus (BioRad) at 0.5 kVcm−1, 250 mF, 250. Transformants were selected on L-agar supplemented with tetracyline at 10 mg/ml or ampicillin at 100 mg/ml. Expression GLK was expressed from the vector pTB375NBSE in E.coli BL21 cells, producing a recombinant protein containing a 6-His tag immediately adjacent to the N-terminal methionine. Alternatively, another suitable vector is pET21(+)DNA, Novagen, Cat number 697703. The 6-His tag was used to allow purification of the recombinant protein on a column packed with nickel-nitrilotriacetic acid agarose purchased from Qiagen (cat no 30250). GLKRP was expressed from the vector pFLAG CTC (IBI Kodak) in E. coli BL21 cells, producing a recombinant protein containing a C-terminal FLAG tag. The protein was purified initially by DEAE Sepharose ion exchange followed by utilisation of the FLAG tag for final purification on an M2 anti-FLAG immunoaffinity column purchased from Sigma-Aldrich (cat no. A1205). Biotinylation of GLK: GLK was biotinylated by reaction with biotinamidocaproate N-hydroxysuccinimide ester (biotin-NHS) purchased from Sigma-Aldrich (cat no. B2643). Briefly, free amino groups of the target protein (GLK) are reacted with biotin-NHS at a defined molar ratio forming stable amide bonds resulting in a product containing covalently bound biotin. Excess, non-conjugated biotin-NHS is removed from the product by dialysis. Specifically, 7.5 mg of GLK was added to 0.31 mg of biotin-NHS in 4 mL of 25 mM HEPES pH7.3, 0.15M KCl, 1 mM dithiothreitol, 1 mM EDTA, 1 mM MgCl2 (buffer A). This reaction mixture was dialysed against 100 mL of buffer A containing a further 22 mg of biotin-NHS. After 4 hours excess biotin-NHS was removed by extensive dialysis against buffer A. The following examples are for illustration purposes and are not intended to limit the scope of this application. Each exemplified compound represents a particular and independent aspect of the invention. In the following non-limiting Examples, unless otherwise stated: (i) evaporations were carried out by rotary evaporation in vacuo and work-up procedures were carried out after removal of residual solids such as drying agents by filtration; (ii) operations were carried out at room temperature, that is in the range 18-25° C. and under an atmosphere of an inert gas such as argon or nitrogen; (iii) yields are given for illustration only and are not necessarily the maximum attainable; (iv) the structures of the end-products of the formula (I) were confirmed by nuclear (generally proton) magnetic resonance (NMR) and mass spectral techniques; proton magnetic resonance chemical shift values were measured on the delta scale in deuterated dimethyl sulphoxide unless otherwise stated, and peak multiplicities are shown as follows: s, singlet; d, doublet; t, triplet; m, multiplet; br, broad; q, quartet, quin, quintet; (v) intermediates were not generally fully characterised and purity was assessed by thin layer chromatography (TLC), high-performance liquid chromatography (HPLC), infra-red (IR) or NMR analysis; (vi) chromatography was performed on silica (Merck Silica gel 60, 0.040-0.063 mm, 230-400 mesh); and (vi) where a “Bondelut” column is referred to, this means a column containing 10 g or 20 g or 50 g or 70 g of silica of 40 micron particle size, the silica being contained in a 60 ml disposable syringe and supported by a porous disc, obtained from Varian, Harbor City, Calif., USA under the name “Mega Bond Elut SI”; “Mega Bond Elut” is a trademark; (vii) the following abbreviations are used: DCM dichloromethane; DMF dimethylformamide; LCMS liquid chromatography/mass spectroscopy; THF tetrahydrofuran. EXAMPLE 1 2-Methyl4-isobutoxy-6-[N-(5-carboxypyridin-2-yl)carbamoyl]benzofuran Sodium hydroxide solution (0.94 ml of 1M, 0.94 mM) was added to a solution of 2-methyl-4-isobutoxy-6-[N-(5-methoxycarbonylpyridin-2-yl)carbamoyl]benzofuran (Method 1; 120 mg, 0.314 mM) in a methanol/THF mixture (1 ml+4 ml), and the resulting solution stirred at ambient temperature. After 4 hrs the reaction mixture was diluted with water (5 ml) and concentrated to half volume in vacuo. The resulting mixture was acidified to pH6 with 1M HCl. The resulting solid precipitate was filtered, washed with water, and dried to give a pale cream solid. This was chromatographed (10 g Bondelut), eluting with DCM containing methanol (0-10% gradient) to give the title compound as a colourless solid. NMR: 1.03 (d, 6H), 2.09 (sept, 1H), 2.45 (s, 3H), 3.97 (d, 2H), 6.66 (s, 1H), 7.44 (s, 1H), 7.85 (s, 1H), 8.31 (t, 2H), 8.87 (s, 1H), 11.10 (bs, 1H); mlz 367 (M+H)+. EXAMPLES 2-7 The following compounds were prepared by the procedure of Example 1 starting fom the appropriate ester. Ex Structure NMR MS SM 2 2.46 (s, 3H), 5.39 (s, 2H), 6.71 (2, 1H), 7.26 (m, 2H), 7.43 (m, 1H), 7.65 (m, 2H), 7.91 (s, 1H), 8.31 (m, 2H), 8.88 (s, 1H), 11.14 (bs, 1H), COOH not seen (M + H)+421 Method 17 3 1.03 (d, 6H), 2.10 (sept, 1H), 2.46 (s, 3H), 3.96 (d, 2H), 6.66 (s, 1H), 7.51 (s, 1H), 7.92 (s, 1H), 8.14 (s, 1H), 12.20 (bs, 1H), COOH not seen (2M + H)+749 Method 18 4 2.44 (s, 3H), 2.49 (s, 3H), 5.43 (s, 2H), 6.42 (s, 1H), 6.71 (s, 1H), 7.66 (s, 1H), 7.93 (s, 1H), 8.36 (m, 2H), 8.90 (s, 1H), 13.10 (bs, 1H), COOH not seen (M + H)+408 Method 19 5 5.41 (s, 2H), 7.03 (s, 1H), 7.30 (m, 2H), 7.44 (m, 1H), 7.64 (m, 2H), 8.00 (s, 1H), 8.08 (d, 1H), 8.33 (m, 2H), 8.89 (s, 1H), 11.21 (bs, 1H), COOH not seen (M + H)+407 (M − H)−405 Method 20 6 2.42 (s, 3H), 5.43 (s, 2H), 6.41 (s, 1H), 7.04 (d, 1H), 7.65 (s, 1H), 8.00 (s, 1H), 8.10 (d, 1H), 8.33 (m, 2H), 8.88 (s, 1H), 11.37 (bs, 1H), COOH not seen (M + H)+394 (M − H)−392 Method 21 7 2.44 (s, 3H), 3.13 (t, 2H), 4.41 (t, 2H), 6.64 (s, 1H), 7.14 (d, 1H), 7.35 (m, 1H), 7.47 (m, 2H), 7.84 (s, 1H), 8.32 (m, 2H), 8.86 (s, 1H), 11.12 (bs, 1H), COOH not seen (M + H)+423 Method 22 EXAMPLE 8 The following compound was prepared by the procedure of Method 1 using 2-aminothiazole. Ex Structure NMR MS 8 1.07 (d, 6H), 2.30 (sept, 1H), 2.50 (s, 3H), 4.01 (d, 2H), 6.60 (s, 1H), 7.27 (d, 1H), 7.52 (s, 1H), 7.58 (d, 1H), 7.92 (s, 1H), 12.56 (bs, 1H) (M + H)+331 (2M + H)+661 Preparation of Starting Materials The starting materials for the Examples above are either commercially available or are readily prepared by standard methods from known materials. For example the following reactions are illustrations but not limitations of the preparation of some of the starting materials used in the above reactions. Method 1 2-Methyl-4-isobutoxy-6-[N-(5-methoxycarbonylpyridin-2-yl)carbamoyl]benzofuran Oxalyl chloride (410 mg, 282 μl, 3.225 mmol, 5 eq) was added to a solution of 2-methyl-4-isobutoxy-6-carboxybenzofuran (Method 2; 0.160 mg, 0.645 mmol) in DCM (5 ml) and the reaction mixture stirred for 4 hrs at ambient temperature. Further reagent was added, the reaction mixture stirred for 16 hrs, and then warmed to 40° C. As starting acid still remained, the solvent was removed in vacuo and the residue treated with neat oxalyl chloride. The reaction mixture was then concentrated in vacuo and dissolved in pyridine (5 ml); to the resulting solution was added methyl 2-aminopyridine-5-carboxylate (98 mg, 0.645 mmol). After stirring for 16 hrs the reddish solution was concentrated in vacuo and the resulting gum dissolved in DCM and chromatographed (20 g Bondelut, eluting with hexane containing ethyl acetate, 0-100%) to give the title compound (122 mg, 49.5% yield) as a colourless gum which slowly set solid; LC-MS 383 (M+H)+, 94.4% strength. Method 2 2-Methyl-4-isobutoxy-6-carboxybenzofuran Sodium hydroxide solution (2.28 ml of 1M, 2.28 mmol, 3 eq) was added to a solution of 2-methyl-4-isobutoxy-6-methoxycarbonylbenzofuran (Method 7; 200 mg, 0.76 mmol; contained ca 15 mol % of isobutyl ester) in MeOH (2.28 ml)/THF (2.28 ml). After 2 hours at 50° C. the reaction mixture was stirred at ambient temperature overnight and then concentrated to half-volume in vacuo. The resulting solution was diluted with water and acidified to pH 5 (1M HCl), and the resulting flocculent precipitate filtered and dried to give the title compound as a colourless solid (165 mg, 88%). NMR: 1.02 (d, 6H), 2.06 (sept, 1H), 2.45 (s, 3H), 3.90 (d, 2H), 6.64 (s, 1H), 7.24 (s, 1H), 7.64 (s, 1H), 12.83 (bs, 1H); m/z 247 (M−H)−, 94.6% by LC-MS. Methods 3-6 The following compounds were prepared by the procedure of Method 2. Method Compound SM 3 2-Methyl-4-(2-fluorobenzyloxy)-6- Method 8 carboxybenzofuran 4 2-Methyl-4-(5-methylisoxazol-3-ylmethoxy)-6- Method 9 carboxybenzofuran 5 4-(2-Fluorobenzyloxy)-6-carboxybenzofuran Method 10 6 4-(5-Methylisoxazol-3-ylmethoxy)-6- Method carboxybenzofuran 11 Method 7 2-Methyl4-isobutoxy-6-methoxycarbonylbenzofuran 2-Methyl-4-hydroxy-6-methoxycarbonylbenzofuran (Method 12; 412 mg, assumed 1.0 mmol) was stirred in anhydrous DMF (10 ml) and the solution treated sequentially with potassium carbonate (690 mg, 5 mmol, 5 eq) and 1-iodo-2-methylpropane (442 mg, 276 μl, 2.4 mmol, 2.4 eq). The reaction mixture was stirred at 90° C. for 3 hours, then cooled and poured into water; the resulting mixture was extracted twice with ethyl acetate, the extracts dried (MgSO4) and evaporated in vacuo to yield a brown oil. This was chromatographed (50 g Bondelut, eluting with hexane containing ethyl acetate, 0-100%) to give the title compound as a clear oil contaminated with ca 15% of the corresponding iso-butyl ester. NMR: 1.02 (d, 6H), 2.06 (sept, 1H), 2.45 (s, 3H), 3.84 (s, 3H), 3.91 (d, 2H), 6.66 (s, 1H), 7.24 (s, 1H), 7.66 (s, 1H); the spectrum also contained signals consistent with isobutyl ester, ca 15 mol %. Methods 8-11 The following compounds were prepared by the procedure of Method 7. Method Compound SM 8 2-Methyl-4-(2-fluorobenzyloxy)-6- Method methoxycarbonylbenzofuran 12 9 2-Methyl-4-(5-methylisoxazol-3-ylmethoxy)-6- Method methoxycarbonylbenzofuran 12 10 4-(2-Fluorobenzyloxy)-6-methoxycarbonylbenzofuran Method 13 11 4-(5-Methylisoxazol-3-ylmethoxy)-6- Method methoxycarbonylbenzofuran 13 Method 12 2-Methyl4-hydroxy-6-methoxycarbonylbenzofuran 2-Methyl-4-acetoxy-6-methoxycarbonylbenzofuran (Method 14; 1.275 g, 5.14 mmol) was added to a suspension of potassium carbonate (1.408 g, 10.3 mmol, 2 eq) in MeOH (100 ml) and water (2 ml), and the mixture stirred for 1 hr at ambient temperature. The supernatant liquor was decanted from the insoluble material and evaporated in vacuo to yield a cream solid (2.19 g, assumed to be contaminated with inorganics). NMR: 2.35 (s, 3H), 3.56 (br s, 1H), 3.73 (s, 3H), 6.46 (s, 1H), 6.69 (s, 1H), 6.86 (s, 1H); m/z 205 (M−H)−, 83% by LC-MS. Method 13 The following compound was prepared by the procedure of Method 12 starting from 4-acetoxy-6-methoxycarbonylbenzofuran (J Chem Soc (C); 1968, 867-9). Method Compound 13 4-Hydroxy-6-methoxycarbonylbenzofuran Method 14 2-Methyl-4-acetoxy-6-methoxycarbonylbenzofuran A mixture of E-3-methoxycarbonyl-4-(5-methylfur-2-yl)-but-3-enoic acid (Method 15; 1.39 g, 6.2 mmol) and potassium acetate (620 mg, 6.3 mmol) in acetic anhydride (12.5 ml) was heated at 140° C. for 15 mins. The reaction mixture was cooled and poured on to a water/ethyl acetate mixture; the aqueous layer was separated and the organic layer washed sequentially with saturated sodium bicarbonate solution and brine, dried (MgSO4) and evaporated in vacuo to yield the crude product as a dark crystalline mass. This was chromatographed (50 g Bondelut, eluting with hexane containing ethyl acetate, 0-100%) to give the title compound as a pale yellow solid, 1.42 g (92%). NMR: 2.36 (s, 3H), 3.34 (s, 3H), 3.87 (s, 3H), 6.68 (s, 1H), 7.56 (s, 1H), 7.96 (s, 1H); m/z 247 (M−H)−, 97.1% by LC-MS. Method 15 E-3-Methoxycarbonyl-4-(5-methylfur-2-yl)-but-3-enoic acid A solution of E-3-methoxycarbonyl-4-(5-methylfur-2-yl)-but-3-enoic acid t-butyl ester (Method 16; 1.39 g, 4.96 mmol) in trifluoroacetic acid/water (20 ml of 90:10 v/v) was stirred at ambient temperature for 20 mins; the reaction mixture was then diluted with toluene (30 ml) and evaporated in vacuo to yield a brown oil. After further azeotroping with toluene (30 ml), this set solid; trituration with isohexane and collection of the residue yielded the title compound as a brown solid (1.05 g, 95%). NMR 2.33 (s, 3H), 3.65 (s, 2H), 3.72 (s, 3H), 6.29 (d, 1H), 6.85 (d, 1H), 7.41 (s, 1H), 12.34 (bs, 1H). Method 16 E-3-methoxycarbonyl-4(5-methylfur-2-yl)-but-3-enoic acid t-butyl ester A solution of 1-methoxycarbonyl-2-t-butoxycarbonyl ethyl phosphorane (JCS Perkin II, 1975, p1030; 2.69 g, 6 mmol, 1.2 eq) and 5-methylfuran-2-al (0.5 ml, 5 mmol) in dry toluene (10 ml) was stirred at 80° C. for 48 hrs, and then evaporated to dryness. The residue was chromatographed (50 g Bondelut, eluting with hexane containing 10% v/v ethyl acetate) to yield the title compound as a brown oil (1.39 g, 100%). NMR: 1.38 (s, 9H), 2.33 (s, 3H), 3.62 (s, 2H), 3.71 (s, 3H), 6.31 (d, 1H), 6.85 (d, 1H), 7.42 (s, 1H). Method 17 2-Methyl-4-(2-fluorobenzyloxy)-6-[N-(4-methoxycarbonylphenyl)carbamoyl]benzofuran A solution of 2-methyl-4-(2-fluorobenzyloxy)-1-benzofuran-6-carboxylic acid (Method 3; 0.60 mg, 0.2 mmol) and methyl 2-aminopyridine-5-carboxylate (61 mg, 0.4 mmol, 2 eq) in pyridine (1 ml) was treated with phosphorus oxychloride (20.5 μl, 0.22 mmol, 1.1 eq), and the reaction mixture stirred for 16 hrs at ambient temperature. The reaction mixture was poured into water and extracted twice with ethyl acetate; the extracts were washed with brine, dried (MgSO4) and evaporated to give a yellow gum. This was chromatographed (10 g Bondelut, eluting with hexane containing ethyl acetate, 0-100%) to give the title compound as a solid (61 mg, 70%). NMR: 2.46 (s, 3H), 3.87 (s, 3H), 5.37 (s, 2H), 6.66 (s, 1H), 7.25 (m, 2H), 7.42 (m, 1H), 7.62 (m, 2H), 7.91 (s, 1H), 8.36 (m, 2H), 8.91 (s, 1H), 11.20 (bs, 1H); m/z 435 (M+H)+, 100% by LC-MS. Methods 18-22 The following compounds were prepared by the procedure of Method 17. Method Compound SM 18 2-Methyl-4-isobutoxy-6-[N-(5-ethoxycarbonylthiazol- Method 2-yl)carbamoyl]benzofuran 2 19 2-Methyl-4-(5-methylisoxazol-3-ylmethoxy)-6-[N- Method (5-methoxycarbonylpyridin-2-yl)carbamoyl]benzofuran 4 20 4-(2-Fluorobenzyloxy)-6-[N-(5- Method methoxycarbonylpyridin-2-yl)carbamoyl]benzofuran 5 21 4-(5-Methylisoxazol-3-ylmethoxy)-6-[N-(5- Method methoxycarbonylpyridin-2-yl)carbamoyl]benzofuran 6 22 2-Methyl-4-(2-thien-3-ylethoxy)-6-[N-(5- Method methoxycarbonylpyridin-2-yl)carbamoyl]benzofuran 23 Method 23 2-Methyl-4-(2-thien-3-ylethoxy)-6-methoxycarbonylbenzofuran To a solution of 2-methyl-4-hydroxy-6-methoxycarbonylbenzofuran (Method 12; 1.24 g, 6.0 mmol) and 2-(3-thienyl) ethanol (768 mg, 0.67 ml, 6.0 mmol) in DCM (DCM, 50 ml) was added polymer-supported triphenyl phosphine (2.5 g, ca 3 mmol/g, 1.5 eq), and the suspension cooled to 5° C. under an argon atmosphere. To this was added di t-butyl azodicarboxylate (1.725 g, 7.5 mmol, 1.5 eq), and the reaction mixture stirred overnight, allowing to warm to ambient temperature. It was then filtered through diatomaceous earth, washed through with DCM, and the filtrate and washings evaporated in vacuo to ˜50 ml total volume. To this was added trifluoroacetic acid (2 ml), and the solution evaporated in vacuo to give a red oil. This was chromatographed (70 g Bondelut, eluting with hexane containing ethyl acetate, 0-50%) to give a red solid; this was re-chromatographed (as previous) to give the title compound as a colourless crystalline solid (150 mg, 8% yield). NMR: 2.46 (s, 3H), 3.10 (t, 2H), 3.83 (s, 3H), 4.33 (t, 2H), 6.64 (s, 1H), 7.12 (dd, 1H), 7.28 (s, 1H), 7.32 (d, 1H), 7.46 (dd, 1H), 7.66 (s, 1H). Pharmaceutical Compositions The following illustrate representative pharmaceutical dosage forms of the invention as defined herein (the active ingredient being termed “Compound X”), for therapeutic or prophylactic use in humans: (a) Tablet I mg/tablet Compound X 100 Lactose Ph.Eur 182.75 Croscarmellose sodium 12.0 Maize starch paste (5% w/v paste) 2.25 Magnesium stearate 3.0 (b) Tablet II mg/tablet Compound X 50 Lactose Ph.Eur 223.75 Croscarmellose sodium 6.0 Maize starch 15.0 Polyvinylpyrrolidone (5% w/v paste) 2.25 Magnesium stearate 3.0 (c) Tablet III mg/tablet Compound X 1.0 Lactose Ph.Eur 93.25 Croscarmellose sodium 4.0 Maize starch paste (5% w/v paste) 0.75 Magnesium stearate 1.0 (d) Capsule mg/capsule Compound X 10 Lactose Ph.Eur 488.5 Magnesium 1.5 (e) Injection I (50 mg/ml) Compound X 5.0% w/v 1M Sodium hydroxide solution 15.0% v/v 0.1M Hydrochloric acid (to adjust pH to 7.6) Polyethylene glycol 400 4.5% w/v Water for injection to 100% (f) Injection II (10 mg/ml) Compound X 1.0% w/v Sodium phosphate BP 3.6% w/v 0.1M Sodium hydroxide solution 15.0% v/v Water for injection to 100% (1 mg/ml, buffered (g) Injection III to pH6) Compound X 0.1% w/v Sodium phosphate BP 2.26% w/v Citric acid 0.38% w/v Polyethylene glycol 400 3.5% w/v Water for injection to 100% (h) Aerosol I mg/ml Compound X 10.0 Sorbitan trioleate 13.5 Trichlorofluoromethane 910.0 Dichlorodifluoromethane 490.0 (i) Aerosol II mg/ml Compound X 0.2 Sorbitan trioleate 0.27 Trichlorofluoromethane 70.0 Dichlorodifluoromethane 280.0 Dichlorotetrafluoroethane 1094.0 (j) Aerosol III mg/ml Compound X 2.5 Sorbitan trioleate 3.38 Trichlorofluoromethane 67.5 Dichlorodifluoromethane 1086.0 Dichlorotetrafluoroethane 191.6 (k) Aerosol IV mg/ml Compound X 2.5 Soya lecithin 2.7 Trichlorofluoromethane 67.5 Dichlorodifluoromethane 1086.0 Dichlorotetrafluoroethane 191.6 (l) Ointment ml Compound X 40 mg Ethanol 300 μl Water 300 μl 1-Dodecylazacycloheptan-2-one 50 μl Propylene glycol to 1 ml Note The above formulations may be obtained by conventional procedures well known in the pharmaceutical art. The tablets (a)-(c) may be enteric coated by conventional means, for example to provide a coating of cellulose acetate phthalate. The aerosol formulations (h)-(k) may be used in conjunction with standard, metered dose aerosol dispensers, and the suspending agents sorbitan trioleate and soya lecithin may be replaced by an alternative suspending agent # such as sorbitan monooleate, sorbitan sesquioleate, polysorbate 80, polyglycerol oleate or oleic acid. REFERENCES 1 Printz, R. L., Magnuson, M. A. and Granner, D. K. (1993) Annual Review of Nutrition 13, 463-96 2 DeFronzo, R. A. (1988) Diabetes 37, 667-87 3 Froguel, P., Zouali, H., Vionnet, N., Velho, G., Vaxillaire, M., Sun, F., Lesage, S., Stoffel, M., Takeda, J. and Passa, P. (1993) New England Journal of Medicine 328, 697-702 4 Bell, G. I., Pilkis, S. J., Weber, I. T. and Polonsky, K. S. (1996) Annual Review of Physiology 58, 171-86 5 Velho, G., Petersen, K. F., Perseghin, G., Hwang, J. H., Rothman, D. L., Pueyo, M. E., Cline, G. W., Froguel, P. and Shulman, G. I. (1996) Journal of Clinical Investigation 98, 1755-61 6 Christesen, H. B., Jacobsen, B. B., Odili, S., Buettger, C., Cuesta-Munoz, A., Hansen, T., Brusgaard, K., Massa, O., Magnuson, M. A., Shiota, C., Matschinsky, F. M. and Barbetti, F. (2002) Diabetes 51, 1240-6 7 Glaser, B., Kesavan, P., Heyman, M., Davis, E., Cuesta, A., Buchs, A., Stanley, C. A., Thornton, P. S., Permutt, M. A., Matschinsky, F. M. and Herold, K. C. (1998) New England Journal of Medicine 338, 226-30 8 Caro, J. F., Triester, S., Patel, V. K., Tapscott, E. B., Frazier, N. L. and Dohm, G. L. (1995) Hormone & Metabolic Research 27, 19-22 9 Desai, U. J., Slosberg, E. D., Boettcher, B. R., Caplan, S. L., Fanelli, B., Stephan, Z., Gunther, V. J., Kaleko, M. and Connelly, S. (2001) Diabetes 50, 2287-95 10 Shiota, M., Postic, C., Fujimoto, Y., Jetton, T. L., Dixon, K., Pan, D., Grimsby, J., Grippo, J. F., Magnuson, M. A. and Cherrington, A. D. (2001) Diabetes 50, 622-9 11 Ferre, T., Pujol, A., Riu, E., Bosch, F. and Valera, A. (1996) Proceedings of the National Academy of Sciences of the United States of America 93, 7225-30 12 Seoane, J., Barbera, A., Telemaque-Potts, S., Newgard, C. B. and Guinovart, J. J. (1999) Journal of Biological Chemistry 274, 31833-8 13 Moore, M. C., Davis, S. N., Mann, S. L. and Cherrington, A. D. (2001) Diabetes Care 24, 1882-7 14 Alvarez, E., Roncero, I., Chowen, J. A., Vazquez, P. and Blazquez, E. (2002) Journal of Neurochemistry 80, 45-53 15 Lynch, R. M., Tompkins, L. S., Brooks, H. L., Dunn-Meynell, A. A. and Levin, B. E. (2000) Diabetes 49, 693-700 16 Roncero, I., Alvarez, E., Vazquez, P. and Blazquez, E. (2000) Journal of Neurochemistry 74, 1848-57 17 Yang, X. J., Kow, L. M., Funabashi, T. and Mobbs, C. V. (1999) Diabetes 48, 1763-1772 18 Schuit, P. C., Huypens, P., Heimberg, H. and Pipeleers, D. G. (2001) Diabetes 50, 1-11 19 Levin, B. E. (2001) International Journal of Obesity 25 20 Alvarez, E., Roncero, I., Chowen, J. A., Thorens, B. and Blazquez, E. (1996) Journal of Neurochemistry 66, 920-7 21 Mobbs, C. V., Kow, L. M. and Yang, X. J. (2001) American Journal of Physiology—Endocrinology & Metabolism 281, E649-54 22 Levin, B. E., Dunn-Meynell, A. A. and Routh, V. H. (1999) American Journal of Physiology 276, R1223-31 23 Spanswick, D., Smith, M. A., Groppi, V. E., Logan, S. D. and Ashford, M. L. (1997) Nature 390, 521-5 24 Spanswick, D., Smith, M. A., Mirshamsi, S., Routh, V. H. and Ashford, M. L. (2000) Nature Neuroscience 3, 757-8 25 Levin, B. E. and Dunn-Meynell, A. A. (1997) Brain Research 776, 146-53 26 Levin, B. E., Govek, E. K. and Dunn-Meynell, A. A. (1998) Brain Research 808, 317-9 27 Levin, B. E., Brown, K. L. and Dunn-Meynell, A. A. (1996) Brain Research 739, 293-300 28 Rowe, I. C., Boden, P. R. and Ashford, M. L. (1996) Journal of Physiology 497, 365-77 29 Fujimoto, K., Sakata, T., Arase, K., Kurata, K., Okabe, Y. and Shiraishi, T. (1985) Life Sciences 37, 2475-82 30 Kurata, K., Fujimoto, K. and Sakata, T. (1989) Metabolism: Clinical & Experimental 38, 46-51 31 Kurata, K., Fujimoto, K., Sakata, T., Etou, H. and Fukagawa, K. (1986) Physiology & Behavior 37, 615-20
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MORRIS, PATRICIA L
BENZOFURAN DERIVATIVES, PROCESS FOR THEIR PREPARATION AND INTERMEDIATES THEREOF
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ACCEPTED
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Satellite system for shallow diving
The present invention refers to a shallow diving system in open sea that consists of a main vessel (2) provided with dynamic positioning system (DP) and with the equipments to monitor diving operations, and give assistance and orientation to the divers (6). The main vessel (2) operates with support vessels (3), and together they set the divers (6) and support team at the work location (4), at a safe distance from the main vessel propulsion system, to perform the job on the offshore units (1). These vessels for supporting diving operation, act like satellites of the main vessel, linked to it by means of a umbilical line (5).
1. Satellite system for shallow diving in open sea characterized by comprehending a main vessel (2) provided with a dynamic positioning system, and with the equipments to monitor the diving operation, to give assistance and orientation to the divers; the main vessel (2) operates with support vessels (3), connected by means of an umbilical line (5) and together they set the divers (6) and the support team at the work location (4), at a safe distance from the main vessel (2) propulsion system. 2. Satellite system for shallow diving in open sea according to claim 1, characterized by the main vessel (2) be provided with all equipments to diving monitoring and to give assistance and orientation to divers (6). 3. Satellite system for shallow diving in open sea according to claim 1, characterized by the main vessel (2) be used as base for diving work. 4. Satellite system for shallow diving in open sea according to claim 1, characterized by the diving boat (3) be connected to the main vessel (2) by supplying umbilical (5). 5. Satellite system for shallow diving in open sea according to claims 1 and 4, characterized by said diving boat (3) supporting diving operation from a point at the surface, above the desired work position (4). 6. Satellite system for shallow diving in open sea according to claim 1, characterized by the umbilical line (5) to be positive buoyancy. 7. Satellite system for shallow diving in open sea according to claim 1, characterized by the umbilical line (5) be used for positioning the support vessel (3) relative to the main vessel (2).
FIELD OF THE INVENTION The present invention deals with a shallow diving system (up to 50 meters), carried out in open sea for the main objective of inspecting, sub aquatic surveying and repairing services in offshore installations, as for example platforms, vessels and equipments that work continuously at the sea. To reach such an objective, the diving system operates externally the offshore installation where the service is required, in a main vessel provided with dynamic positioning system, and where are arranged the support equipment necessary to the diving operation. The main vessel is suitably positioned nearby the location where the diving will be executed, using a secondary vessel for direct support and assistance. This secondary vessel functions like a satellite of the main vessel. BACKGROUND OF THE INVENTION Nowadays, the shallow diving systems used in oil exploitation and production offshore platforms that operate in deep waters are based and operated from the same unit where the inspecting work will be performed. In offshore platforms the physical space is limited. After installing exploitation systems, their facilities, safety systems, accommodations, loading areas, winches, cranes, heliport and escape routes, there are few remaining spaces on board. Diving systems in use are arranged in these remaining spaces, and they utilize as a transportation mean to access the submerse region, an open bottom diving bell or basket, that is kept suspended and vertically lowered by means of an articulated structure that extends outside the platform structure. These systems, however, can only control the open bottom diving bell positioning in the vertical direction, the necessary horizontal displacement is obtained by moving the divers away from it, at the depth work, by using an umbilical line that links them. Due to the few available space for installing the diving equipments, the distances between diving places and work places demand the use of long umbilical lines, that require a greater physical effort from the divers, and increase considerably the risk of the operation that may become unsafe or not be feasible in different points of the unit. Many occurrences have demonstrated that the arrangements made for launching and rescuing the divers, as those used for shallow diving systems, located in platforms, could not guarantee the immediate rescue of injured/endangered divers. Generally the only way for doing the rescue, is with the open bottom diving bell itself or the diving basket, that most of the time can not be placed where the diver is, or can not be immediately raised due to untangled umbilical lines and/or other reasons. Floating production, storage and off-loading units, known as FPSO, that are authorized to operate for periods up to twenty years, without dry-docking, have their structural integrity verified by programmed sub aquatic surveys, together with non destructive test (NDT) inspection, in all the hull extension, and the execution of the repairs identified as necessary. The activities comprised in the job for sub aquatic inspection and repairing demand a peculiar structure entirely dedicated, with facilities to give support to the divers' life and adequate working conditions, safety and effectiveness for the job. The optimization of space on the production units clearly indicates that an improvement in the actual operating conditions for diving systems will be reached only with an evolution within the concept that overtakes the present critical points, listed bellow: difficulty in rescuing the divers in an emergency situation; short range for the horizontal reaching capability, limited by the umbilical line length that can be handled securely; great difficulty to access different points of the platforms; divers physical effort due to the use of long umbilical line; necessity to move (re install) the support equipments; there is the need of two men in the water: one man working, and the other to handle the umbilical line, from the open bottom diving bell or basket; any emergency assistance or rescue activity become more difficult to provide since the other persons remain on the platform deck, 15 meters above; delivering material and tools to the divers, at their work location; job poor performance figures; no space on the platforms for the installation of support equipments; no accommodations for extra crew; SUMMARY OF THE INVENTION The present invention is a new concept of shallow diving system (up to 50 meters), in open sea, that is a safer and a more efficient alternative to carry out this job, which makes possible for the divers to move around in order to get access and operate in safe conditions in all points of the hull. The diving system, including all the support equipment, operates from another vessel, provided with dynamic positioning system, located nearby the job place, on board of which are arranged the auxiliary equipment necessary to support the diving operation. The system now proposed consists of a main vessel, provided with a dynamic positioning system (DP) and with the equipments to monitor the diving operation, to give assistance and orientation to the divers. The main vessel operates with support vessels, and together they set the divers and the support team at the work location, at a safe distance from the main vessel propulsion system. These vessels for direct supporting the diving operation, act like satellites of the main vessel, linked to it by means of umbilical lines. BRIEF DESCRIPTION OF DRAWINGS FIG. 1 shows a schematic plan view of the diving system object of the present invention. FIG. 2 represents a schematic profile view of the system presented in FIG. 1. DETAILED DESCRIPTION OF THE INVENTION The invention will be better understood if described together with the Figures, which are part of this report. The shallow diving system in open sea utilizes a vessel, named main vessel 2, which is positioned nearby the installation unit 1, and is used as a base for working, that operates together with an auxiliary support vessel 3, smaller, referred as diving boat, from now on. The main vessel 2 is provided with a dynamic positioning system, an uninterrupted power generation system for the diving system, capable of assure the divers' decompression in emergency situation but, in accordance with the procedures adopted during normal conditions, and being able to comply with the legal regulations established for shallow diving operations. The diving boat, vessel 3, must provide the operational and safety utilities. It must have redundancy in the propulsion power system by dual water jet units in order to guarantee the motion, positioning and protection of the people in the water, and also have a control panel for three divers, two actually diving and one diver in safety “stand by”, an operation control panel to make possible a complete control and follow-up, through audio, video and registered data, of the supplied pressures and depths, and a video camera for each diver in the water and one camera placed under the hull. That means audio and video communication, to guide and register the operations, from the main diving control center, located near the dynamic positioning system control in the main vessel, up to the divers working in the water, with control of the diving supervisor in the diving boat. Further, the diving boat must have an emergency air compression system, which consists of two high pressure bottles with enough capacity to decompress two divers (about 60 liters/3000 psi), considering the maximum time foreseen in a 50 meters diving. The diving boat shall have an arrangement to handle the diving umbilical lines, space for a stretcher with a person laying down, equipment for first aid and be able to transport eight people, as a minimum, i.e., a diving supervisor, two support divers, one diver as in stand by, two official divers, one boat operator and one auxiliary man. DESCRIPTION OF THE PREFERRED EMBODIMENT According to previous description, the main vessel 2 must have the accommodations for the crew and the diving system team, space to assemble the auxiliary equipment, and be a fixed referenced platform for the whole system positioning. When it is positioned nearby the unit in the sea, installation 1, it shall make possible the correct positioning of the diving boat, vessel 3, on the desired work location, indicated as 4. The diving boat 3, connected to the main vessel 2 by means of supply umbilical, indicated as 5, render possible the assistance and support to the diving operation, from a point at the surface straight above the desired work location, and also provide a minimum distance between the divers, indicated as 6, and the main vessel propeller system for a safe operation (about 30 meters). The umbilical line has positive buoyancy and is used as an auxiliary device for the positioning of the diving boat in relation to the main vessel. During the diving operation the umbilical line is kept at the proper length and tension in the desired direction by the diving boat puling on the line, the load is applied and controlled by the diving boat and this keeps the desired diving position stable. Among other advantages the following ones are emphasized: the divers and the team for supporting the diving activity work as near as possible to the desired work location; guarantee immediate rescue of the divers in emergency conditions; improve the assistance to the divers in normal conditions by facilitating the delivering of tools and material to do the job; make feasible the work of two divers concomitantly, with a third one as a safety stand-by diver, inside the diving boat; provide an unlimited supply, from the main vessel, of the utilities required for normal diving operation conditions, through the umbilical line that connects the diving boat to the main vessel, that also limits the maximum distance between the boats; guarantee the diving boat autonomy in relation to the diving systems provisions, and position keeping capabilities to stay at the desired position after disconnecting the umbilical line that links it to the main vessel, in order to realize the rescue of the divers safely in emergency conditions; redundancy in the launching and rescue systems of the diving boat, provided that the operation may be executed with the boat at its full capacity, with the crew inside it. An extraordinary improvement in job performance comes forth when using this new concept for shallow diving system, and is clearly noticed by those with a skill in the art.
<SOH> BACKGROUND OF THE INVENTION <EOH>Nowadays, the shallow diving systems used in oil exploitation and production offshore platforms that operate in deep waters are based and operated from the same unit where the inspecting work will be performed. In offshore platforms the physical space is limited. After installing exploitation systems, their facilities, safety systems, accommodations, loading areas, winches, cranes, heliport and escape routes, there are few remaining spaces on board. Diving systems in use are arranged in these remaining spaces, and they utilize as a transportation mean to access the submerse region, an open bottom diving bell or basket, that is kept suspended and vertically lowered by means of an articulated structure that extends outside the platform structure. These systems, however, can only control the open bottom diving bell positioning in the vertical direction, the necessary horizontal displacement is obtained by moving the divers away from it, at the depth work, by using an umbilical line that links them. Due to the few available space for installing the diving equipments, the distances between diving places and work places demand the use of long umbilical lines, that require a greater physical effort from the divers, and increase considerably the risk of the operation that may become unsafe or not be feasible in different points of the unit. Many occurrences have demonstrated that the arrangements made for launching and rescuing the divers, as those used for shallow diving systems, located in platforms, could not guarantee the immediate rescue of injured/endangered divers. Generally the only way for doing the rescue, is with the open bottom diving bell itself or the diving basket, that most of the time can not be placed where the diver is, or can not be immediately raised due to untangled umbilical lines and/or other reasons. Floating production, storage and off-loading units, known as FPSO, that are authorized to operate for periods up to twenty years, without dry-docking, have their structural integrity verified by programmed sub aquatic surveys, together with non destructive test (NDT) inspection, in all the hull extension, and the execution of the repairs identified as necessary. The activities comprised in the job for sub aquatic inspection and repairing demand a peculiar structure entirely dedicated, with facilities to give support to the divers' life and adequate working conditions, safety and effectiveness for the job. The optimization of space on the production units clearly indicates that an improvement in the actual operating conditions for diving systems will be reached only with an evolution within the concept that overtakes the present critical points, listed bellow: difficulty in rescuing the divers in an emergency situation; short range for the horizontal reaching capability, limited by the umbilical line length that can be handled securely; great difficulty to access different points of the platforms; divers physical effort due to the use of long umbilical line; necessity to move (re install) the support equipments; there is the need of two men in the water: one man working, and the other to handle the umbilical line, from the open bottom diving bell or basket; any emergency assistance or rescue activity become more difficult to provide since the other persons remain on the platform deck, 15 meters above; delivering material and tools to the divers, at their work location; job poor performance figures; no space on the platforms for the installation of support equipments; no accommodations for extra crew;
<SOH> SUMMARY OF THE INVENTION <EOH>The present invention is a new concept of shallow diving system (up to 50 meters), in open sea, that is a safer and a more efficient alternative to carry out this job, which makes possible for the divers to move around in order to get access and operate in safe conditions in all points of the hull. The diving system, including all the support equipment, operates from another vessel, provided with dynamic positioning system, located nearby the job place, on board of which are arranged the auxiliary equipment necessary to support the diving operation. The system now proposed consists of a main vessel, provided with a dynamic positioning system (DP) and with the equipments to monitor the diving operation, to give assistance and orientation to the divers. The main vessel operates with support vessels, and together they set the divers and the support team at the work location, at a safe distance from the main vessel propulsion system. These vessels for direct supporting the diving operation, act like satellites of the main vessel, linked to it by means of umbilical lines.
20050512
20070911
20060727
64647.0
B63C1100
0
LAGMAN, FREDERICK LYNDON
SATELLITE SYSTEM FOR SHALLOW DIVING
SMALL
0
ACCEPTED
B63C
2,005
10,534,690
ACCEPTED
Pump driving method and device therefor
A pump driving apparatus has a characteristic changing section which receives a set pressure, a set flowing amount, a set horse power, and a DC voltage of the converter section as input, outputs modified values of pressure, flowing amount, and horse power, and supplies the modified values to the horse power command generation section. Therefore, the motor can be driven to suit the change in power voltage so that the motor capacity can be utilized sufficiently.
1. A pump driving method comprising: driving a motor based upon a command value using a discharge pressure—discharge flow characteristic; carrying out feedback control of a discharge pressure, and driving a pump using the motor to change the discharge pressure—discharge flow characteristic in correspondence with a power voltage. 2. A pump driving method as set forth in claim 1, further comprising holding, the discharge pressure—discharge flow characteristics corresponding to a plurality of power voltage, respectively, and selecting a corresponding one of the discharge pressure—discharge flow characteristics in correspondence with a detection value of the power voltage. 3. A pump driving method as set forth in claim 1, further comprising defining a predetermined pressure, flowing amount, and horse power as characteristic values for a predetermined power voltage, and changing the discharge pressure—discharge flow characteristic in correspondence with a detection value of the power voltage. 4. A pump driving method comprising: driving a motor based upon a command value using discharge pressure—discharge flow characteristic, carrying out feedback control of a discharge pressure, driving a pump using the motor based on whether or not a DC voltage of an inverter for supplying a driving voltage to the motor is an ideal DC voltage value of an alternate current power voltage, changing the discharge pressure—discharge flow characteristic for the DC voltage upon judging that the DC voltage is the ideal DC voltage value of the alternate current power voltage, and maintaining a changed discharge pressure—discharge flow characteristic upon judging that the DC voltage is not the ideal DC voltage value of the alternate current power voltage and when just previously judged the DC voltage was the ideal DC voltage value of the alternate current power voltage. 5. The pump driving method as set forth in claim 4, wherein the maintaining of the changed discharge pressure—discharge flow characteristic is accomplished by maintaining a power voltage value instead the maintaining of the discharge pressure—discharge flow characteristic. 6. A pump driving apparatus comprising: a motor configured to be driven based upon a command value using a discharge pressure—discharge flow characteristic to feedback control a discharge pressure, a pump operatively coupled to the motor, and a characteristic changing section configured to change the discharge pressure—discharge flow characteristic in correspondence with a power voltage. 7. The pump driving apparatus as set forth in claim 6, wherein the characteristic changing section is configured to hold the discharge pressure—discharge flow characteristics corresponding to a plurality of power voltage, respectively, and to select a corresponding one of the discharge pressure—discharge flow characteristics in correspondence with a detection value of the power voltage. 8. The pump driving apparatus as set forth in claim 6, wherein the characteristic changing section is configured to define a predetermined pressure, flowing amount, and horse power as characteristic values for a predetermined power voltage, and to change the discharge pressure—discharge flow characteristic in correspondence with a detection value of the power voltage. 9. A pump driving apparatus comprising: a motor configured to be driven based upon a command value using a discharge pressure—discharge flow characteristic to feedback control a discharge pressure, a pump operatively coupled to the motor, and judgment means for judging whether or not a DC voltage of an inverter for supplying a driving voltage to a motor is an ideal DC voltage value of an alternate current power voltage, for changing a discharge pressure—discharge flow characteristic for the DC voltage when it is judged that the DC voltage is the ideal DC voltage value of the alternate current power voltage, and for maintaining the changed discharge pressure—discharge flow characteristic upon judging that the DC voltage is not the ideal DC voltage value of the alternate current power voltage and when the just previously judged the DC voltage was the ideal DC voltage value of the alternate current power voltage. 10. The A pump driving apparatus as set forth in claim 9, wherein the judgment means maintains a power voltage value instead the maintaining of the discharge pressure—discharge flow characteristic.
TECHNICAL FIELD The present invention relates to a pump driving method and apparatus thereof which drive a motor based upon a command value using discharge pressure—discharge flow characteristic and carrying out feedback of the discharge pressure, and drive a pump using the motor. BACKGROUND ART From the past, a pump driving apparatus is proposed which drives a motor based upon a command value using discharge pressure—discharge flow characteristic and carrying out feedback of the discharge pressure, and drives a pump using the motor. FIG. 1 is a block diagram illustrating a conventional pump driving apparatus. The pump driving apparatus comprises a converter section 101, an inverter section 102, a motor 103, and a pump 104. The converter section 101 receives an alternate current power source as input and generates a direct current voltage. The inverter section 102 receives the direct current voltage as input and outputs an alternate current voltage. The motor 103 is supplied the alternate current voltage. The pump 104 is connected to an output shaft of the motor 103. The pump driving apparatus also comprises a horse power command generation section 105, a subtraction section 106, a proportional controller 107, an integral controller 108, an integrator 109, an addition section 110, a speed control section 111, and a current control section 112. The horse power command generation section 105 generates a horse power command based upon discharge pressure—discharge flow characteristic (hereinafter, referred to as P-Q characteristic), a current pressure, and a current flowing amount, the P-Q characteristic being generated, as is illustrated in FIG. 5, by a set pressure, a set flowing amount, and a set horse power defined for a predetermined power voltage. The subtraction section 106 calculates a difference between the horse power command output from the horse power command generation section 105 and a current horse power. The proportional controller 107 receives the horse power difference as input, and carries out the proportional control. The integral controller 108 receives the horse power difference as input, and carries out the integral control. The integrator 109 integrates the integral control result. The addition section 110 adds the proportional control result and the integration result so as to obtain a proportion-integration control result (speed command). The speed control section 111 receives the speed command as input, carries out the speed control operation, and outputs a current command. The current control section 112 receives the current command and a DC voltage of the converter section 101, carries out the current control operation so as to generate a duty command, and supplies the duty command to the inverter section 102. The pump driving apparatus further comprises a speed detection section 114, a flowing amount detection section 117, a pressure sensor 115, and a horse power operation section 116. The speed detection section 114 receives a pulse output from a pulse generator 113 which is connected to the motor 103, and calculates a current speed of the motor 103 based upon a pulse interval. The flowing amount detection section 117 receives the current speed as input, and calculates a discharge flow by taking a pump volume and the like into consideration. The pressure sensor 115 detects a current pressure of discharge fluid from the pump 104. The horse power operation section 116 calculates a current horse power based upon the current flowing amount and the current pressure. Therefore, adequate pump control can be realized in which the defined P-Q characteristic is determined to be a maximum area. However, a power voltage is not guaranteed to be kept to a predetermined voltage. A power voltage affects driving, stopping, and the like of adjacent apparatus and the like, and varies accordingly. Therefore, sufficient capacity cannot be realized when a pump is driven using P-Q characteristic which is defined for the predetermined power voltage. Description is made further. When a power voltage becomes lower than a predetermined rated voltage, a discharge pressure which is actually possible to be output becomes lower than the discharge pressure {circumflex over (1)} for the predetermined rated voltage, as is illustrated with {circumflex over (3)} in FIG. 2. This P-Q characteristic can be converted to torque—revolution speed characteristic of a motor (refer to FIG. 3). And, {circumflex over (1)}{circumflex over (2)}{circumflex over (3)} in FIG. 2 correspond to {circumflex over (1)}{circumflex over (2)}{circumflex over (3)} in FIG. 3, respectively. As a result, a condition continues where a current value does not reach for the command value corresponding to the P-Q characteristic illustrated with {circumflex over (1)}. And, for this time period, the integrator 109 of the PQ control continues the integration, therefore, the discharge pressure greatly overshoots after the integration result exceeding the constant horse power region (windup phenomenon). Therefore, in the past, the P-Q characteristic is determined, as is illustrated with {circumflex over (3)}, for not causing problem in control response even when a power voltage is lowered to some degree. As a result, a disadvantage arises in that a motor capacity cannot be utilized sufficiently. On the contrary, when the discharge pressure which is actually possible to be output becomes higher than the discharge pressure {circumflex over (1)} for the predetermined rated voltage, as is illustrated with {circumflex over (2)} in FIG. 2, the output following the P-Q characteristic illustrated with {circumflex over (2)} becomes possible. However, a command value only corresponds to the P-Q characteristic illustrated with {circumflex over (1)}, therefore, a disadvantage arises in that a motor capacity cannot be utilized sufficiently, similarly. SUMMARY OF THE INVENTION The present invention was made in view of the above problems. It is an object of the present invention to provide a pump driving method and apparatus thereof in which a motor capacity cannot be utilized sufficiently following varying in a power voltage. A pump driving method of a first aspect changes discharge pressure—discharge flow characteristic in correspondence with a power voltage when a motor is driven based upon a command value using discharge pressure—discharge flow characteristic and feedback of the discharge pressure is carried out, and a pump is driven using the motor. A pump driving method of a second aspect holds discharge pressure—discharge flow characteristics corresponding to a plurality of power voltage, respectively, and selects a corresponding discharge pressure—discharge flow characteristic in correspondence with a detection value in power voltage. A pump driving method of a third aspect defines a predetermined pressure, flowing amount, and horse power as characteristic values for a predetermined power voltage, and changes a discharge pressure—discharge flow characteristic in correspondence with a detection value in power voltage. A pump driving method of a fourth aspect judges whether or not a DC voltage of an inverter for supplying a driving voltage to a motor is a ideal DC voltage value of an alternate current power voltage, changes a discharge pressure—discharge flow characteristic for the DC voltage when it is judged that the DC voltage is the ideal DC voltage value of the alternate current power voltage, and maintains the changed discharge pressure—discharge flow characteristic when it is judged that the DC voltage is not the ideal DC voltage value of the alternate current power voltage and when the just prior DC voltage is the ideal DC voltage value of the alternate current power voltage, when a motor is driven based upon a command value using discharge pressure—discharge flow characteristic and feedback of the discharge pressure is carried out, and a pump is driven using the motor. A pump driving method of a fifth aspect maintains a power voltage value instead the maintaining of the discharge pressure—discharge flow characteristic. A pump driving apparatus of a sixth aspect drives a motor based upon a command value using discharge pressure—discharge flow characteristic and carries out feedback of the discharge pressure, and drives a pump using the motor, the apparatus comprises characteristic changing means for changing discharge pressure—discharge flow characteristic in correspondence with a power voltage. A pump driving apparatus of a seventh aspect employs means for holding discharge pressure—discharge flow characteristics corresponding to a plurality of power voltage, respectively, and for selecting a corresponding discharge pressure—discharge flow characteristic in correspondence with a detection value in power voltage, as the characteristic changing means. A pump driving apparatus of an eighth aspect employs means for defining a predetermined pressure, flowing amount, and horse power as characteristic values for a predetermined power voltage, and for changing a discharge pressure—discharge flow characteristic in correspondence with a detection value in power voltage, as the characteristic changing means. A pump driving apparatus of a ninth aspect drives a motor based upon a command value using discharge pressure—discharge flow characteristic and carries out feedback of the discharge pressure, and drives a pump using the motor, the apparatus comprises judgment means for judging whether or not a DC voltage of an inverter for supplying a driving voltage to a motor is a ideal DC voltage value of an alternate current power voltage, for changing a discharge pressure—discharge flow characteristic for the DC voltage when it is judged that the DC voltage is the ideal DC voltage value of the alternate current power voltage, and for maintaining the changed discharge pressure—discharge flow characteristic when it is judged that the DC voltage is not the ideal DC voltage value of the alternate current power voltage and when the just prior DC voltage is the ideal DC voltage value of the alternate current power voltage, when a motor is driven based upon a command value using discharge pressure—discharge flow characteristic and feedback of the discharge pressure is carried out, and a pump is driven using the motor. A pump driving apparatus of a tenth aspect employs means for maintaining a power voltage value instead the maintaining of the discharge pressure—discharge flow characteristic, as the judgment means. When the pump driving method of a first aspect is employed, the discharge pressure—discharge flow characteristic is changed in correspondence with a power voltage when a motor is driven based upon a command value using discharge pressure—discharge flow characteristic and feedback of the discharge pressure is carried out, and a pump is driven using the motor. Therefore, the motor can be driven to match a value which can be actually output, and the motor capacity can be made the best use of sufficiently. When the pump driving method of a second aspect is employed, the discharge pressure—discharge flow characteristics corresponding to a plurality of power voltage are held, respectively, and a corresponding discharge pressure—discharge flow characteristic is selected in correspondence with a detection value in power voltage. Therefore, performing of the processing rapidly can be realized, and operation and effect similar to those of the first aspect can be realized. When the pump driving method of a third aspect is employed, a predetermined pressure, flowing amount, and horse power are defined as characteristic values for a predetermined power voltage, and a discharge pressure—discharge flow characteristic is changed in correspondence with a detection value in power voltage. Therefore, a required memory capacity can be made smaller, and operation and effect similar to those of the first aspect can be realized. When the pump driving method of a fourth aspect is employed, it is judged whether or not a DC voltage of an inverter for supplying a driving voltage to a motor is a ideal DC voltage value of an alternate current power voltage, a discharge pressure—discharge flow characteristic is changed for the DC voltage when it is judged that the DC voltage is the ideal DC voltage value of the alternate current power voltage, and the changed discharge pressure—discharge flow characteristic is maintained when it is judged that the DC voltage is not the ideal DC voltage value of the alternate current power voltage and when the just prior DC voltage is the ideal DC voltage value of the alternate current power voltage, when a motor is driven based upon a command value using discharge pressure—discharge flow characteristic and feedback of the discharge pressure is carried out, and a pump is driven using the motor. Therefore, instability in transition condition is dissolved, the motor can be driven to match a value which can be actually output, and the motor capacity can be made the best use of sufficiently. When the pump driving method of a fifth aspect is employed, a power voltage value is maintained instead the maintaining of the discharge pressure—discharge flow characteristic. Therefore, held data amount can be made smaller, and operation and effect similar to those of the fourth aspect can be realized. When the pump driving apparatus of a sixth aspect is employed, the discharge pressure—discharge flow characteristic is changed in correspondence with a power voltage by the characteristic changing means when a motor is driven based upon a command value using discharge pressure—discharge flow characteristic and feedback of the discharge pressure is carried out, and a pump is driven using the motor. Therefore, the motor can be driven to match a value which can be actually output, and the motor capacity can be made the best use of sufficiently. When the pump driving apparatus of a seventh aspect is employed, means for holding discharge pressure—discharge flow characteristics corresponding to a plurality of power voltage, respectively, and for selecting a corresponding discharge pressure—discharge flow characteristic in correspondence with a detection value in power voltage, is employed as the characteristic changing means. Therefore, performing of the processing rapidly can be realized, and operation and effect similar to those of the sixth aspect can be realized. When the pump driving apparatus of an eighth aspect is employed, means for defining a predetermined pressure, flowing amount, and horse power as characteristic values for a predetermined power voltage, and for changing a discharge pressure—discharge flow characteristic in correspondence with a detection value in power voltage, is employed as the characteristic changing means. Therefore, a required memory capacity can be made smaller, and operation and effect similar to those of the sixth aspect can be realized. When the pump driving apparatus of a ninth aspect is employed, it is judged whether or not a DC voltage of an inverter for supplying a driving voltage to a motor is a ideal DC voltage value of an alternate current power voltage, a discharge pressure—discharge flow characteristic is changed for the DC voltage when it is judged that the DC voltage is the ideal DC voltage value of the alternate current power voltage, and the changed discharge pressure—discharge flow characteristic is maintained when it is judged that the DC voltage is not the ideal DC voltage value of the alternate current power voltage and when the just prior DC voltage is the ideal DC voltage value of the alternate current power voltage, by the judgment means, when a motor is driven based upon a command value using discharge pressure—discharge flow characteristic and feedback of the discharge pressure is carried out, and a pump is driven using the motor. Therefore, instability in transition condition is dissolved, the motor can be driven to match a value which can be actually output, and the motor capacity can be made the best use of sufficiently. When the pump driving apparatus of a tenth aspect is employed, means for maintaining a power voltage value instead the maintaining of the discharge pressure—discharge flow characteristic, is employed as the judgment means. Therefore, held data amount can be made smaller, and operation and effect similar to those of the ninth aspect can be realized. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a block diagram illustrating a conventional pump driving apparatus; FIG. 2 is a diagram illustrating P-Q characteristic; FIG. 3 is a diagram illustrating torque—revolution speed characteristic in correspondence with the P-Q characteristic of FIG. 2; FIG. 4 is a block diagram illustrating a pump driving apparatus of an embodiment according to the present invention; FIG. 5 is a diagram useful in understanding generation of P-Q characteristic; FIG. 6 is a block diagram illustrating a main portion of the pump driving apparatus of the embodiment according to the present invention; FIG. 7 is a block diagram illustrating a main portion of a pump driving apparatus of another embodiment according to the present invention; and FIG. 8 is a block diagram illustrating a main portion of a pump driving apparatus of a further embodiment according to the present invention. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, referring to the attached drawings, we explain embodiments of a pump driving method and apparatus thereof according to the present invention. FIG. 4 is a block diagram illustrating a pump driving apparatus of an embodiment according to the present invention. FIG. 6 is a block diagram illustrating a characteristic changing section 18 of FIG. 4 in more detail. The pump driving apparatus comprises a converter section 1, an inverter section 2, a motor 3, and a pump 4. The converter section 1 receives an alternate current power source as input and generates a direct current voltage. The inverter section 2 receives the direct current voltage as input and outputs an alternate current voltage. The motor 3 is supplied the alternate current voltage. The pump 4 is connected to an output shaft of the motor 3. The pump driving apparatus also comprises a characteristic changing section 18, a horse power command generation section 5, a subtraction section 6, a proportional controller 7, an integral controller 8, an integrator 9, an addition section 10, a speed control section 11, and a current control section 12. The characteristic changing section 18 receives a set pressure, a set flowing amount, a set horse power, and a DC voltage of the converter section 1 as input, outputs modified values of pressure, flowing amount, and horse power, and supplies the modified values to the horse power command generation section 5. The horse power command generation section 5 calculates a horse power command based upon the modified values of pressure, flowing amount, and horse power, and current pressure, and current flowing amount. The subtraction section 6 calculates a difference between the horse power command output from the horse power generation section 5 and a current horse power. The proportional controller 7 receives the horse power difference as input, and carries out the proportional control. The integral controller 8 receives the horse power difference as input, and carries out the integral control. The integrator 9 integrates the integral control result. The addition section 10 adds the proportional control result and the integration result so as to obtain a poroportion-integration control result (speed command). The speed control section 11 receives the speed command as input, carries out the speed control operation, and outputs a current command. The current control section 12 receives the current command and a DC voltage of the converter section 1, carries out the current control operation so as to generate a duty command, and supplies the duty command to the inverter section 2. The pump driving apparatus further comprises a speed detection section 14, a flowing amount detection section 17, a pressure sensor 15, and a horse power operation section 16. The speed detection section 14 receives a pulse output from a pulse generator 13 which is connected to the motor 3, and calculates a current speed of the motor 3 based upon a pulse interval. The flowing amount detection section 17 receives the current speed as input, and calculates a discharge flow by taking a pump volume and the like into consideration. The pressure sensor 15 detects a current pressure of discharge fluid from the pump 4. The horse power operation section 16 calculates a current horse power based upon the current flowing amount and the current pressure. The pump driving apparatus further comprises a ratio calculation section 27, and a multiplication section 28. The ratio calculation section 27 calculates a ratio between a predetermined power voltage 26 and the DC voltage of the converter section 1. The multiplication section 28 multiplies the operation result (voltage change ratio) calculated by the ratio calculation section 27 to the set horse power so as to generate the modified horse power. Operation of the pump driving apparatus having the above arrangement is as follows. Operation in a case where the predetermined voltage is equal to the predetermined power voltage is similar to that of the pump driving apparatus in FIG. 1, therefore, description for the case is omitted. Only operation in a case where the power voltage is changed, is described. When a power voltage is different from the predetermined power voltage, the DC voltage output from the converter section I changes in correspondence with the changing of the power voltage. The characteristic changing section 18 supplies modified values (pressure, flowing amount, horse power) to the horse power command generation section 5 in correspondence with the DC voltage, even when the set pressure, the set flowing amount, and the set horse power are constant. As a result, the horse power command generation section 5 generates a horse power command based upon the adequate P-Q characteristic, and the pump 4 is driven based upon the generated horse power command. In other words, the motor can be driven to suit a value which can actually be output so that the motor capacity can be utilized sufficiently. It is preferable that the horse power command generation section 5 generates characteristic for every region a, b, and c illustrated in FIG. 5, based upon the modified pressure, flowing amount, and horse power. In the above embodiment, P-Q characteristic is changed using the DC voltage. However, it is possible that P-Q characteristic is changed using an AC power voltage. When AC power is three phase power, it is required to detect power voltages for three phases to deal with the unbalanced supply voltage. Therefore, it is preferable that the DC voltage is used in view of simplification in arrangement, and reduction in cost. FIG. 7 is a block diagram illustrating a main portion of a characteristic changing section 18 of a pump driving apparatus of another embodiment according to the present invention. The characteristic changing section in FIG. 7 comprises a low-pass filter 222, a driving condition stability judgment section 223, a ratio calculation section 227, and a multiplication section 228. The low-pass filter 222 removes high frequency noises and the like included in the input DC voltage. The driving condition stability judgment section 223 judges whether or not driving condition is stable. The ratio calculation section 227 calculates a ratio between the output voltage from the low-pass filter 222 and the predetermined power voltage output from a predetermined power voltage holding section 226. The multiplication section 228 multiplies the operation result (voltage change ratio) calculated by the ratio calculation section 227 to the set horse power so as to generate a modified horse power. A section for judging that driving condition is stable, for example, when a condition is continuing equal to or more than 500 msec, in the condition the motor 3 is driven equal to or less than 2000 rpm and when speed change under the condition is equal to or less than 500 rpm, or when a condition is continuing equal to or more than 500 msec, in the condition the motor 3 is driven equal to or less than 2000 rpm and when speed change under the condition exceeds 500 rpm and when the motor 3 is driven equal to or less than 2000 rpm after 500 msec has passed, is employed as the driving condition stability judgment section 223. However, it is possible to employ other conditions. When the arrangement in FIG. 7 is employed, only when it is judged that driving condition is stable, a switch 224 is turned on so as to sample-hold the corrected set horse power which is the output value of the multiplication section 228, and to hold the corrected set horse power in a modified horse power holding section 225. When it is judged that driving condition is not stable, the switch 224 is turned off so as to generate a modified horse power which is held by the modified horse power holding section 225. Therefore, driving of the pump with more stability is realized. Description is made further. When the power voltage is detected from the DC voltage, for example, power regeneration may be generated due to deceleration of the motor so that the DC voltage may be raised temporally. When P-Q characteristic is changed by taking the DC voltage into consideration as power voltage change directly for such case, the control condition may become unstable. However, when the arrangement of FIG. 7 is employed, the motor 3 continues power running for some time period depending upon the motor speed and the degree of power voltage change so that the power is consumed, the power corresponding to the raise due to the power regeneration. The correction of P-Q characteristic is carried out only in a case that the DC voltage is supposed to become the ideal DC voltage value of the AC power voltage (AC voltage×21/2). In transient state, the modified horse power is continuously used, the modified horse power being held by the modified horse power holding section 225 prior to becoming transient state. Consequently, the pump 4 can be controlled stably. By employing a section for judging that driving condition is stable, for example, when a condition is continuing equal to or more than 500 msec, in the condition the motor 3 is driven equal to or less than 2000 rpm and when speed change under the condition is equal to or less than 500 rpm, or when a condition is continuing equal to or more than 500 msec, in the condition the motor 3 is driven equal to or less than 2000 rpm and when speed change under the condition exceeds 500 rpm and when the motor 3 is driven equal to or less than 2000 rpm after 500 msec has passed, as the driving condition stability judgment section 223, it is possible that P-Q characteristic is corrected only in dwelling condition. When the AC power voltage is directly detected, the above disadvantages and the like are not generated. Therefore, it is not necessary that the arrangement of FIG. 7 is employed. By allowing the current voltage holding section 325 to hold the output voltage from the low-pass filter 322 by turning the switch 325 on/off using the output of the driving condition stability judgment section 323, as is illustrated in FIG. 8, operation and effect similar to those of FIG. 7 can be realized.
<SOH> BACKGROUND ART <EOH>From the past, a pump driving apparatus is proposed which drives a motor based upon a command value using discharge pressure—discharge flow characteristic and carrying out feedback of the discharge pressure, and drives a pump using the motor. FIG. 1 is a block diagram illustrating a conventional pump driving apparatus. The pump driving apparatus comprises a converter section 101 , an inverter section 102 , a motor 103 , and a pump 104 . The converter section 101 receives an alternate current power source as input and generates a direct current voltage. The inverter section 102 receives the direct current voltage as input and outputs an alternate current voltage. The motor 103 is supplied the alternate current voltage. The pump 104 is connected to an output shaft of the motor 103 . The pump driving apparatus also comprises a horse power command generation section 105 , a subtraction section 106 , a proportional controller 107 , an integral controller 108 , an integrator 109 , an addition section 110 , a speed control section 111 , and a current control section 112 . The horse power command generation section 105 generates a horse power command based upon discharge pressure—discharge flow characteristic (hereinafter, referred to as P-Q characteristic), a current pressure, and a current flowing amount, the P-Q characteristic being generated, as is illustrated in FIG. 5 , by a set pressure, a set flowing amount, and a set horse power defined for a predetermined power voltage. The subtraction section 106 calculates a difference between the horse power command output from the horse power command generation section 105 and a current horse power. The proportional controller 107 receives the horse power difference as input, and carries out the proportional control. The integral controller 108 receives the horse power difference as input, and carries out the integral control. The integrator 109 integrates the integral control result. The addition section 110 adds the proportional control result and the integration result so as to obtain a proportion-integration control result (speed command). The speed control section 111 receives the speed command as input, carries out the speed control operation, and outputs a current command. The current control section 112 receives the current command and a DC voltage of the converter section 101 , carries out the current control operation so as to generate a duty command, and supplies the duty command to the inverter section 102 . The pump driving apparatus further comprises a speed detection section 114 , a flowing amount detection section 117 , a pressure sensor 115 , and a horse power operation section 116 . The speed detection section 114 receives a pulse output from a pulse generator 113 which is connected to the motor 103 , and calculates a current speed of the motor 103 based upon a pulse interval. The flowing amount detection section 117 receives the current speed as input, and calculates a discharge flow by taking a pump volume and the like into consideration. The pressure sensor 115 detects a current pressure of discharge fluid from the pump 104 . The horse power operation section 116 calculates a current horse power based upon the current flowing amount and the current pressure. Therefore, adequate pump control can be realized in which the defined P-Q characteristic is determined to be a maximum area. However, a power voltage is not guaranteed to be kept to a predetermined voltage. A power voltage affects driving, stopping, and the like of adjacent apparatus and the like, and varies accordingly. Therefore, sufficient capacity cannot be realized when a pump is driven using P-Q characteristic which is defined for the predetermined power voltage. Description is made further. When a power voltage becomes lower than a predetermined rated voltage, a discharge pressure which is actually possible to be output becomes lower than the discharge pressure {circumflex over ( 1 )} for the predetermined rated voltage, as is illustrated with {circumflex over ( 3 )} in FIG. 2 . This P-Q characteristic can be converted to torque—revolution speed characteristic of a motor (refer to FIG. 3 ). And, {circumflex over ( 1 )}{circumflex over ( 2 )}{circumflex over ( 3 )} in FIG. 2 correspond to {circumflex over ( 1 )}{circumflex over ( 2 )}{circumflex over ( 3 )} in FIG. 3 , respectively. As a result, a condition continues where a current value does not reach for the command value corresponding to the P-Q characteristic illustrated with {circumflex over ( 1 )}. And, for this time period, the integrator 109 of the PQ control continues the integration, therefore, the discharge pressure greatly overshoots after the integration result exceeding the constant horse power region (windup phenomenon). Therefore, in the past, the P-Q characteristic is determined, as is illustrated with {circumflex over ( 3 )}, for not causing problem in control response even when a power voltage is lowered to some degree. As a result, a disadvantage arises in that a motor capacity cannot be utilized sufficiently. On the contrary, when the discharge pressure which is actually possible to be output becomes higher than the discharge pressure {circumflex over ( 1 )} for the predetermined rated voltage, as is illustrated with {circumflex over ( 2 )} in FIG. 2 , the output following the P-Q characteristic illustrated with {circumflex over ( 2 )} becomes possible. However, a command value only corresponds to the P-Q characteristic illustrated with {circumflex over ( 1 )}, therefore, a disadvantage arises in that a motor capacity cannot be utilized sufficiently, similarly.
<SOH> SUMMARY OF THE INVENTION <EOH>The present invention was made in view of the above problems. It is an object of the present invention to provide a pump driving method and apparatus thereof in which a motor capacity cannot be utilized sufficiently following varying in a power voltage. A pump driving method of a first aspect changes discharge pressure—discharge flow characteristic in correspondence with a power voltage when a motor is driven based upon a command value using discharge pressure—discharge flow characteristic and feedback of the discharge pressure is carried out, and a pump is driven using the motor. A pump driving method of a second aspect holds discharge pressure—discharge flow characteristics corresponding to a plurality of power voltage, respectively, and selects a corresponding discharge pressure—discharge flow characteristic in correspondence with a detection value in power voltage. A pump driving method of a third aspect defines a predetermined pressure, flowing amount, and horse power as characteristic values for a predetermined power voltage, and changes a discharge pressure—discharge flow characteristic in correspondence with a detection value in power voltage. A pump driving method of a fourth aspect judges whether or not a DC voltage of an inverter for supplying a driving voltage to a motor is a ideal DC voltage value of an alternate current power voltage, changes a discharge pressure—discharge flow characteristic for the DC voltage when it is judged that the DC voltage is the ideal DC voltage value of the alternate current power voltage, and maintains the changed discharge pressure—discharge flow characteristic when it is judged that the DC voltage is not the ideal DC voltage value of the alternate current power voltage and when the just prior DC voltage is the ideal DC voltage value of the alternate current power voltage, when a motor is driven based upon a command value using discharge pressure—discharge flow characteristic and feedback of the discharge pressure is carried out, and a pump is driven using the motor. A pump driving method of a fifth aspect maintains a power voltage value instead the maintaining of the discharge pressure—discharge flow characteristic. A pump driving apparatus of a sixth aspect drives a motor based upon a command value using discharge pressure—discharge flow characteristic and carries out feedback of the discharge pressure, and drives a pump using the motor, the apparatus comprises characteristic changing means for changing discharge pressure—discharge flow characteristic in correspondence with a power voltage. A pump driving apparatus of a seventh aspect employs means for holding discharge pressure—discharge flow characteristics corresponding to a plurality of power voltage, respectively, and for selecting a corresponding discharge pressure—discharge flow characteristic in correspondence with a detection value in power voltage, as the characteristic changing means. A pump driving apparatus of an eighth aspect employs means for defining a predetermined pressure, flowing amount, and horse power as characteristic values for a predetermined power voltage, and for changing a discharge pressure—discharge flow characteristic in correspondence with a detection value in power voltage, as the characteristic changing means. A pump driving apparatus of a ninth aspect drives a motor based upon a command value using discharge pressure—discharge flow characteristic and carries out feedback of the discharge pressure, and drives a pump using the motor, the apparatus comprises judgment means for judging whether or not a DC voltage of an inverter for supplying a driving voltage to a motor is a ideal DC voltage value of an alternate current power voltage, for changing a discharge pressure—discharge flow characteristic for the DC voltage when it is judged that the DC voltage is the ideal DC voltage value of the alternate current power voltage, and for maintaining the changed discharge pressure—discharge flow characteristic when it is judged that the DC voltage is not the ideal DC voltage value of the alternate current power voltage and when the just prior DC voltage is the ideal DC voltage value of the alternate current power voltage, when a motor is driven based upon a command value using discharge pressure—discharge flow characteristic and feedback of the discharge pressure is carried out, and a pump is driven using the motor. A pump driving apparatus of a tenth aspect employs means for maintaining a power voltage value instead the maintaining of the discharge pressure—discharge flow characteristic, as the judgment means. When the pump driving method of a first aspect is employed, the discharge pressure—discharge flow characteristic is changed in correspondence with a power voltage when a motor is driven based upon a command value using discharge pressure—discharge flow characteristic and feedback of the discharge pressure is carried out, and a pump is driven using the motor. Therefore, the motor can be driven to match a value which can be actually output, and the motor capacity can be made the best use of sufficiently. When the pump driving method of a second aspect is employed, the discharge pressure—discharge flow characteristics corresponding to a plurality of power voltage are held, respectively, and a corresponding discharge pressure—discharge flow characteristic is selected in correspondence with a detection value in power voltage. Therefore, performing of the processing rapidly can be realized, and operation and effect similar to those of the first aspect can be realized. When the pump driving method of a third aspect is employed, a predetermined pressure, flowing amount, and horse power are defined as characteristic values for a predetermined power voltage, and a discharge pressure—discharge flow characteristic is changed in correspondence with a detection value in power voltage. Therefore, a required memory capacity can be made smaller, and operation and effect similar to those of the first aspect can be realized. When the pump driving method of a fourth aspect is employed, it is judged whether or not a DC voltage of an inverter for supplying a driving voltage to a motor is a ideal DC voltage value of an alternate current power voltage, a discharge pressure—discharge flow characteristic is changed for the DC voltage when it is judged that the DC voltage is the ideal DC voltage value of the alternate current power voltage, and the changed discharge pressure—discharge flow characteristic is maintained when it is judged that the DC voltage is not the ideal DC voltage value of the alternate current power voltage and when the just prior DC voltage is the ideal DC voltage value of the alternate current power voltage, when a motor is driven based upon a command value using discharge pressure—discharge flow characteristic and feedback of the discharge pressure is carried out, and a pump is driven using the motor. Therefore, instability in transition condition is dissolved, the motor can be driven to match a value which can be actually output, and the motor capacity can be made the best use of sufficiently. When the pump driving method of a fifth aspect is employed, a power voltage value is maintained instead the maintaining of the discharge pressure—discharge flow characteristic. Therefore, held data amount can be made smaller, and operation and effect similar to those of the fourth aspect can be realized. When the pump driving apparatus of a sixth aspect is employed, the discharge pressure—discharge flow characteristic is changed in correspondence with a power voltage by the characteristic changing means when a motor is driven based upon a command value using discharge pressure—discharge flow characteristic and feedback of the discharge pressure is carried out, and a pump is driven using the motor. Therefore, the motor can be driven to match a value which can be actually output, and the motor capacity can be made the best use of sufficiently. When the pump driving apparatus of a seventh aspect is employed, means for holding discharge pressure—discharge flow characteristics corresponding to a plurality of power voltage, respectively, and for selecting a corresponding discharge pressure—discharge flow characteristic in correspondence with a detection value in power voltage, is employed as the characteristic changing means. Therefore, performing of the processing rapidly can be realized, and operation and effect similar to those of the sixth aspect can be realized. When the pump driving apparatus of an eighth aspect is employed, means for defining a predetermined pressure, flowing amount, and horse power as characteristic values for a predetermined power voltage, and for changing a discharge pressure—discharge flow characteristic in correspondence with a detection value in power voltage, is employed as the characteristic changing means. Therefore, a required memory capacity can be made smaller, and operation and effect similar to those of the sixth aspect can be realized. When the pump driving apparatus of a ninth aspect is employed, it is judged whether or not a DC voltage of an inverter for supplying a driving voltage to a motor is a ideal DC voltage value of an alternate current power voltage, a discharge pressure—discharge flow characteristic is changed for the DC voltage when it is judged that the DC voltage is the ideal DC voltage value of the alternate current power voltage, and the changed discharge pressure—discharge flow characteristic is maintained when it is judged that the DC voltage is not the ideal DC voltage value of the alternate current power voltage and when the just prior DC voltage is the ideal DC voltage value of the alternate current power voltage, by the judgment means, when a motor is driven based upon a command value using discharge pressure—discharge flow characteristic and feedback of the discharge pressure is carried out, and a pump is driven using the motor. Therefore, instability in transition condition is dissolved, the motor can be driven to match a value which can be actually output, and the motor capacity can be made the best use of sufficiently. When the pump driving apparatus of a tenth aspect is employed, means for maintaining a power voltage value instead the maintaining of the discharge pressure—discharge flow characteristic, is employed as the judgment means. Therefore, held data amount can be made smaller, and operation and effect similar to those of the ninth aspect can be realized.
20051012
20090915
20060713
70988.0
F04B4906
0
KASTURE, DNYANESH G
PUMP DRIVING METHOD AND DEVICE THEREFOR
UNDISCOUNTED
0
ACCEPTED
F04B
2,005
10,534,700
ACCEPTED
Method for producing software modules for field appliances used in the process automation technique
In a method for producing software modules for field devices for process automation technology (PROFIBUS), wherein the software modules serve as device descriptions and have defined interfaces, in accordance with the FDT/DTM, for application programs in process control systems, syntactically and semantically correct, standard device descriptions are produced in EDD 1.1 from PDM, HCF or company-specific device descriptions for field devices, and the EDD 1.1 versions are then converted into corresponding software modules by means of a compiler C.
1-4. (canceled) 5. A method for producing software modules for field devices for process automation technology, wherein the software modules serve as device descriptions and have defined interfaces for application programs in process control systems, comprising the steps of: producing standard device descriptions from standard device descriptions for field devices, syntactically and semantically correct; converting the standard device descriptions by means of a compiler into corresponding software modules. 6. The method as claimed in claim 5, wherein: interfaces and the software modules meet the FDT/DTM specifications (PROFIBUS Guideline—Order No. 2.162 “Specification for Profibus Device Descriptions and Device Integration”, Volume 3). 7. The method as claimed in claim 5, wherein: the standard device descriptions are one of: PDM device descriptions, HCF device descriptions or company-specific device descriptions. 8. The method as claimed in claim 5, wherein: the syntactically and semantically correct, device description is an EDD 1.1 device description (PROFIBUS Guideline—Order No. 2.162 “Specification for Profibus Device Descriptions and Device Integration”, Volume 2).
The invention relates to a method for producing software modules for field devices of process automation technology. In process automation technology, field devices are frequently used, which serve for registering and/or influencing process variables. Examples of such field devices are fill level measuring devices, mass flow meters, pressure meters, meters for measuring temperature, etc., which register the corresponding process variables fill level, mass flow rate, pressure, and temperature. Serving for the influencing of process variables are so-called actuators, which, e.g. as valves, influence the flow of a liquid in a section of pipeline. The field devices are usually connected to a data bus, and are, as a rule, connected with a central control-, or engineering-, system, which controls the entire process flow and/or enables a direct access to the individual field devices. In the control system, the measured values of the different process variables are evaluated and/or monitored, and appropriate actuators are correspondingly activated for influencing the process. Data transmission between field device and control occurs according to the known international standards for field busses, such as e.g. Hart, Foundation Fieldbus, Profibus, CAM, etc. Today's automated plants frequently involve a large number of different field devices of a widest variety of manufacturers. Before startup and/or during operation, adjustments must occur at the field devices. These adjustments must frequently be made on site. To this end, the individual field device manufacturers provide different configuration programs for the different devices. Becoming competent with the different programs, including the different operating philosophies, demands extreme effort and time on the part of the user. The parametering of individual field devices or the configuring of certain groups of field devices in an automated plant having a multiplicity of field devices is extremely complex and expensive, because of the various communications interfaces and the required protocols. The configuring, operating, and maintaining of a field device in an automated plant should be considerably simpler to perform. Desired is the integration of field devices into control systems or engineering applications via a Plug and Play capability, such as is already known e.g. for printers in Windows environments. Various field device manufacturers have, therefore, come together in PNO (PROFIBUS Nutzerorganisation e.V.), for the purpose of enabling a simpler handling of field devices. The field device manufacturers develop special software modules for their field devices. These software modules are delivered with the field devices to the customers. Each software module encapsulates all data and functions of the particular field device and represents, in principle, a black box. Additionally, the device manufacturer can integrate into these software modules its own “look and feel”. I.e., the user interface always looks the same to the user, independently of the particular application. The application program, which serves e.g. for configuring, visualizing, operating and maintaining the different field devices, accesses the particular software modules of the field device via a defined interface. One possibility is the FDT/DTM interface specification, as given in the Profibus Guideline—Order No. 2.162 of November 2000, which can be obtained via the PNO, Karlsruhe, Germany (www.profibus.com). The content of such guideline is incorporated here by reference. At the moment, corresponding software modules are available only for a few field devices. For a large number of field devices, the software modules still have to be produced by the pertinent manufacturers. One possibility is to convert available device descriptions by means of compilers, or generators, into corresponding software modules. The available device descriptions, however, do not exist in a uniform form, or language. There are PDM device descriptions, HCF device descriptions, as well as company-specific device descriptions stored in internal company databases. For each of these categories of different device descriptions, a separate compiler is necessary. Disadvantageous in the case of such method is that one must generate different compilers for different categories of device descriptions. A further disadvantage of such method is that, in the case of changes, all utilized compilers always have to be revised, in order to prevent inconsistencies. This makes the generating of software modules for field devices by means of present device descriptions very complex. It is an object of the invention to provide a method for producing software modules for field devices of process automation technology, wherein the desired software modules are produced in simple and cost-favorable manner from existing device descriptions. This object is achieved by the method steps given in claim 1. An essential idea of the invention is not to apply different compilers for different groups of existing device descriptions, but, instead, to produce, from standard device descriptions for field devices, syntactically and semantically correct, standard device descriptions and then to convert these by means of a compiler into the corresponding software modules. Advantageous further developments of the invention are set forth in the dependent claims. The invention will now be explained in greater detail on the basis of an example illustrated in the drawing, the figures of which show as follows: FIG. 1 schematic diagram of an installation for automation; and FIG. 2 schematic illustration of essential elements of the method of the invention. FIG. 1 is a schematic diagram of an installation for automation. A control system L is connected via a data bus D with a plurality of field devices F1, F2, F3, etc. The field devices F1-F3 can be e.g. pressure meters, temperature meters, or flow meters. The control system L communicates via the data bus D with the relevant field device, e.g. F1. In this way, measured values or parameters of the field device can be transmitted to the control system L. At the same time, the parametering of the field device F1 can occur from the control system L. Data communication on the data bus D occurs according to corresponding international standards, such as e.g. HART, Profibus, FF or CAN. For currently marketed field devices, there exist many groups of device descriptions in different forms and languages. Examples are, as given in FIG. 2, PDM device descriptions, HCF device descriptions and a database DB containing company-internal device descriptions. At least the PDM device descriptions, as well as the HCF device descriptions, contain ambiguities. In a first method step, syntactically and semantically correct, standard device descriptions are created from standard device descriptions (PDM device descriptions, HCF device descriptions, firm-specific device descriptions). Used for this purpose is the generator G1, or the compiler C1, as the case may be. Serving as an example of a semantically and syntactically correct, standard device description is EDD 1.1. Then, the semantically and syntactically correct, standard device description is converted with the help of a compiler C into a software module SM (e.g. DTM), which has defined interfaces to application programs in the process control system. By producing the software module SM by way of the intermediate step through an EDD, the essential advantages of the method of the invention are obtained. Only a single compiler C is needed to produce the software module SM. Furthermore, from the standard device descriptions (EDD 1.1) then available in syntactically and semantically correct form, PDM device descriptions can likewise be easily produced. Beyond this, from device descriptions in EDD 1.1, a generator G2 can be used to produce graphical user interfaces in XML language GUI.XML for the corresponding, field-device-specific components (configuration, help-functions, etc.). For this, also the generator G1 can be used, for processing information from the database DB. The components produced in this way can then likewise be processed in the compiler C. A further opportunity is to produce general graphical user interfaces GUIs and to store these in a library B (DTM-Studio component library). These components can likewise be linked in the compiler C, so that the software module SM also has proprietary interfaces for GUIs, or for components EC, or Lin., as the case may be. In this way, an envelope curve presentation capability (component EC), or a linearizing capability (component Lin.), as the case may be, can be integrated in simple manner into corresponding software modules SM.
20060425
20130219
20070118
84710.0
G06F945
0
WU, JUNCHUN
METHOD FOR PRODUCING SOFTWARE MODULES FOR FIELD DEVICES OF PROCESS AUTOMATION TECHNOLOGY
UNDISCOUNTED
0
ACCEPTED
G06F
2,006
10,534,862
ACCEPTED
Multilayer planar or tubular fooodstuff wrapping or film
Multilayer planar or tubular food casing or film The present invention for the first time furnishes a multilayer planar or tubular food casing or film for food packagings such as, e.g., sausage casings, shrink bags or the like, which comprises a layered structure having at least five, preferably at least seven layers.
1-10. (canceled) 11. Multilayer planar or tubular food casing or film for food packagings such as, e.g., sausage casings, shrink bags etc., characterized by a layered structure having at least five, preferably at least seven layers, with one of the at least five layers containing PVA as a layer constituent, and wherein the layer containing PVA is embedded between two layers containing polyamide as a layer constituent. 12. Multilayer tubular food casing or film for sausage casings, characterized by a layered structure having at least five, preferably at least seven layers, with one of the at least five layers containing PVA as a layer constituent, and having the following layered structure when counted from the outside to the inside: a) the first layer from the outside contains polyamide as a layer constituent, the second layer from the outside contains PVA as a layer constituent, the third layer from the outside contains an adhesion promoter as a layer constituent, the fourth layer from the outside contains a polyolefin, preferably polyethylene, as a layer constituent, the fifth layer from the outside contains an adhesion promoter as a layer constituent, and the sixth layer from the outside contains polyamide as a layer constituent, or b) the first layer from the outside contains polyamide as a layer constituent, the second layer from the outside contains PVA as a layer constituent, the third layer from the outside contains polyamide as a layer constituent, the fourth layer from the outside contains an adhesion promoter as a layer constituent, the fifth layer from the outside contains a polyolefin, preferably polyethylene, as a layer constituent, the sixth layer from the outside contains an adhesion promoter as a layer constituent, and the seventh layer from the outside contains polyamide as a layer constituent, or c) the first layer from the outside contains polyamide as a layer constituent, the second layer from the outside contains an adhesion promoter as a layer constituent, the third layer from the outside contains polyamide as a layer constituent, the fourth layer from the outside contains PVA as a layer constituent, the fifth layer from the outside contains polyamide as a layer constituent, the sixth layer from the outside contains an adhesion promoter as a layer constituent, and the seventh layer from the outside contains polyamide as a layer constituent. 13. Multilayer planar or tubular food casing or film for shrink bags, characterized by a layered structure having at least five, preferably at least seven layers, with one of the at least five layers containing PVA as a layer constituent, and having the following layered structure when counted from the outside to the inside: a) the first layer from the outside contains a polyolefin, preferably polyethylene, as a layer constituent, the second layer from the outside contains an adhesion promoter as a layer constituent, the third layer from the outside contains polyamide as a layer constituent, the fourth layer from the outside contains PVA as a layer constituent, the fifth layer from the outside contains polyamide as a layer constituent, the sixth layer from the outside contains an adhesion promoter as a layer constituent, and the seventh layer from the outside contains a polyolefin, preferably polyethylene, as a layer constituent, or b) the first layer from the outside contains PET as a layer constituent, the second layer from the outside contains an adhesion promoter as a layer constituent, the third layer from the outside contains polyamide as a layer constituent, the fourth layer from the outside contains PVA as a layer constituent, the fifth layer from the outside contains polyamide as a layer constituent, the sixth layer from the outside contains an adhesion promoter as a layer constituent, and the seventh layer from the outside contains a polyolefin, preferably polyethylene, as a layer constituent, or c) the first layer from the outside contains a polyolefin, preferably polyethylene, as a layer constituent, the second layer from the outside contains EVA as a layer constituent, the third layer from the outside contains an adhesion promoter as a layer constituent, the fourth layer from the outside contains PVA as a layer constituent, the fifth layer from the outside contains an adhesion promoter as a layer constituent, the sixth layer from the outside contains EVA as a layer constituent, and the seventh layer from the outside contains a polyolefin, preferably polyethylene, as a layer constituent. 14. Food casing or film for food packagings in accordance with claim 11, characterized in that layers containing a polyolefin, preferably polypropylene, as a layer constituent alternatively also contain additional polyolefins, polypropylene, EVA (ethyl vinyl alcohol), EM(M)A, ionomers, or mixtures of these, etc. 15. Food casing or film for food packagings in accordance with claim 11, characterized in that layers containing an adhesion promoter include an adhesion promoter based on PE, EVA, EM(M)A or an ionomer as a base material. 16. Food casing or film for food packagings in accordance with claim 1 1, characterized in that layers including an adhesion promoter as a constituent alternatively contain a mixture of polyolefin and adhesion promoter or a mixture of EVA and/or EM(M)A and adhesion promoter. 17. Food casing or film for food packagings in accordance with claim 11, characterized in that layers including PVA as a layer constituent alternatively contain MXD6 (modified polyamide 6). 18. Food casing or film for food packagings in accordance with claim 11, characterized in that layers including polyamide as a layer constituent alternatively contain an ionomer. 19. Food casing or film for food packagings in accordance with claim 11, characterized in that layers including polyamide as a layer constituent alternatively contain MXD6. 20. Food casing or film for food packagings in accordance with claim 11, characterized in that layers including polyamide as a layer constituent contain polycaprolactame (PA 6), polyhexamethylene adipinamide (PA 66), PA 6/66, PA 11, PA 12, or mixtures of these polyamides, etc.
The present invention relates to a multilayer planar or tubular food casing or film for food packagings such as, e.g., sausage casings, shrink bags or the like, in accordance with the preamble of Claim 1. DE 32 12 343 A1 discloses a tubular casing of two-layer film laminate for packaging. Furthermore a multilayer, tubular casing for packaging pasty stuffings, in particular an artificial sausage casing, on the basis of polyamide is discussed in DE 40 17 046 A1 as well as in EP 0 467 039 A2. In practice, such sausage casings or artificial casings are utilized for packaging sausage or pasty matter. The product to be packaged, such as a sausage mass, is filled into the artificial casing, scalded in it, cooled, and stored. From this there arise demands such as, e.g., a distinct dimensional stability throughout the entire working process or a sufficient protection of the stuffing against external influences such as, e.g., penetration of oxygen, UV radiation, desiccation, or the like. The classical sausage casings known in practice may roughly be classified into three types: The classical one-layer sausage casing of polyamide, having as an essential drawback the lack of a water vapor barrier. A widely used sausage casing of three layers containing, from the outside to the inside, polyamide, polyolefin, preferably polyethylene, polyamide. The water vapor barrier, which is lacking in the one-layer sausage casing, is formed by the central polyolefin layer. The inner layer of polyamide provides sufficient adhesion of stuffing and prevents precipitation or settling of jelly. This polyamide layer may also be replaced with a correspondingly pre-treated (corona) PE layer, in which case the PE layer then has to be modified in order to enter a satisfactory connection with the PA. In recent times, sausage casings having five layers have found acceptance in practice. The five layers, counted from the outside to the inside, contain PA, an adhesion promoter, PE, an adhesion promoter, and finally again PA. The approach of this structure corresponds to the one of the three-layer sausage casing, however has between PA and PE, and between PE and PA, a respective separate adhesive layer or a respective separate adhesion promoter. As a result the central polyolefin layer may be modified more strongly with regard to the starting materials used. Irrespective of this, the oxygen barrier and also the aroma barrier thereby available are not yet formed with sufficient tightness. It is accordingly an object of the present invention to further develop a generic multilayer planar or tubular food casing or film while avoiding the above mentioned disadvantages, such that a sufficiently tight oxygen barrier may be furnished concurrently with a satisfactory aroma barrier. This object is achieved through the features of Claim 1. In accordance with the invention a multilayer planar or tubular food casing or film for food packagings, such as, e.g., sausage casings, shrink bags etc., is being proposed, which is for the first time characterized by a layered structure having at least five, preferably at least seven layers, with one of the at least five layers containing PVA as a layer constituent. For particularly preferred variants of the multilayer planar or tubular food casing or film for food packagings in accordance with the invention, the following layered structures, counted from the outside to the inside, are being proposed for the first time: a) the first layer from the outside contains polyamide as a layer constituent, the second layer PVA, the third layer an adhesion promoter, the fourth layer a polyolefin, preferably polyethylene, the fifth layer an adhesion promoter, and the sixth layer from the outside, being at the same time the innermost layer or the layer facing the food to be packaged, a polyamide as a layer constituent, ‘or b) the first layer from the outside contains polyamide as a layer constituent, the second layer PVA, the third layer polyamide, the fourth layer an adhesion promoter, the fifth layer a polyolefin, preferably polyethylene, the sixth layer an adhesion promoter, and the seventh layer from the outside, being at the same time the innermost layer or the layer facing the food to be packaged, a polyamide as a layer constituent, or c) the first layer from the outside contains polyamide as a layer constituent, the second layer an adhesion promoter, the third layer polyamide, the fourth layer PVA, the fifth layer polyamide, the sixth layer an adhesion promoter, and the seventh layer from the outside, being at the same time the innermost layer or the layer facing the food to be packaged, a polyamide as a layer constituent. Furthermore particularly preferred variants of a multilayer planar or tubular food casing or film for food packagings in accordance with the invention are for the first time proposed which have a layered structure wherein, when counted from the outside to the inside: a) the first layer from the outside contains as a layer constituent a polyolefin, preferably polyethylene, the second layer an adhesion promoter, the third layer polyamide, the fourth layer PVA, the fifth layer polyamide, the sixth layer an adhesion promoter, and the seventh layer from the outside, being at the same time the innermost layer, a polyolefin, preferably polyethylene, or b) the first layer from the outside contains as a layer constituent PET, the second layer an adhesion promoter, the third layer polyamide, the fourth layer PVA, the fifth layer polyamide, the sixth layer an adhesion promoter, and the seventh layer from the outside, being at the same time the innermost layer, a polyolefin, preferably polyethylene, or c) the first layer from the outside contains as a layer constituent a polyolefin, preferably polyethylene, the second layer EVA, the third layer an adhesion promoter, the fourth layer PVA, the fifth layer an adhesion promoter, the sixth layer EVA, and the seventh layer from the outside, being at the same time the innermost layer, a polyolefin, preferably polyethylene. PVA advantageously results in the desired high oxygen barrier, with a simultaneously substantially enhanced aroma barrier. Furthermore a smoother and softer film is thereby achieved, which is substantially improved with a view to its suitability for further mechanical processing. PVA in this context designates polyvinyl alcohol which may also be abbreviated PVOH or PVAL. PVA is to designate both PVA and mixtures of PVA with other polymers. The PA allows to ensure the desired mechanical properties. The PE provides the possibility of positively influencing sealing. With EVA, high shrink as well as a further possibility of influencing the mechanical properties are moreover obtained, in which case a supplementary electron beam treatment is to be provided. The polyolefins encompass both PE and PP as well as EVA and EM(M)A within the meaning of the present application, as well as mixtures of polyolefins as such as well as with ionomers. The adhesion promoters (short: AP) represent an adhesive layer. PA generally designates PA as well as PA 6, PA 66, PA 6/66, PA 6/12 or the like, and also mixtures of these, as well as mixtures of PA with other polymers. EVA furthermore designates both EVA and mixtures of EVA with polymers. Thus a food casing or film for food packagings, in particular for sausage casings or the like is advantageously furnished, whereby a specific shrink of at least 10 to 20%, preferably of at least 12 to 15%, is readily possible. Specifically in the case of shrink bags or the like, it is advantageously possible with the layered structures proposed for the first time, to achieve a particularly high shrink that is at least 20 to 60%, preferably at least 30 to 50%, at a water temperature of about 95° C. The overelongation factor thus available at the same time is at least 5 to 15%, preferably 10 to 12% for both sausage casings and shrink bags. For the sealing layers to be provided on the inside and/or outside of shrink bags, it is possible with the layered structures proposed for the first time to advantageously provide, e.g., a polyolefin, preferably PE, LLDPE, EVA, or ionomers or mixtures of these etc., as a starting material. Thanks to the particularly strongly pronounced oxygen barrier obtained through the layer constituent PVA, excellent preservation of the foodstuff thereby packaged, in particular of a sausage mass placed in the sausage casing, is ensured over more than six weeks without any quality reduction. Thanks to the extremely well formed oxygen barrier, the food casing or film of the invention for the first time provides a food packaging whereby even goods that are particularly sensitive to air do not undergo any color changes or even run a risk of aging or changing taste due to a penetration of oxygen, even with long storage periods. Thus the layer constituent PVA is in a preferred layered structure embedded, in the manner of a sandwich, between two layers including polyamide as a layer constituent, which results in a highest possible oxygen barrier and at the same time ensures excellent embedding and stabilization of the PVA layer between the two polyamide layers as carrier layers. At the same time a particularly excellent water vapor barrier is available with the layered structure of the invention, which is crucial particularly in the case of sausage or other foodstuffs that need to be kept fresh. Foods packaged with the food casing or film of the invention therefore remain fresh for a particularly long period of time. Furthermore the food casing or film of the invention is suited as a shrink film and may moreover be sealed well during bonding. Where the food casing or film of the invention is used as a sausage casing, pure bonding is equally possible without any problems. The outermost layer of the food casing or film proposed for the first time takes inscriptions or print particularly well. In addition, the food casing or film of the invention is particularly well suited to be manufactured and further processed with corresponding systems of the present applicant. Advantageous developments of the invention result from the features of the subclaims. Thus it is provided in a preferred embodiment of the food casing or film for food packagings in accordance with the invention that layers including polypropylene or polyolefin as a layer constituent alternatively also contain polypropylene, EVA (ethyl vinyl alcohol), EM(M)A, ionomers, or mixtures of these etc. Furthermore it is provided in a preferred embodiment that layers containing an adhesion promoter include an adhesion promoter on the basis of PE, EVA, EM(M)A or an ionomer as a base material. In accordance with a further preferred embodiment it is provided that layers including an adhesion promoter as a constituent alternatively contain a mixture of polyolefin and adhesion promoter or a mixture of EVA and/or EM(M)A and adhesion promoter. In accordance with a further preferred embodiment it is provided that layers including PVA as a layer constituent alternatively contain MXD6 (modified polyamide 6). In accordance with a further preferred embodiment of the food casing or film of the invention it is provided that layers including polyamide as a layer constituent alternatively contain an ionomer. Furthermore it is provided in accordance with a preferred embodiment that layers including polyamide as a layer constituent alternatively contain MXD6. Not last it is provided in accordance with a preferred embodiment that layers including polyamide as a layer constituent contain polycaprolactame (PA 6), polyhexamethylene adipinamide (PA 66), PA 6/66, PA 11, PA 12 or mixtures of these polyamides etc. By the present invention a planar or tubular food casing or film having a layered structure with at least five layers, preferably at least seven layers, is thus proposed for the first time.
20050518
20090310
20060209
59667.0
B32B2734
0
MIGGINS, MICHAEL C
MULTILAYER PLANAR OR TUBULAR FOOD CASING OR FILM
UNDISCOUNTED
0
ACCEPTED
B32B
2,005
10,535,115
ACCEPTED
Apparatus and method for receiving emergency alert signals
An apparatus such as a television signal receiver provides an emergency alert function, according to an exemplary embodiment, the television signal receiver includes a first tuner for tuning a first channel when the television signal receiver is in an on mode. A second tuner is provided for tuning a second channel when the television signal receiver is in the on mode and an off/standby mode. The second channel provides emergency alert signals capable of activating the emergency alert function.
1. A television signal receiver having an emergency alert function, comprising: first tuning means for tuning first signals including video signals when said television signal receiver is in an on mode; second tuning means for tuning second signals including emergency alert signals when said television signal receiver is in said on mode and an off/standby mode; and wherein said emergency alert function is activated if said emergency alert signals indicate an emergency event corresponding to a user selected geographical area and a user selected event type. 2. The television signal receiver of claim 1, wherein said second tuning means is included in a modem apparatus. 3. The television signal receiver of claim 2, wherein said modem apparatus is internal to said television signal receiver. 4. The television signal receiver of claim 2, wherein said modem apparatus is external to said television signal receiver. 5. The television signal receiver of claim 4, wherein said modem apparatus includes alert means for providing an alert output when said emergency alert function is activated. 6. The television signal receiver of claim 5, wherein said alert means includes a visual output element. 7. The television signal receiver of claim 5, wherein said alert means includes an aural output element. 8. A method for controlling a television signal receiver having an emergency alert function, comprising: enabling a first tuner to tune first signals including video signals when said television signal receiver is in an on mode; enabling a second tuner to tune second signals including emergency alert signals when said television signal receiver is in said on mode and an off/standby mode; and wherein said emergency alert function is activated if said emergency alert signals indicate an emergency event corresponding to a user selected geographical area and a user selected event type. 9. The method of claim 8, wherein said second tuner is included in a modem apparatus. 10. The method of claim 9, wherein said modem apparatus is internal to said television signal receiver. 11. The method of claim 9, wherein said modem apparatus is external to said television signal receiver. 12. The method of claim 11, further comprised of providing an alert output via an alert system of said modem apparatus when said emergency alert function is activated. 13. The method of claim 12, wherein said alert output includes a visual output. 14. The method of claim 12, wherein said alert output includes an aural output. 15. A modem apparatus having an emergency alert function, comprising: a modulator operative to modulate upstream signals provided to a network; a demodulator operative to demodulate downstream signals provided from said network, said downstream signals including emergency alert signals capable of activating said emergency alert function; an alert system operative to provide an alert output when said emergency alert function is activated; and wherein said emergency alert function is activated if said emergency alert signals indicate an emergency event corresponding to a user selected geographical area and a user selected event type. 16. The modem apparatus of claim 15, wherein said alert system includes a visual output element. 17. The modem apparatus of claim 15, wherein said alert system includes an aural output element. 18. The modem apparatus of claim 15, wherein said network includes a cable network. 19. The modem apparatus of claim 15, wherein said network includes a DSL network. 20. The modem apparatus of claim 15, wherein: said modem apparatus is operatively coupled to an external device; and said external device provides a second alert output when said emergency alert function is activated. 21. The modem apparatus of claim 20, wherein said external device includes a television signal receiver. 22. The modem apparatus of claim 20, wherein said external device includes a computer.
The present invention generally relates to apparatuses such as a television signal receiver and/or modem which provide an emergency alert function, and more particularly, to techniques for receiving emergency alert signals using such apparatuses. Emergency events such as severe weather, natural disasters, fires, civil emergencies, war acts, toxic chemical spills, radiation leaks, or other such conditions can be devastating to unprepared individuals. With weather-related emergencies, authorities such as the National Weather Service (NWS) and the National Oceanographic and Atmospheric Administration (NOAA) are generally able to detect severe weather conditions prior to the general public. Through the use of modem weather detection devices, such as Doppler radar and weather satellites, the NWS and NOAA are able to issue early warnings of severe weather conditions which have saved many lives. However, for such warnings to be effective, they must be communicated to their intended recipients. With certain apparatuses such as television signal receivers, warnings for emergency events may be provided when the receiver is tuned to a particular channel which provides such warnings. For example, in any given geographical area, certain local channels may provide information regarding emergency events affecting that geographical area. However, if a viewer is not tuned to such a local channel when an emergency event occurs, the viewer may not be notified of the emergency event, and may therefore be placed in a potentially dangerous situation. Accordingly, there is a need for an apparatus and method for providing notification of emergency events which avoids the foregoing problems, and thereby increases the likelihood that users are promptly notified of emergency events. The present invention addresses these and other issues. In accordance with an aspect of the present invention, a television signal receiver having an emergency alert function is disclosed. According to an exemplary embodiment, the television signal receiver comprises first tuning means for tuning a first channel when the television signal receiver is in an on mode. Second tuning means are provided for tuning a second channel when the television signal receiver is in the on mode and an off/standby mode. The second channel provides emergency alert signals capable of activating the emergency alert function. In accordance with another aspect of the present invention, a method for controlling a television signal receiver having an emergency alert function is disclosed. According to an exemplary embodiment, the method comprises steps of enabling a first tuner to tune a first channel when the television signal receiver is in an on mode, and enabling a second tuner to tune a second channel when the television signal receiver is in the on mode and an off/standby mode. The second channel provides emergency alert signals capable of activating the emergency alert function. In accordance with still another aspect of the present invention, a modem apparatus having an emergency alert function is disclosed. According to an exemplary embodiment, the modem apparatus comprises a modulator operative to modulate upstream signals provided to a network. A demodulator is operative to demodulate downstream signals provided from the network. The downstream signals include emergency alert signals capable of activating the emergency alert function. An alert system is operative to provide an alert output when the emergency alert function is activated. The above-mentioned and other features and advantages of this invention, and the manner of attaining them, will become more apparent and the invention will be better understood by reference to the following description of embodiments of the invention taken in conjunction with the accompanying drawings, wherein: FIG. 1 is an exemplary environment suitable for implementing the present invention; FIG. 2 is a block diagram of a television signal receiver according to an exemplary embodiment of the present invention; FIG. 3 is a flowchart illustrating steps according to an exemplary embodiment of the present invention; FIG. 4 is a block diagram of a modem apparatus according to an exemplary embodiment of the present invention; and FIG. 5 is another diagram of a modem apparatus according to an exemplary embodiment of the present invention. The exemplifications set out herein illustrate preferred embodiments of the invention, and such exemplifications are not to be construed as limiting the scope of the invention in any manner. Referring now to the drawings, and more particularly to FIG. 1, an exemplary environment 100 suitable for implementing the present invention is shown. In FIG. 1, environment 100 comprises signal transmission means such as signal transmission source 10, dwelling means such as dwelling units 15 (i.e., 1, 2, 3 . . . N, where N may be any positive integer), and signal receiving means such as television signal receivers 20. In FIG. 1, dwelling units 15 may represent residences, businesses and/or other dwelling places located within a particular geographical area, such as but not limited to, a particular continent, country, region, state, area code, zip code, city, county, municipality, subdivision, and/or other definable geographical area. According to an exemplary embodiment, each of the dwelling units 15 is equipped with at least one television signal receiver 20 having an emergency alert function. According to the present invention, the emergency alert function enables television signal receiver 20 to receive emergency alert signals and provide one or more alert outputs to notify individuals of an emergency event. As will be discussed later herein, television signal receiver 20 is also capable of, among other things, receiving emergency alert signals from a separate channel which ensures that emergency events can be detected during all operational modes of television signal receiver 20, namely an on mode and an off/standby mode. According to an exemplary embodiment, the on mode is an operational mode where television signal receiver 20 is turned on (i.e., providing audio and/or video outputs), while the off/standby mode is an operational mode where television signal receiver 20 is turned off (i.e., no audio and/or video outputs) but still receives electrical power. Television signal receiver 20 may for example be switched from the off/standby mode to the on mode responsive to a user input. According to an exemplary embodiment, signal transmission source 10 transmits signals including emergency alert signals which may be received by each television signal receiver 20. The emergency alert signals may be provided from an authority such as the NWS, or other authorities such as governmental entities or the like. Signal transmission source 10 may transmit the emergency alert signals in their original form as provided by the authority, or may append digital data representative of the emergency alert signals to other data, or may modify the emergency alert signals in some manner appropriate for its specific transmission format needs. In response to the emergency alert signals, each television signal receiver 20 may provide one or more alert outputs to thereby notify individuals of the emergency event. Signal transmission source 10 may transmit such emergency alert signals to television signal receivers 20 via any wired or wireless link such as, terrestrial, cable, satellite, fiber optic, digital subscriber line (DSL), and/or any other type of broadcast and/or multicast means. Referring to FIG. 2, a block diagram of an exemplary embodiment of television signal receiver 20 of FIG. 1 is shown. In FIG. 2, television signal receiver 20 comprises signal receiving means such as signal receiving element 21, signal splitting means such as signal splitter 22, first tuning means such as tuner 23, first demodulation means such as demodulator 24, second tuning means such as second tuner 25, second demodulation means such as demodulator 26, decoding means such as decoder 27, processing means and memory means such as processor and memory 28, audio amplification means such as audio amplifier 29, audio output means such as speaker 30, video processing means such as video processor 31, and visual output means such as display 32. Some of the foregoing elements may for example be embodied using integrated circuits (ICs). For clarity of description, certain conventional elements of television signal receiver 20 including control signals may not be shown in FIG. 2. According to an exemplary embodiment, television signal receiver 20 may receive and process signals in analog and/or digital formats. Signal receiving element 21 is operative to receive signals including audio, video and/or emergency alert signals from signal sources, such as signal transmission source 10 in FIG. 1. According to an exemplary embodiment, emergency alert signals may be received as separate data packets in a digital transmission system. According to another exemplary embodiment, received signals may include digitally encoded emergency alert signals. Signal receiving element 21 may be embodied as any signal receiving element such as an antenna, input terminal or other element. Signal splitter 22 is operative to split the signals provided from signal receiving element 21 into first and second frequency channels. According to an exemplary embodiment, television signal receiver 20 may include a picture-in-picture (PIP) function wherein the first channel includes audio and/or video signals for a main picture, and the second channel includes audio and/or video signals for the PIP function. Tuner 23 is operative to tune signals including audio, video and/or emergency alert signals in the first channel when television signal receiver 20 is in the on mode. Accordingly, tuner 23 may tune signals for the main picture of television signal receiver 20. Demodulator 24 is operative to demodulate signals provided from tuner 23, and may demodulate signals in analog and/or digital transmission formats. Tuner 25 is operative to tune signals including audio, video and/or emergency alert signals in the second channel when television signal receiver 20 is in the on mode. Accordingly, tuner 25 may tune signals for the PIP function of television signal receiver 20. Additionally, tuner 25 is operative to tune signals including emergency alert signals in the second channel when television signal receiver 20 is in the off/standby mode. In this manner, tuner 25 enables television signal receiver 20 to receive emergency alert signals in both the on mode, and the off/standby mode. Demodulator 26 is operative to demodulate signals provided from tuner 25, and may demodulate signals in analog and/or digital transmission formats. Decoder 27 is operative to decode signals including audio, video and/or emergency alert signals provided from demodulators 24 and 26. According to an exemplary embodiment, decoder 27 decodes digital data which represents emergency alert signals indicating an emergency event. Decoder 27 may also perform other decoding functions, such as decoding data which represents emergency alert signals included in the vertical blanking interval (VBI) of an analog television signal. According to an exemplary embodiment, the emergency alert signals include data comprising Specific Area Message Encoding (SAME) data associated with the emergency event. SAME data comprises a digital code representing information such as the specific geographical area affected by the emergency event, the type of emergency event (e.g., tornado watch, radiological hazard warning, civil emergency, etc.), and the expiration time of the event alert. SAME data is used by the NWS and other authorities to improve the specificity of emergency alerts and to decrease the frequency of false alerts. Other data and information may also be included in the emergency alert signals according to the present invention. Processor and memory 28 are operative to perform various processing, control, and data storage functions of television signal receiver 20. According to an exemplary embodiment, processor 28 is operative to process the audio and video signals provided from decoder 27, and may for example perform analog processing, such as National Television Standards Committee (NTSC) signal processing and/or digital processing, such as Motion Picture Expert Group (MPEG) processing. Processor 27 is also operative to receive the emergency alert signals from decoder 27 and determine whether the emergency alert function of television signal receiver 20 is activated based on data included in the emergency alert signals. According to an exemplary embodiment, processor 28 compares data in the emergency alert signals to user setup data stored in memory 28 to determine whether the emergency alert function is activated. As will be described later herein, a setup process for the emergency alert function of television signal receiver 20 allows a user to select items such as an applicable geographical area(s), and type(s) of emergency events (e.g., tornado watch, radiological hazard warning, civil emergency, etc.) which activate the emergency alert function. When the emergency alert function of television signal receiver 20 is activated, processor 28 outputs one or more control signals which enable various operations. According to an exemplary embodiment, such control signals enable one or more alert outputs (e.g., aural and/or visual) to thereby notify individuals of the emergency event. Such control signals may also enable other operations of television signal receiver 20, such as causing it to be switched from the off/standby mode to the on mode. Further details regarding these aspects of the present invention will be provided later herein. Audio amplifier 29 is operative to amplify the audio signals provided from processor 28. Such audio signals may for example represent audio content such as an NWS audio message, a warning alert tone and/or other audio content. Speaker 30 is operative to aurally output the amplified audio signals provided from audio amplifier 29. Video processor 31 is operative to process the video signals provided from processor 28. According to an exemplary embodiment, such video signals may include embedded messages such as NWS text messages and/or other messages that provide details regarding emergency events. Video processor 31 may include closed caption circuitry which enables closed caption displays. Display 32 is operative to provide visual displays corresponding to processed signals provided from video processor 31. According to an exemplary embodiment, display 32 may provide visual displays including the aforementioned messages that provide details regarding emergency events. Turning now to FIG. 3, a flowchart 300 illustrating exemplary steps according to the present invention is shown. For purposes of example and explanation, the steps of FIG. 3 will be described with reference to television signal receiver 20 of FIG. 2. The steps of FIG. 3 are merely exemplary, and are not intended to limit the present invention in any manner. At step 301, a setup process for the emergency alert function of television signal receiver 20 is performed. According to an exemplary embodiment, a user performs this setup process by providing inputs to television signal receiver 20 (e.g., using a remote control device not shown) responsive to an on-screen menu displayed via display 32. Such an on-screen menu may for example be part of an electronic program guide (EPG) function of television signal receiver 20. According to an exemplary embodiment, the user may select at least the following items during the setup process at step 301: A. Enable/Disable—The user may select whether to enable or disable the emergency alert function. B. Frequency Selection—The user may select the monitoring channel to tune to in order to receive emergency alert signals. For example, the user may select a terrestrial, cable, satellite or other channel which will be monitored for emergency alert signals. The selection of a monitoring channel may for example be facilitated through a frequency scanning operation which scans various frequency channels to thereby identify the monitoring channels that provide the highest signal strength. C. Geographical Areas—The user may select one or more geographical areas of interest. For example, the user may select a particular continent, country, region, state, area code, zip code, city, county, municipality, subdivision, and/or other definable geographical area. According to an exemplary embodiment, such geographical area(s) may be represented in memory 28 by location data, such as one or more Federal Information Processing Standard (FIPS) location codes. D. Event Types—The user may select one or more types of emergency events which activate the emergency alert function. For example, the user may designate that events such as civil emergencies, radiological hazard warnings, and/or tornado warnings activate the emergency alert function, but that events such as a thunderstorm watch does not, etc. The user may also select whether the conventional warning audio tone provided by the NWS and/or other alert mechanism activates the emergency alert function. According to the present invention, different severity or alert levels (e.g., statement, watch, warning, etc.) may represent different “events.” For example, a thunderstorm watch may be considered a different event from a thunderstorm warning. E. Alert Outputs—The user may select one or more alert outputs to be provided when the emergency alert function is activated. According to an exemplary embodiment, the user may select visual and/or aural outputs to be provided for each type of emergency event that activates the emergency alert function. For example, the user may select to display a visual message (e.g., an NWS text message as a closed caption display) and/or tune television signal receiver 20 to a specific channel. The user may also for example select to aurally output a warning tone (e.g., chime, siren, etc.) and/or an audio message (e.g., NWS audio message), and the desired volume of each. Moreover, the alert outputs may be selected on an event-by-event basis. Other types of alert outputs may also be provided according to the present invention. According to the present invention, other menu selections may also be provided at step 301 and/or some of the menu selections described above may be omitted. Data corresponding to the user's selections during the setup process of step 301 is stored in memory 28. At step 302, a determination is made by processor 28 as to whether television signal receiver 20 is in the on mode. As previously indicated herein, the on mode is an operational mode where television signal receiver 20 is turned on (i.e., providing audio and/or video outputs), while the off/standby mode is an operational mode where television signal receiver 20 is turned off (i.e., no audio and/or video outputs) but still receives electrical power. Television signal receiver 20 may for example be switched from the off/standby mode to the on mode responsive to a user input. If the determination at step 302 is positive, process flow advances to step 303 where television signal receiver 20 monitors the first and second channels for emergency alert signals using tuners 23 and 25, respectively, under the control of processor 28. According to an exemplary embodiment, the first channel monitored by tuner 23 provides a main picture and may be selected by a user through inputs to television signal receiver 20 as part of a normal channel selection process. Also according to this embodiment, the second channel monitored by tuner 25 may be selected by the user during the setup process of step 301 (i.e., item B). Since tuner 25 may enable a PIP function of television signal receiver 20, the use of tuner 25 to monitor the second channel at step 303 may be conditioned on the PIP function being turned off. Accordingly, assuming the PIP function is turned off and tuner 25 is available, tuners 23 and 25 monitor the first and second channels, respectively, at step 303 and one of the tuners 23 and 25 may thereby receive incoming emergency alert signals. If the determination at step 302 is negative, television signal receiver 20 is deemed to be in the off/standby mode and process flow advances to step 304 where tuner 25 monitors the second channel under the control of processor 28 and may thereby receive incoming emergency alert signals. At step 305, a determination is made as to whether the emergency alert function of television signal receiver 20 is activated. According to an exemplary embodiment, processor 28 makes this determination by comparing data included in the incoming emergency alert signals to data stored in memory 28. As previously indicated herein, the emergency alert signals may include data such as SAME data which represents information including the type of emergency event (e.g., tornado watch, radiological hazard warning, civil emergency, etc.) and the specific geographical area(s) affected by the emergency event. According to an exemplary embodiment, processor 28 compares this SAME data to corresponding user setup data (i.e., items C and D of step 301) stored in memory 28 to thereby determine whether the emergency alert function is activated. In this manner, the emergency alert function of television signal receiver 20 is activated when the emergency event indicated by the emergency alert signals corresponds to: (1) the geographical area(s) selected by the user for item C of step 301 and (2) the event type(s) selected by the user for item D of step 301. If the determination at step 305 is negative, process flow loops back to step 302 where processor 28 determines whether television signal receiver 20 is in the on mode. Alternatively, if the determination at step 305 is positive, process flow advances to step 306 where television signal receiver 20 provides one or more alert outputs to thereby notify individuals of the emergency event. According to an exemplary embodiment, processor 28 enables the one or more alert outputs at step 306 in accordance with the user's selections during the setup process of step 301 (i.e., item E), and such alert outputs may be aural and/or visual in nature. For example, aural outputs such as a warning tone and/or an NWS audio message may be provided at step 306 via speaker 30, and the volume of such aural outputs may be controlled in accordance with the volume level set by the user during the setup process of step 301. Visual outputs may also be provided at step 306 via display 32 to notify individuals of the emergency event. According to an exemplary embodiment, an auxiliary information display such as an NWS text message (e.g., as a closed caption display) and/or a video output from a specific channel may be provided at step 306 via display 32 under the control of processor 28. When an alert output results from emergency alert signals received via the second channel when television signal receiver 20 is in the on mode, processor 28 may enable a visual alert output (e.g., NWS text message, etc.) to be overlaid upon a visual output on display 32 provided via the first channel. If digital transmission is employed, the data packets received via the second channel may be inserted into the data stream from the first channel. This allows alert information (e.g., audio, video, text, etc.) from the second channel to simply replace information from the first channel. In this manner, normal programming provided via the first channel may be interrupted or augmented to provide the alert output and thereby ensure that users are notified of an emergency event. According to another exemplary embodiment, the alert output(s) provided at step 306 may be based on the severity or alert level of the particular emergency event. For example, emergency events may be classified in one of three different alert level categories, such as statement, watch, and warning. With such a classification scheme, the alert output for an emergency event at a level 1 or statement level may be provided by an unobtrusive notification means such as a blinking light emitting diode (LED) since it is the least severe type of emergency event. The alert output for an emergency event at a level 2 or watch level may have some type of audio component (e.g., radio message). The alert output for an emergency event at a level 3 or warning level may be provided by a siren or other type of alarm since it is the most severe type of emergency event. Other types of aural and/or visual alert outputs than those expressly described herein may also be provided at step 306 according to the present invention. Referring now to FIG. 4, a block diagram of a modem apparatus 40 according to an exemplary embodiment of the present invention is shown. Modem apparatus 40 may for example be embodied as a cable modem and/or a DSL modem. According to an exemplary embodiment, modem apparatus 40 includes an emergency alert function which enables it to receive emergency alert signals and provide one or more alert outputs to notify individuals of an emergency event. According to this exemplary embodiment, modem apparatus 40 is a stand-alone device which may be operatively coupled to one or more external devices such as television signal receiver 20 and/or a computer which may each provide an emergency alert function. Accordingly, the emergency alert function of modem apparatus 40 may be separate and independent from the emergency alert functions of such other devices. In this manner, modem apparatus 40 may serve as the primary alerting device when such external devices are turned off. Moreover, the emergency alert function of modem apparatus 40 may be used in combination with the emergency alert functions of other devices such that modem apparatus 40 and the other devices each provide one or more alert outputs responsive to emergency alert signals, and thereby increase the likelihood that individuals are notified of emergency events. FIG. 5 is an exemplary diagram of modem apparatus 40 according to an exemplary embodiment of the present invention. According to another exemplary embodiment, modem apparatus 40 may be combined with another device such that it is internal to the other device. For example, modem apparatus 40 may be included as internal circuitry within the chassis of television signal receiver 20, and thereby serve as a separate and independent monitoring device for emergency alert signals, either in substitution of, or in addition to, tuner 25. In FIG. 4, modem apparatus 40 comprises signal diplexer means such as diplexer 41, tuning means such as tuner 42, demodulation means such as demodulator 43, modulation means such as modulator 44, decoding means such as decoder 45, processing means and memory means such as processor and memory 46, alert means such as alert system 47, control means such as controller 48. Some of the foregoing elements may for example be embodied using ICs. For clarity of description, certain conventional elements of modem apparatus 40 including control signals may not be shown in FIG. 4. Diplexer 41 is operative to enable bi-directional transmission of signals between modem apparatus 40 and a network, such as a cable, satellite, fiber optic, DSL, terrestrial or other type of wired and/or wireless network. The signals received by modem apparatus 40 from the network may be referred to herein as downstream signals, and the signals transmitted to the network from modem apparatus 40 may be referred to herein as upstream signals. The downstream signals received by modem apparatus 40 may include emergency alert signals capable of activating the emergency alert function of cable modem 40 and/or another external device such as television signal receiver 20. Tuner 42 is operative to tune the downstream signals received from the network via diplexer 41. Demodulator 43 is operative to demodulate the downstream signals provided from tuner 42. According to an exemplary embodiment, tuner 42 and demodulator 43 are operative to provide at least the same functionality as tuner 25 and demodulator 26 of television signal receiver 20, respectively, as previously described herein. Modulator 44 is operative to modulate the upstream signals provided to the network. Decoder 45 is operative to provide at least the same functionality as decoder 27 of television signal receiver 20, as previously described herein. Accordingly, decoder 45 is operative to decode downstream signals that may include emergency alert signals. Such emergency alert signals may for example be represented as packets of digital data, or may be analog signals including digitally encoded signals. As indicated in FIG. 4, decoder 45 may be operatively coupled to processor 28 of television signal receiver 20 when modem apparatus 40 is combined with television signal receiver 20. If modem apparatus 40 is included as internal circuitry within television signal receiver 20, elements of FIG. 4 which are downstream of decoder 45, namely processor and memory 46, alert system 47, and controller 48, may be redundant. Processor and memory 46 are operative to provide at least the same functionality as processor and memory 28 of television signal receiver 20, as previously described herein. Accordingly, processor and memory 46 may be programmed through a setup process such as the one described in step 301 of FIG. 3 to thereby establish user settings for the emergency alert function of modem apparatus 40. As previously indicated herein, the emergency alert function of modem apparatus 40 may be separate and independent from the emergency alert functions of connected devices such as television signal receiver 20. According to an exemplary embodiment, processor and memory 46 may be programmed via input means of modem apparatus 40 (not shown), from an external device (e.g., television signal receiver 20, computer, etc.), or via data provided from the network. Once programmed, processor 46 may compare data in received emergency alert signals to user setup data stored in memory 46 to determine whether the emergency alert function of modem apparatus 40 is activated. When the emergency alert function of modem apparatus 40 and/or another device is activated, processor 46 outputs one or more control signals which enable one or more alert outputs (e.g., aural and/or visual) to thereby notify individuals of the emergency event. Alert system 47 is operative to provide one or more alert outputs under the control of processor 46 when the emergency alert function of modem apparatus 40 and/or another device is activated. According to an exemplary embodiment, alert system 47 includes visual and/or aural output means, such as visual output element 47a and aural output element 47b shown in FIG. 5. Visual output element 47a may for example be embodied as an LED and/or other type of visual indicator element. Aural output element 47b may for example be embodied as a speaker and/or other type of aural output element. Controller 48 is operative to control the transmission of signals to and from an external device, such as a computer. According to an exemplary embodiment, controller 48 may be embodied as an Ethernet or other type of controller. Accordingly, controller 48 may provide alert information to an external device (e.g., computer), or may provide direct inputs to audio and video processing circuitry of a device if modem apparatus 40 has been integrated into the device. As described herein, the present invention provides techniques for receiving emergency alert signals using an apparatus such as a television signal receiver and/or modem. The present invention may be applicable to various apparatuses, either with or without a display device. Accordingly, the phrase “television signal receiver” as used herein may refer to systems or apparatuses capable of receiving and processing television signals including, but not limited to, television sets, or monitors that include a display device, and systems or apparatuses such as set-top boxes, video cassette recorders (VCRs), digital versatile disk (DVD) players, video game boxes, personal video recorders (PVRs), or other apparatuses that may not include a display device. While this invention has been described as having a preferred design, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.
20050516
20100511
20060316
63726.0
G08B2300
0
POPE, DARYL C
APPARATUS AND METHOD FOR RECEIVING EMERGENCY ALERT SIGNALS
UNDISCOUNTED
0
ACCEPTED
G08B
2,005
10,535,413
ACCEPTED
Composition containing organic substance having double bond with improved oxidative stability
To an organic substance having a double bond such as a polyunsaturated fatty acid was added an antioxidative component containing an antioxidative sesame component and ascorbic acid or an ascorbyl fatty acid ester. The above method provides a composition containing an organic substance having a double bond exhibiting enhanced oxidative stability. Particularly, it extremely improves oxidative stability of fat and oil which contains polyunsaturated fatty acid. General-purpose refined fish oil which is easy to handle can be provided for food, medicine or feed uses.
1. A composition having oxidative stability comprising: an organic substance having a double bond which contains an antioxidant comprising an antioxidative sesame component which is purified form sesame or synthesized and ascorbic acid or an ascorbyl fatty acid ester. 2. A composition according to claim 1, wherein the double bond has active methylene, or located at the end of the organic substance. 3. A composition according to claim 1, wherein the organic substance having the double bond is a poly unsaturated fatty acid or its salt or ester. 4. A composition according to claim 3, wherein the poly unsaturated fatty acid contains at least one of eicosapentaenoic acid and docosahexaenoic acid. 5. A composition according to claim 3, wherein the ester of the poly unsaturated fatty acid is a triglyceride containing the poly unsaturated fatty acid as a constituent, or a lower alcohol ester of the poly unsaturated fatty acid. 6. A composition according to claim 3, wherein the ester of the poly unsaturated fatty acid is added in a form of refined fish oil. 7. A composition according to claim 1, wherein the antioxidative sesame component is at least one of the substances represented by peaks detected by high-performance liquid chromatography using an electrochemical detector at elution times of about 2.66, 3.40, 3.84, 4.57, 4.98, 5.82, 7.00, 8.67, 9.84, 11.24, 12.29, 12.49, 13.36, 14.04, 14.32, 14.74, 15.22, 15.60, 15.82, 16.34, 16.98, 18.10, 18.43, and 34.91 minutes. 8. A composition according to claim 1, wherein the antioxidative sesame component is extracted from sesame, sesame oil, or sesame residue, using a solvent, a lipid, or an emulsifier singly or in combination. 9. A composition according to claim 1, wherein the antioxidative sesame component is at least one selected from the group consisting of sesamol, sesaminol, episesaminol, pinoresinol, epipinoresinol, syringaresinol, samine, sesamolinol, and 2,3-di(4′-hydroxy-3′-methoxybenzyl)-2-buten-4-olide. 10. A composition according to claim 1, wherein the antioxidative sesame component is sesamol. 11. A composition according to claim 1, wherein the antioxidative sesame component is extracted from sesame residue. 12. A composition according to claim 11, wherein the antioxidative sesame component extracted from sesame residue is extraction using a solvent, a lipid, or an emulsifier singly or in combination. 13. A composition according to claim 1, wherein the ascorbyl fatty acid ester contains ascorbyl palmitate or ascorbyl stearate. 14. A composition according to claim 1, wherein the ascorbic acid or the ascorbyl fatty acid ester is contained in an excessive amount more than the amount soluble in the poly unsaturated fatty acid or its salt or ester. 15. A composition according to claim 14, wherein the excessive amount of the ascorbic acid is in a powder or solid form. 16. A composition according to claim 1, further comprising tocopherol. 17. A food containing the composition as set forth in claim 1. 18. A powdered oil or fat containing the composition as set forth in claim 1. 19. A powdered baby milk containing the composition as set forth in claim 1. 20. A health food containing the composition as set forth in claim 1.
TECHNICAL FIELD The present invention relates to a composition containing an organic substance having a double bond with improved oxidative stability. More specifically, the present invention relates to a composition with improved oxidative stability that is prepared by adding an antioxidative sesame component and ascorbic acid or an ascorbyl fatty acid ester as antioxidants to an easily oxidizable organic substance having a double bond, such as a polyunsaturated fatty acid. In the present invention, the polyunsaturated fatty acid refers to a fatty acid having at least three double bonds. BACKGROUND ART It has recently become known that oils and fats, particularly those containing polyunsaturated fatty acids, have physiologic activity. Accordingly, such oils and fats have been increasingly and widely used in food and animal feed as additives, from the viewpoint of health. Eicosapentaenoic acid and docosahexaenoic acid are polyunsaturated fatty acids mainly contained in fish oil. It has been found that they have the effect of, for example, preventing hyperlipemia, high blood pressure, skin aging, and the like, and they have been used in medical drugs and food with health-promoting benefits. Unfortunately, oils and fats containing such a polyunsaturated fatty acid have low oxidative stability. Accordingly, food to which such an oil or fat can be added is limited, or if added to food or the like, the oil or fat undesirably generates an odor due to its oxidation, even slight oxidation. How the oil or fat is handled needs to be taken into account. For example, refined fish oil remaining after use must be hermetically sealed with the can of the fish oil filled with nitrogen gas. Thus, there are limits in use, such as of product type, distribution temperature, content, and storage conditions. Since, for example, docosahexaenoic acid and eicosapentaenoic acid play an important role to develop the brain and retinas and the memory and learning function of babies and breast milk contains these fatty acids, modified milk for babies to which fish oil containing docosahexaenoic acid and eicosapentaenoic acid has been added is commercially available. Also, since arachidonic acid plays an important role for growth and is contained in breast milk, addition of arachidonic acid to the modified baby milk has been attempted. However, it is necessary to take care not to oxidize polyunsaturated fatty acids when these polyunsaturated fatty acids are blended into the modified baby milk. Otherwise, oxidized odor is generated by oxidation, so that not only the modified milk becomes difficult to ingest, but also the modified milk itself may be degraded to be toxic. Encapsulated eicosapentaenoic acid ethyl esters are commercially available as medical drugs for oral administration. Refined fish oil containing eicosapentaenoic acid and docosahexaenoic acid is also available in form of capsule as health food. Since these fatty acids are liable to be oxidized, their use is limited, except for use in capsules. In order enhance the oxidative stability, the oils and fats can be powdered. For example, oil or fat may be encapsulated into microcapsules to be powdered, or enclosed with cyclodextrin and powdered so that stable powdered oil or fat is provided. However, this approach makes the production steps complicated and decreases productivity. In addition, capsules may be broken during storage, and the type of capsule applicable for food and animal feed is limited, disadvantageously. In order to enhance the oxidative stability of oils and fats, various types of antioxidant have been used. For example, plural types of antioxidant are used in combination, or a synergist, such as phosphoric acid, citric acid, or ascorbic acid, is added to an antioxidant to enhance the antioxidant properties. However, the oxidation stabilities of fish oils and other oils and fats having extremely low oxidative stability cannot be sufficiently enhanced by only such combinations of antioxidants and synergists. Dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), gallic acid, propyl gallate, tocopherols, and the like are approved as antioxidants for oils and fats and food containing oil or fat, in order to prevent oils and fats from oxidizing. In medical drugs and the like, synthetic antioxidants are used, such as BHT, BHA, TBHQ, and ethoxyquin. Sesame oil is relatively stable to oxidation, and it has been known since a long time ago that sesame contains antioxidative components, such as sesamol and other lignans (Japanese Unexamined Patent Application Publication No. 58-132076; Shoku no Kagaku, 225 (11) pp. 40-48 (1996); Shoku no Kagaku, 225 (11) pp. 32-36 (1996)). Sesamol is an antioxidant for oils and fats and food containing oil or fat, and is approved as a food additive. It is however reported that sesamol is not effective for oils and fats exhibiting extremely low oxidative stability, such as fish oil (NOF Corporation, from fiscal Heisei 4 (1994) to Heisei 8 (1996), DHA Koudo Seisei Chushutsu Gijutsu Kaihatsu Jigyo, Kekka Gaiyou (DHA Koudo Seisei Chushutsu Gijutsu Kenkyu Kumiai) pp. 74-79 (2002)). Sesamol is not used for enhancing the oxidative stability of fish oil. Ascorbic acid and ascorbic acid derivatives are also approved as food additives and used as antioxidants for oils and fats and food containing oil or fat. However, they are not effective for oils and fats exhibiting extremely low oxidative stability, such as fish oil, if they are used alone, and even their combined use with tocopherol does not produce satisfactory effects. In order to prevent the oxidation of oils and fats, combined use of various types of antioxidant has been attempted. For example, Japanese Unexamined Patent Application Publication No. 2002-142673 has disclosed a lipophilic antioxidant prepared by emulsifying gallic acid, a water-soluble antioxidant, and an oil-soluble antioxidant into a water-in-oil form with a lipophilic emulsifier. In this application, examples of the water-soluble antioxidant include vitamin C, citric acid, chlorogenic acid, their derivatives, sugar-amino reaction products, proanthocyanidin, flavone derivatives, tea extracts, grape seed extracts, and rutin, and examples of the oil-soluble antioxidant include tocopherol, ascorbyl palmitate, sesamol, and γ-oryzanol. Effects of antioxidants have been compared for pyrolysis of tocopherol in vegetable oils in Nippon Eiyo Shokuryo Gakkaishi (Journal of Japanese Society of Nutrition and Food Science), 44 (6) pp. 493-498 (1991), 45 (3) pp. 291-295 (1992), and 45 (3) pp. 285-290 (1992). Although some of the antioxidants use sesamol and an ascorbic acid ester in combination, they do not produce effects particularly superior to other antioxidants. These literatures discuss effects in oxidation of vegetable oils (having 3 or less unsaturated bonds) at high temperatures, but not in oxidation of polyunsaturated fatty acids (having at least three unsaturated bonds) during storage at room temperature; hence different objects are used under different conditions. This is probably because the combination of sesamol and an ascorbic acid ester does not produce superior effects. In addition, the thermal instability of the antioxidants may affect antioxidant properties. Demand for oil or fat containing an unsaturated fatty acid is increasingly growing. Accordingly, it is highly desired to solve the problem of oxidative stability, including how to handle the oil or fat, in a strict sense. DISCLOSURE OF INVENTION The object of the present invention is to provide an organic substance, particularly a polyunsaturated fatty acid or its ester, having a double bond with extremely improved oxidative stability. The inventors of the present invention have conducted intensive research in order to enhance the oxidative stability of oils and fats (oils and fats containing a high proportion of polyunsaturated fatty acid, such as oils of fish and aquatic animals). As a result, the inventors found that the oxidative stability of oils and fats can be extremely enhanced by adding an antioxidative component of sesame, such as sesamol, an ascorbic acid or ascorbyl fatty acid ester in combination. In addition, the present inventors found that the antioxidant properties of antioxidative sesame component other than sesamol are also extremely enhanced by combination with ascorbic acid or ascorbyl fatty acid ester, and thus accomplished the present invention. The main points of the present invention are the composition described in the following (1) to (13). (1) A composition having oxidative stability comprising: an organic substance having a double bond which contains an antioxidant comprising an antioxidative sesame component and ascorbic acid or an ascorbyl fatty acid ester. (2) A composition according to (1), wherein the double bond has active methylene, or located at the end of the organic substance. (3) A composition according to (1), wherein the organic substance having the double bond is a polyunsaturated fatty acid or its salt or ester. (4) A composition according to (3), wherein the polyunsaturated fatty acid contains at least one of eicosapentaenoic acid and docosahexaenoic acid. (5) A composition according to (3) or (4), wherein the ester of the polyunsaturated fatty acid is a triglyceride containing the polyunsaturated fatty acid as a constituent, or a lower alcohol ester of the polyunsaturated fatty acid. (6) A composition according to (3) or (4), wherein the ester of the polyunsaturated fatty acid is added in a form of refined fish oil. (7) A composition according to any one of (1) to (6), wherein the antioxidative sesame component is at least one of the substances represented by peaks detected by high-performance liquid chromatography using an electrochemical detector at elution times of about 2.66, 3.40, 3.84, 4.57, 4.98, 5.82, 7.00, 8.67, 9.84, 11.24, 12.29, 12.49, 13.36, 14.04, 14.32, 14.74, 15.22, 15.60, 15.82, 16.34, 16.98, 18.10, 18.43, and 34.91 minutes. (8) A composition according to any one of (1) to (6), wherein the antioxidative sesame component is extracted from sesame, sesame oil, or sesame residue, using a solvent, a lipid, or an emulsifier singly or in combination. (9) A composition according to any one of (1) to (6), wherein the antioxidative sesame component is at least one selected from the group consisting of sesamol, sesaminol, episesaminol, pinoresinol, epihinoresinol, syringaresinol, samine, sesamolinol, and 2,3-di(4′-hydroxy-3′-methoxybenzyl)-2-buten-4-olide. (10) A composition according to any one of (1) to (9), wherein the ascorbyl fatty acid ester contains ascorbyl palmitate or ascorbyl stearate. (11) A composition according to any one of (1) to (10), wherein the ascorbic acid or the ascorbyl fatty acid ester is contained in an excessive amount more than the amount soluble in the polyunsaturated fatty acid or its salt or ester. (12) A composition according to (11), wherein the excessive amount of the ascorbic acid is in a powder or solid form. (13) A composition according to any one of (1) to (12), further comprising tocopherol. (14) A food containing the composition as set forth in any one of (1) to (13). (15) A powdered oil or fat containing the composition as set forth in any one of (1) to (13). (16) A powdered baby milk containing the composition as set forth in any one of (1) to (13). (17) A health food containing the composition as set forth in any one of (1) to (13). ADVANTAGES The present invention can extremely enhance the oxidative stability of a composition containing an organic substance with low oxidative stability which has a double bond having active methylene, or a double bond at its end, particularly containing a polyunsaturated fatty acid. The present invention can make easy the addition of a composition containing a polyunsaturated fatty acid to medical drugs, cosmetic preparations, food, and the like, which has been conventionally limited. Also, the content of such a composition can be increased. Since the antioxidative sesame component and ascorbic acid or an ascorbyl fatty acid ester used in the present invention have been ingested as food for a long time, a safe antioxidant can be provided for food as well. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows amounts of oxygen absorbed by oil or fat in Example 1. FIG. 2 shows amounts of oxygen absorbed by oil or fat in Example 2. FIG. 3 shows amounts of oxygen absorbed by oil or fat in Example 3. FIG. 4 shows amounts of oxygen absorbed by oil or fat in Example 4. FIG. 5 shows amounts of oxygen absorbed by oil or fat in Example 5. FIG. 6 is a high-performance liquid chromatographic chart of sesame residue extract 1, obtained with an electrochemical detector in Example 6. FIG. 7 shows changes with time in the amount of oxygen absorbed by samples of Example 6. FIG. 8 shows changes with time in the malondialdehyde content in samples of Example 7. FIG. 9 shows changes with time in the alkenal content in samples of Example 7. FIG. 10 shows changes with time in the amounts of oxygen absorbed by a sample (sesamol, 0.5%) and the remaining amounts of antioxidants in Example 8. FIG. 11 shows changes with time in the amounts of oxygen absorbed by a sample (sesamol, 1.0%) and the remaining amounts of antioxidants in Example 8. FIG. 12 shows changes with time in the amounts of oxygen absorbed by samples and the remaining amounts of antioxidants in the case where ascorbyl palmitate was added after 4 days in Example 8. FIG. 13 shows changes with time in the PV of samples of Example 9. FIG. 14 shows comparison in antioxidant property between BHT and the antioxidant preparation according to the present invention. BEST MODE FOR CARRYING OUT THE INVENTION The organic substance having a double bond, used in the present invention is liable to naturally oxidize even under storage at room temperature. For example, the organic substance has a double bond having active methylene, or a double bond at its end. Examples of such substances include unsaturated fats and polymer materials (monomers). Among the unsaturated fats, polyunsaturated fatty acids having at least four double bonds are particularly easily oxidized, and accordingly conventionally used antioxidants cannot sufficiently prevent the oxidation. The polyunsaturated fatty acid or its salt or ester used herein refers to a polyunsaturated fatty acid, a lower alcohol ester of the polyunsaturated fatty acid, and a triglyceride containing the polyunsaturated fatty acid as a constituent. Its examples include oils of fish and aquatic animals containing a high proportion of eicosapentaenoic acid, docosahexaenoic acid, or the like, and their esters, such as eicosapentaenoic acid ethyl ester and docosahexaenoic acid ethyl ester. The polyunsaturated fatty acid refers to a fatty acid having 3 or more double bonds. Fatty acids having 4 or more double bonds are particularly effective. Exemplary polyunsaturated fatty acids having 3 or more double bonds include α-linolenic acid, arachidonic acid, eicosapentaenoic acid, and docosahexaenoic acid. Also, polyunsaturated fatty acid-based compounds used in the present invention include esters of such fatty acids, such as methyl esters, ethyl esters, triglycerides, ditriglycerides, and monoglycerides. Eicosapentaenoic acid is a generic name of fatty acids having a carbon number of 20 and five double bonds, and natural eicosapentaenoic acids are cis-type pentavalent straight-chain unsaturated n-3 fatty acids having double bonds at the 5, 8, 11, 14, and 17 positions. Docosahexaenoic acid is a straight-chain hexenoic acid having a carbon number of 22 and cis-double bonds at the 4, 7, 10, 13, 16, and 19 positions. These EPAs and DHAs derived from nature are contained in natural oils and fats, particularly in oils and fats of marine products, such as tuna, bonito, chub mackerel, sardine, and pacific cod. They may be present in a form of glyceride or other derivatives. In the present invention, any material can be used as long as it results in an oil or fat containing a polyunsaturated fatty acid having 3 or more double bonds. Examples of the material for oil or fat containing the polyunsaturated fatty acid include marine fish, such as sardine, chub mackerel, saury, tuna, and bonito; and fats derived from microorganisms; crustaceans, such as euphausiid and shrimp and lobster; fish oil; animal and vegetable oils; and genetically modified vegetable oils. The polyunsaturated fatty acid having 3 or more double bonds can be concentrated by wintering or enzymatically treating oil or fat containing the polyunsaturated fatty acid. Alternatively, the oil or fat containing a polyunsaturated fatty acid having 3 or more double bonds may be esterified with alcohol or hydrorified to fatty acid, and then subjected to distillation, urea addition, column treatment, enzymatic treatment, or supercritical carbon dioxide treatment. Thus, the polyunsaturated fatty acid can be concentrated. The antioxidant used in the present invention does not reduce substances that have been already oxidized. It is therefore necessary that oxides be removed from the organic substance having a double bond before adding the antioxidant. For a polyunsaturated fatty acid or its salt or ester, it is also necessary to remove oxides by degumming, deacidification, decolorization, deodorization, or the like. Preferably, the organic substance is refined to a PV of 3.0 meq/kg or less and an AV of 1.0 or less, and has no odor in terms of sensory testing. The antioxidant used in the present invention does not reduce substances that have been already oxidized. It is therefore desired the organic substance to be added has a high refining degree as much as possible by removing oxides. Since odors resulting form oxidation are generated even by slight oxidation, it is necessary to sufficiently refine the organic substance before adding the antioxidant. If refined fish oil is used, it is preferably refined to a PV of 3.0 meq/kg or less and an AV of 1.0 or less so as to be odorless in terms of sensory testing. Oil or fat constituted of the unsaturated fatty acid contained in the composition of the present invention may be acidified by hydrolysis or oxidation. The oxidation produces hydroperoxides and decomposition products of the hydroperoxides deteriorate taste and flavor. For example, soybean oil is oxidized to produce propionaldehyde, 2-pentenal, caproic aldehyde, acetaldehyde, and crotonaldehyde. These oxidation products from the polyunsaturated fatty acid are causes of disagreeable odors of fish oil, and thus a fishy odor peculiar to fish oil is generated. Refined oils containing the unsaturated fatty acid, such as fish oil, soybean oil, linseed oil, and rape-seed oil, may generate disagreeable odor or change in color in the very early stages of their oxidation. This phenomenon is called “Modori” (deterioration). The “Modori” phenomenon in color of decolorized refined vegetable oil is caused by an oxidation product from vitamin E, chromane-5,6-quinone. The present invention is intended to prevent the unsaturated fatty acid from oxidizing, and produces remarkable effects particularly in animal oil having a low oxidative stability. The organic substance having a double bond, used in the present invention may be provided in form of tape, poultice, or adhesive tape that contains a medical drug using a polymer having a double bond as the base material. Accordingly, the present invention can be applied to rubber polymers, such as butadiene rubber, styrene butadiene rubber, butyl rubber, chloroprene rubber, acrylic rubber, natural rubber, isoprene rubber, and styrene-isoprene-styrene block copolymer. The composition of the present invention may be used in combination with an antioxidant generally used in these rubber polymers. The antioxidative sesame component used in the present invention may be of phenol form. Examples such antioxidative components include sesamol, sesaminol, episesaminol, pilsinol, epihinoresinol, syringaresinol, samine, sesamolinol, and 2,3-di(4′-hydroxy-3′-methoxybenzyl)-2-buten-4-olide. In FIG. 6, the peaks of the HPLC chart, which were detected by an electrochemical detector, represent their respective antioxidative components. This chart shows that sesame contains many antioxidative components. While these components, including sesamol, can produce a satisfactory effect independently, mixtures of these components exhibit stronger antioxidant properties. The antioxidative sesame components may be used singly or in combination. Hence, the antioxidative sesame component used in the present invention may be highly purified antioxidative component from sesame, or a lightly purified antioxidative component including sesamol, which is also containing the other substance derived from sesame, such as sesame lignan, or tocopherol. The antioxidative sesame component may be synthesized. Furthermore, sesame oil may be used as it is, as long as there is no problem with the odor peculiar to sesame oil. Specifically, the antioxidative component can be extracted from sesame seeds, sesame oil, or degreased sesame residue after expressing sesame oil. Alternatively, it can be obtained from scum, which is a component prepared by distillation during deodorization of sesame oil. Preferably, roasted sesame is used because the antioxidative component is increased by roasting. Since non-roasted sesame contains a certain proportion of antioxidative component, it can also be used. For extraction from sesame seeds, it is preferable that the principal constituent or neutral lipid be expressed, or removed with a nonpolar solvent, such as hexane. Although sesame oil can be used as it is, its application is limited because the absolute quantity of the neutral lipid is high and, accordingly, the antioxidative component content is low. The sesame extract used in the present invention may be prepared by any method, as long as antioxidative components such as represented by HPLS peaks shown in FIG. 6 can be extracted. For example, the antioxidative components can be extracted by use of a solvent, a lipid, or an emulsifier. More specifically, the antioxidative components can be extracted from sesame, sesame oil, or sesame residue by use of organic solvents, such as nitrous oxide, acetone, ethanol, ethyl methyl ketone, glycerol, ethyl acetate, methyl acetate, diethyl ether, cyclohexane, dichloromethane, 1,1,1,2-tetrafluoroethane, 1,1,2-trichloroethane, carbon dioxide, 1-butanol, 2-butanol, butane, 1-propanol, 2-propanol, propane, propylene glycol, hexane, and methanol; lipids, such as triglyceride, diglyceride, and monoglyceride; and emulsifiers, such as propylene glycol fatty acid esters, polyglycerol fatty acid esters, and sorbitan fatty acid esters. In addition, after removal of the solvent by evaporation, the extract is redissolved in an organic solvent. Then, water-soluble constituents are removed by partition with water, or insoluble constituents are removed by filtration. Thus, the antioxidative component can be concentrated. In the present invention, the amount of antioxidant used in the external composition can be varied depending on the storage conditions and period or the base material used. If sesamol of sesame is used as the antioxidant, a content of 0.5% or more to the polyunsaturated fatty acid is effective. 1% or more is preferable. Although at most about 0.1% of ascorbyl fatty acid ester can be dissolved in the polyunsaturated fatty acid, it can be appropriately increased according to the application because the duration of antioxidant properties can be enhanced by adding an excessive amount of the antioxidant. For example, a composition prepared by adding 0.1% of sesamol and 0.1% of ascorbyl palmitate to refined fish oil can be preserved for 2 to 3 months at room temperature under open conditions. Examples of the ascorbic acid or ascorbyl fatty acid ester used in the present invention include ascorbic acid and ascorbyl fatty acid esters such as ascorbyl palmitate and ascorbyl stearate. As an alternative to these materials, salts of ascorbic acid can also be used. Preferred are materials having a high solubility in lipids. In the case of use of the ascorbic acid or ascorbyl fatty acid ester among antioxidants used in the present invention, the antioxidant properties can be further maintained by using an excessive amount of the antioxidant more than its soluble amount. Since it is considered that the antioxidant used for oil or fat is not effective unless it is dissolved, an amount of antioxidant more than saturated concentration is not generally added. However, as shown in Examples 11 and 12, the antioxidant properties can be further maintained by adding an excessive amount of ascorbic acid or an ascorbyl fatty acid ester, rather than by adding a saturated concentration. The presence of an excessive amount of ascorbic acid or ascorbyl fatty acid ester is effective even if the antioxidative sesame component is constant. The excessive amount of ascorbic acid or ascorbyl fatty acid ester is effective irrespective of whether it is in powder form or solid form. If the ascorbic acid or ascorbyl fatty acid ester is used under conditions not allowing natural diffusion, preferably, it is finely powdered and uniformly dispersed. In addition to the antioxidative sesame component and the ascorbic acid or ascorbyl fatty acid ester, a tocopherol may be added. The tocopherol may be selected from among α-, β-, γ-, and δ-tocopherols and mixed tocopherol, but preferably δ-tocopherol is used. Tocopherol is often added to commercially available polyunsaturated fatty acids and their salts and esters, such as refined fish oil, in the stage of production. Hence, use of these raw materials naturally results in a product containing tocopherol. Whether tocopherol is present or absent does not affect the synergistic effect of the antioxidative sesame component and the ascorbic acid or ascorbyl fatty acid ester. The oil or fat whose oxidative stability has been enhanced by adding an antioxidative sesame component and ascorbic acid or an ascorbyl fatty acid ester can exhibit satisfactory oxidative stability alone, but it may be used in combination with another antioxidant. Also, it may be mixed with another oil or fat having superior oxidative stability (for example, vegetable oil). Other antioxidants include erythorbic acid, sodium erythorbate, isopropyl citrate, dibutylhydroxytoluene (BHT), and butylhydroxyanisole (BHA). Antioxidants used in combination in food include: food additives, such as tocopherols, hollyhock flower extract, Azuki extract, aspergillus terreus extract, calcium disodium ethylenediaminetetraacetate, disodium ethylenediaminetetraacetate, ellagic acid, erythorbic acid, sodium erythorbate, enju extract, γ-oryzanol, catechin, licorice oil extract, guajac resin, quercetin, isopropyl citrate, clove extract, enzymatically modified isoquercitrin, enzymatically modified rutin (extract), enzymatically decomposed apple extract, sesame seed oil unsaponifiable matter, rice bran oil extract, enzymatically decomposed rice bran, L-cysteine hydrochloride, dibutylhydroxytoluene, Queensland arrowroot extract, essential oil-removed fennel extract, horseradish extract, sesamoline, sage extract, dropwort extract, buckwheat extract, amino acid-sugar reaction product, tea extract, tempeh extract, dokudami extract, rape seed oil extract, coffee bean extract, nordihydroguajaretic acid, sunflower seed extract, pimento extract, ferulic acid, butylhydroxyanisole, grape seed extract, blueberry leaf extract, propolis extract, hego-ginkgo leaf extract, hesperetin, pepper extract, garden balsam extract, gallic acid, propyl gallate, melaleuca oil, morin, chinese bayberry extract, eucalyptus leaf extract, gentian root extract, enzymatically decomposed rutin, rutin (extract), and rosemary extract; and antioxidants approved in other countries, such as thiodipropionic acid, distearyl thiodipropionate, octyl gallate, dodecyl gallate, and tert-butylhydroquinone. Since the composition of the present invention has superior oxidative stability, it can be added to various types of food. For example, skimmed milk, milk casein, milk protein, lactose, oligosaccharide, cane sugar, or dextrin is dissolved in hot water to mix, and then vitamins and minerals are dissolved in the water phase. The oil or fat of the present invention is added to the water phase and mixed with a homo-mixer or the like, followed by homogenizing with a homogenizer. The resulting emulsion is sterilized, concentrated, or spray-dried in the usual manner to yield modified powder milk. Also, the composition of the present invention may be powdered oil using various types of powder base material in the same manner. If the composition is added to food, it is determined whether the composition is in oil or fat form or powdered oil form, depending on the characteristics of the food. The composition may be added to general food, or encapsulated or tableted to prepare health food or a supplement. EXAMPLES The present invention will be further described with reference to the following examples, but the invention is not limited to the examples. In the examples, the following materials were used as the refined fish oil, sesamol, ascorbyl palmitate, ascorbic acid, δ-tocopherol. Refined fish oil (containing 0.5% by weight of δ-tocopherol): DD Oil Type 3 (refined fish oil produced by refining tuna oil to a peroxide value of 5 meq/kg or less, an acid value of 1 or less, and a color Gardner of 3 or less by degumming, deacidification, deodorization, or other process), produced by Nippon Suisan Kaisha, Ltd. Refined fish oil (not containing δ-tocopherol): taken as a sample before adding δ-tocopherol in the process of DD Oil Type 3 preparation, produced by Nippon Suisan Kaisha, Ltd. Refined fish oil (sardine oil): DD Oil Type 2 (refined fish oil produced by refining sardine oil to a peroxide value of 5 meq/kg or less, an acid value of 1 or less, and a color Gardner of 3 or less by degumming, deacidification, deodorization, or other process; containing 28% by weight of EPA, 12% by weight of DHA, and 0.5% by weight of δ-tocopherol), produced by Nippon Suisan Kaisha, Ltd. Sesamol: sesamol (purity: 98%) produced by Nacalai Tesque, Inc. Ascorbyl palmitate: ascorbyl palmitate (purity: 95% or more) produced by Sankyo Foods Co. Ltd. Ascorbic acid: L(+)-ascorbic acid (purity: 99.5%) produced by Nacalai Tesque, Inc. δ-Tocopherol: D-δ-tocopherol (purity: 90%) produced by Wako Pure Chemical Industries Eicosapentaenoic acid ethyl ester: prepared by ethanolysis of sardine oil in the presence of metallic sodium to prepare sardine oil ethyl ester and purifying the ester by distillation and HPLC to a purity of 99%. α-Tocopherol: (±)-α-tocopherol (purity: 98%) produced by Wako Pure Chemical Industries Example 1 <Test for Effect of Sesamol+Ascorbyl Palmitate+δ-Tocopherol> The following antioxidant preparations were added separately to refined fish oil (containing 0.5% by weight of δ-tocopherol) to prepare samples. sesamol (1.0% by weight)+ascorbyl palmitate (0.01% by weight) sesamol (1.0% by weight) alone ascorbyl palmitate (0.01% by weight) alone After 3 mL of the samples were placed separately in respective 30 mL brown bottles and hermetically sealed with septums, the samples were stored at 60° C. After 2 days, the concentration of oxygen in the headspace was measured by gas chromatography and the amount of oxygen absorbed by (reacted with) the oil was calculated. The results are shown in FIG. 1. FIG. 1 shows that the combined use of sesamol and ascorbyl palmitate in the refined fish oil reduced the amount of absorbed oxygen and much more increased the oxidative stability of the refined fish oil than the case where sesamol or ascorbyl palmitate was singly added. Example 2 <Test for Effect of Sesamol+Ascorbic Acid+δ-Tocopherol> The following antioxidant preparations were added separately to refined fish oil (containing 0.5% by weight of δ-tocopherol) to prepare samples. sesamol (1.0% by weight)+ascorbic acid (0.01% by weight) ascorbic acid (0.01% by weight) alone After 4 mL of the samples were placed separately in respective 30 mL brown bottles, storage tests were performed in the same manner as in Example 1. The results are shown in FIG. 2. FIG. 2 shows that the combined use of sesamol and ascorbic acid in the refined fish oil reduced the amount of absorbed oxygen and much more increased the oxidative stability of the refined fish oil than the case where ascorbic acid was singly added. Example 3 <Content Dependence of Sesamol and Ascorbyl Palmitate> The antioxidant preparations constituted of δ-tocopherol, sesamol, and ascorbyl palmitate in the following proportions were added separately to refined fish oil (containing 0.5% by weight of δ-tocopherol) to prepare samples. 0.5%:0.5%:0.05% 0.5%:0.5%:0.1% 0.5%:1.0%:0.05% 0.5%:1.0%:0.1% The samples were subjected to the same storage test as in Example 2 for 11 days. FIG. 3 shows the results. The results suggest that as the contents of sesamol and ascorbyl palmitate in the refined fish oil are increased, the amount of absorbed oxygen is reduced, and that the oxidative stability of the refined fish oil can be increased with content dependence. Example 4 <Test for Effect of Sesamol+Ascorbyl Palmitate> An antioxidant preparation of sesamol (1.0% by weight)+ascorbyl palmitate (0.01% by weight) was added to refined fish oil (not containing δ-tocopherol) to prepare a sample. The resulting sample was subjected to the same storage test as in Example 1. The results are shown in FIG. 4. It has been found that the combined used of sesamol and ascorbyl palmitate can reduce the absorption of oxygen and greatly increase the oxidative stability of the refined fish oil, without using tocopherol. Example 5 <Test for Effect of Sesame Oil Extract+Ascorbyl Palmitate (0.1% by weight)+δ-Tocopherol> To 8.23 g of roasted sesame oil was added 100 mL of methanol, and the mixture was strongly agitated. Then, methanol was evaporated from the methanol phase to obtain 0.28 g of extract. It was confirmed that this extract from methanol contained sesamol, by thin layer chromatography (thin layer: Kiesolgel 60 F254, 0.25 mm, produced by Merck & Co., Inc.; developing solvent:hexane:diethyl ether:acetic acid=70:30:1; coloring reagent: 1,1-diphenyl-2-picrylhydrazyl, free Radical). The following antioxidant preparations were added separately to refined fish oil (containing 0.5% by weight of δ-tocopherol) to prepare samples. methanol extract of sesame oil (2.0% by weight)+ascorbyl palmitate (0.1% by weight) methanol extract of sesame oil (2.0% by weight) alone ascorbyl palmitate (0.1% by weight) alone The samples were subjected to the same storage test as in Example 2. The results are shown in FIG. 5. It has been found that the methanol extract of sesame oil as well as sesamol does not produce the effect by itself, and that combined use with ascorbyl palmitate reduces the amount of absorbed oxygen and increases the oxidative stability of the refined fish oil. Example 6 <Test for Effect of Roasted Sesame residue Extract+Ascorbyl Palmitate+δ-Tocopherol> (1) Roasted Sesame Residue Extract 1 To 1.0 kg of roasted sesame residue was added 2.0 kg of 95% ethanol, and the mixture was strongly agitated at 40° C. for 2 hours. Then, the roasted sesame residue was filtrated to obtain an extract. To the roasted sesame residue subjected to the filtration, 1.5 kg of 95% ethanol was added again. The mixture was strongly shaken at 40° C. for one hour, and then filtrated to obtain an extract. The total extract obtained by 2 cycles of filtration was concentrated, and 240 g of ethyl acetate and 80 g of water were added, followed by strongly shaking at 45° C. for 1 hour. After shaking, the water phase was removed, and 40 g of propylene glycol monooleate was added to the ethyl acetate phase. The ethyl acetate was evaporated to yield 58 g of roasted sesame residue extract 1 (18 g of roasted sesame residue extract in real terms because the extract contained 40 g of propylene glycol monooleate). (2) Roasted Sesame Residue Extract 2 To 1.0 kg of roasted sesame residue was added 2.0 kg of 95% ethanol, and the mixture was strongly agitated at 40° C. for 2 hours. Then, the roasted sesame residue was filtrated to obtain an extract. To the roasted sesame residue subjected to the filtration, 1.5 kg of 95% ethanol was added again. The mixture was strongly shaken at 40° C. for one hour, and then filtrated to obtain an extract. To the total extract obtained by 2 cycles of filtration was added 40 g of propylene glycol monooleate. Then, the 95% ethanol was evaporated to yield 50 g of roasted sesame residue extract (10 g of roasted sesame residue extract in real terms because the extract contained 40 g of propylene glycol monooleate). (3) Roasted Sesame Residue Extract 3 To 200 g of roasted sesame residue was added 300 mL of 95% ethanol, and the mixture was strongly shaken at 40° C. for 2 hours. Then, the roasted sesame residue was filtrated to obtain an extract. To the roasted sesame residue subjected to the filtration, 300 mL of 95% ethanol was added again. Then, the mixture was strongly agitated at 40° C. for 2 hours, and then filtrated to obtain an extract. The total extract obtained by 2 cycles of filtration was concentrated. Then, 150 mL of ethyl acetate and 50 mL of water were added, and the mixture was strongly agitated at room temperature for one hour. After the agitation, the water phase was removed, and further ethyl acetate was evaporated to yield 9.0 g of roasted sesame residue extract. Roasted sesame residue extract 1 was subjected to a measurement by high-performance liquid chromatography with an electrochemical detector. The measurement was performed under the following conditions. The chart was shown in FIG. 6. Since the peaks were detected by the electrochemical detector, all the substances represented by the peaks have antioxidant properties. Thus, it is shown that the roasted sesame residue contains many antioxidative components, including sesamol and pinoresinol. Measurement Conditions Column: TSK-gel ODS-80Ts 4.6×150 mm Eluant: 0-5 min., methanol:water (containing 2% of 1 M ammonium acetate buffer (pH 4.4))=40:60 10-17 min., methanol:water (containing 2% of 1 M ammonium acetate buffer (pH 4.4))=70:30 22-40 min., methanol:water (containing 2% of 1 M ammonium acetate buffer (pH 4.4))=100:0 Flow rate: 1.0 mL/min. Column temperature: 35° C. Sample concentration: 10-12 mg/mL Sample solvent: methanol:ethanol:hexane=5:4:1 Injection volume: 10 μL Electrode 1 (reduction potential): −1 V Electrode 2 (oxidation potential): 500 mV Range: 20 μA Samples were prepared by adding the following antioxidant preparations separately to refined fish oil (containing 0.5% by weight of δ-tocopherol). roasted sesame residue extract 1 (1.0% by weight)+ascorbyl palmitate (0.05% by weight) roasted sesame residue extract 1 (1.0% by weight)+ascorbyl palmitate (0.1% by weight) roasted sesame residue extract 1 (1.0% by weight) alone ascorbyl palmitate (0.1% by weight) alone roasted sesame residue extract 2 (1.0% by weight)+ascorbyl palmitate (0.1% by weight) roasted sesame residue extract 3 (1.0% by weight)+ascorbyl palmitate (0.1% by weight) The samples were subjected to the same storage test as in Example 2. The results are shown in FIG. 7. It has been found that the roasted sesame residue extracts can reduce the amount of absorbed oxygen and increase the oxidative stability of the refined fish oil, by using them in combination with ascorbyl palmitate, as in the case of sesamol. Example 7 <Test for Effect of Roasted Sesame Residue Extract+Ascorbyl Palmitate+δ-Tocopherol> Samples were prepared by separately adding antioxidant preparations of Example 6: roasted sesame residue extract 1 (1.0% by weight)+ascorbyl palmitate (0.1% by weight); and roasted sesame residue extract 2 (1.0% by weight)+ascorbyl palmitate (0.1% by weight). In 20 mL brown bottles were placed 10 mL of the samples separately. Each mixture was stored at 60° C. with the bottle open, and changes in concentration of malondialdehyde and alkenals were measured during storage with SafTest produced by Saftest Inc. The results are shown in FIGS. 8 and 9. These figures show that by adding a roasted sesame residue extract and ascorbyl palmitate to refined fish oil, the generation of malondialdehyde and alkenals resulting from oxidation decomposition of fish oil, which are odorants of deteriorated fish oil, can be highly suppressed and thus the fish oil can be stabilized. Example 8 Sesaminol obtained from roasted sesame residue extract 3 with a silica gel open column ODS-HPLC was used instead of the sesamol of Example 1. As a result, the same effect was produced. Example 9 Pinoresinol obtained from roasted sesame residue extract 3 with a silica gel open column ODS-HPLC was used instead of the sesamol of Example 1. As a result, the same effect was produced. Example 10 2,3-Di(4′-hydroxy-3′-methoxybenzyl)-2-buten-4-olide obtained from roasted sesame residue extract 3 with a silica gel open column ODS-HPLC was used instead of the sesamol of Example 1. As a result, the same effect was produced. Example 11 <Test for Effect of Excessive Amount of Ascorbic Acid Ester> The following antioxidant preparations were added separately to refined fish oil (containing 0.5% by weight of δ-tocopherol) to prepare samples. sesamol (0.5%)+ascorbyl palmitate (0.1%) sesamol (1.0%)+ascorbyl palmitate (0.1%) After 4 mL of the samples were placed separately in respective 30 mL brown bottles and hermetically sealed with septums, the samples were stored at 60° C. The concentration of oxygen during storage was measured by gas chromatography, and thus the amount of oxygen reacted with (absorbed by) the oil was calculated. Also, the remaining antioxidant contents were analyzed by HPLC with an electrochemical detector. The results are shown in FIGS. 10 and 11. The figures show that, in either case, ascorbyl palmitate was consumed (oxidized) to be lost first, and then the refined fish oil, δ-tocopherol, and sesamol simultaneously started oxidizing. It is therefore assumed that ascorbyl palmitate plays an important role when the antioxidant preparation contains δ-tocopherol, sesamol, and ascorbyl palmitate. In order to confirm this assumption, 0.1% of ascorbyl palmitate was further added to the same system as in FIG. 11 on day four. The results are shown in FIG. 12. FIG. 11 shows that the oil was not oxidized until ascorbyl palmitate was consumed (around day ten); FIG. 12, in which ascorbyl palmitate was added on day four, shows that oxidation of the oil was continuously suppressed even after day ten. Thus, it has been shown that it is important that ascorbyl palmitate is present in the antioxidant system of the present invention. Example 12 <Tests for Effect on Eicosapentaenoic Acid Ethyl Ester of the Present Invention, and for Effect of Excessive Amount of Ascorbyl Palmitate> Samples were prepared by adding the following antioxidant preparations separately to eicosapentaenoic acid ethyl ester with a purity of 99% (containing 0.2% of α-tocopherol) sesamol (1.0%)+ascorbyl palmitate (0.1%) sesamol (1.0%)+ascorbyl palmitate (0.5%) Each sample was stored at 60° C., and the peroxide value (PV) was measured. The results are shown in FIG. 13. The antioxidant property of the antioxidant preparation containing an excessive amount of ascorbyl palmitate (0.5%) was maintained in comparison with that of the antioxidant preparation containing a soluble amount of ascorbyl palmitate (0.1%). Example 13 <Comparison with Antioxidant (t-Butylhydroxytoluene (BHT)) Generally Used in External Preparations)> The antioxidant preparation of the present invention was compared with t-butylhydroxytoluene (BHT), which is an antioxidant generally used. Samples were prepared by adding 0.5%, 1.5%, or 10.0% of BHT, or 1.0% of sesamol and 0.5% of ascorbyl palmitate to refined fish oil (sardine oil) containing 0.5% of δ-tocopherol. To 30 mL brown bottles, 4 mL of the samples were placed separately. The bottles were hermetically sealed with septums and stored at 37° C. The oxygen concentration in the headspace was measured with time by gas chromatography and thus the amount of oxygen reacted with (absorbed by) the oil was calculated. Results FIG. 14 shows the comparison of the antioxidant properties between BHT and the antioxidant preparation of the present invention. The results show that the antioxidant preparation of the present invention exhibited higher antioxidant property than the same amount (1.5%) of BHT as the total amounts of the antioxidants in the antioxidant preparation of the present invention, and also than a much larger amount (10.0%) of BHT. INDUSTRIAL APPLICABILITY The present invention can provide oils and fats having oxidative stability far superior to known oils and fats containing a polyunsaturated fatty acid. Consequently, when a polyunsaturated fatty acid is added to food, medical drugs, and the like for health promotion, such products can be easily produced and preserved. Also, the types of food to which the composition is added and the polyunsaturated fatty acid content can be easily increased. Specifically, general-purpose refined fish oil containing EPA and DHA can be provided for health food or the like.
<SOH> BACKGROUND ART <EOH>It has recently become known that oils and fats, particularly those containing polyunsaturated fatty acids, have physiologic activity. Accordingly, such oils and fats have been increasingly and widely used in food and animal feed as additives, from the viewpoint of health. Eicosapentaenoic acid and docosahexaenoic acid are polyunsaturated fatty acids mainly contained in fish oil. It has been found that they have the effect of, for example, preventing hyperlipemia, high blood pressure, skin aging, and the like, and they have been used in medical drugs and food with health-promoting benefits. Unfortunately, oils and fats containing such a polyunsaturated fatty acid have low oxidative stability. Accordingly, food to which such an oil or fat can be added is limited, or if added to food or the like, the oil or fat undesirably generates an odor due to its oxidation, even slight oxidation. How the oil or fat is handled needs to be taken into account. For example, refined fish oil remaining after use must be hermetically sealed with the can of the fish oil filled with nitrogen gas. Thus, there are limits in use, such as of product type, distribution temperature, content, and storage conditions. Since, for example, docosahexaenoic acid and eicosapentaenoic acid play an important role to develop the brain and retinas and the memory and learning function of babies and breast milk contains these fatty acids, modified milk for babies to which fish oil containing docosahexaenoic acid and eicosapentaenoic acid has been added is commercially available. Also, since arachidonic acid plays an important role for growth and is contained in breast milk, addition of arachidonic acid to the modified baby milk has been attempted. However, it is necessary to take care not to oxidize polyunsaturated fatty acids when these polyunsaturated fatty acids are blended into the modified baby milk. Otherwise, oxidized odor is generated by oxidation, so that not only the modified milk becomes difficult to ingest, but also the modified milk itself may be degraded to be toxic. Encapsulated eicosapentaenoic acid ethyl esters are commercially available as medical drugs for oral administration. Refined fish oil containing eicosapentaenoic acid and docosahexaenoic acid is also available in form of capsule as health food. Since these fatty acids are liable to be oxidized, their use is limited, except for use in capsules. In order enhance the oxidative stability, the oils and fats can be powdered. For example, oil or fat may be encapsulated into microcapsules to be powdered, or enclosed with cyclodextrin and powdered so that stable powdered oil or fat is provided. However, this approach makes the production steps complicated and decreases productivity. In addition, capsules may be broken during storage, and the type of capsule applicable for food and animal feed is limited, disadvantageously. In order to enhance the oxidative stability of oils and fats, various types of antioxidant have been used. For example, plural types of antioxidant are used in combination, or a synergist, such as phosphoric acid, citric acid, or ascorbic acid, is added to an antioxidant to enhance the antioxidant properties. However, the oxidation stabilities of fish oils and other oils and fats having extremely low oxidative stability cannot be sufficiently enhanced by only such combinations of antioxidants and synergists. Dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), gallic acid, propyl gallate, tocopherols, and the like are approved as antioxidants for oils and fats and food containing oil or fat, in order to prevent oils and fats from oxidizing. In medical drugs and the like, synthetic antioxidants are used, such as BHT, BHA, TBHQ, and ethoxyquin. Sesame oil is relatively stable to oxidation, and it has been known since a long time ago that sesame contains antioxidative components, such as sesamol and other lignans (Japanese Unexamined Patent Application Publication No. 58-132076; Shoku no Kagaku, 225 (11) pp. 40-48 (1996); Shoku no Kagaku, 225 (11) pp. 32-36 (1996)). Sesamol is an antioxidant for oils and fats and food containing oil or fat, and is approved as a food additive. It is however reported that sesamol is not effective for oils and fats exhibiting extremely low oxidative stability, such as fish oil (NOF Corporation, from fiscal Heisei 4 (1994) to Heisei 8 (1996), DHA Koudo Seisei Chushutsu Gijutsu Kaihatsu Jigyo, Kekka Gaiyou (DHA Koudo Seisei Chushutsu Gijutsu Kenkyu Kumiai) pp. 74-79 (2002)). Sesamol is not used for enhancing the oxidative stability of fish oil. Ascorbic acid and ascorbic acid derivatives are also approved as food additives and used as antioxidants for oils and fats and food containing oil or fat. However, they are not effective for oils and fats exhibiting extremely low oxidative stability, such as fish oil, if they are used alone, and even their combined use with tocopherol does not produce satisfactory effects. In order to prevent the oxidation of oils and fats, combined use of various types of antioxidant has been attempted. For example, Japanese Unexamined Patent Application Publication No. 2002-142673 has disclosed a lipophilic antioxidant prepared by emulsifying gallic acid, a water-soluble antioxidant, and an oil-soluble antioxidant into a water-in-oil form with a lipophilic emulsifier. In this application, examples of the water-soluble antioxidant include vitamin C, citric acid, chlorogenic acid, their derivatives, sugar-amino reaction products, proanthocyanidin, flavone derivatives, tea extracts, grape seed extracts, and rutin, and examples of the oil-soluble antioxidant include tocopherol, ascorbyl palmitate, sesamol, and γ-oryzanol. Effects of antioxidants have been compared for pyrolysis of tocopherol in vegetable oils in Nippon Eiyo Shokuryo Gakkaishi (Journal of Japanese Society of Nutrition and Food Science), 44 (6) pp. 493-498 (1991), 45 (3) pp. 291-295 (1992), and 45 (3) pp. 285-290 (1992). Although some of the antioxidants use sesamol and an ascorbic acid ester in combination, they do not produce effects particularly superior to other antioxidants. These literatures discuss effects in oxidation of vegetable oils (having 3 or less unsaturated bonds) at high temperatures, but not in oxidation of polyunsaturated fatty acids (having at least three unsaturated bonds) during storage at room temperature; hence different objects are used under different conditions. This is probably because the combination of sesamol and an ascorbic acid ester does not produce superior effects. In addition, the thermal instability of the antioxidants may affect antioxidant properties. Demand for oil or fat containing an unsaturated fatty acid is increasingly growing. Accordingly, it is highly desired to solve the problem of oxidative stability, including how to handle the oil or fat, in a strict sense.
<SOH> BRIEF DESCRIPTION OF THE DRAWINGS <EOH>FIG. 1 shows amounts of oxygen absorbed by oil or fat in Example 1. FIG. 2 shows amounts of oxygen absorbed by oil or fat in Example 2. FIG. 3 shows amounts of oxygen absorbed by oil or fat in Example 3. FIG. 4 shows amounts of oxygen absorbed by oil or fat in Example 4. FIG. 5 shows amounts of oxygen absorbed by oil or fat in Example 5. FIG. 6 is a high-performance liquid chromatographic chart of sesame residue extract 1, obtained with an electrochemical detector in Example 6. FIG. 7 shows changes with time in the amount of oxygen absorbed by samples of Example 6. FIG. 8 shows changes with time in the malondialdehyde content in samples of Example 7. FIG. 9 shows changes with time in the alkenal content in samples of Example 7. FIG. 10 shows changes with time in the amounts of oxygen absorbed by a sample (sesamol, 0.5%) and the remaining amounts of antioxidants in Example 8. FIG. 11 shows changes with time in the amounts of oxygen absorbed by a sample (sesamol, 1.0%) and the remaining amounts of antioxidants in Example 8. FIG. 12 shows changes with time in the amounts of oxygen absorbed by samples and the remaining amounts of antioxidants in the case where ascorbyl palmitate was added after 4 days in Example 8. FIG. 13 shows changes with time in the PV of samples of Example 9. FIG. 14 shows comparison in antioxidant property between BHT and the antioxidant preparation according to the present invention. detailed-description description="Detailed Description" end="lead"?
20051117
20140513
20060622
60981.0
A61K4700
0
WINSTON, RANDALL O
COMPOSITION CONTAINING ORGANIC SUBSTANCE HAVING DOUBLE BOND WITH IMPROVED OXIDATIVE STABILITY
UNDISCOUNTED
0
ACCEPTED
A61K
2,005
10,535,516
ACCEPTED
Game image display control program, game device, and recording medium
A game image display control program in which even in the case where a radar image is displayed on display devices with different screen ratios, a range which is actually in a visual field can match with radar visual field display is provided. The program has a function for displaying a video picture captured from a first visual point position in a virtual three-dimensional space as a main screen of a game on a display unit, and displaying a predetermined range where the virtual three-dimensional space is captured from a second visual point position and a visual field area, where an area in which the virtual three-dimensional space is captured from the first or a third visual point position at a predetermined azimuthal angle is projected in the predetermined range, as a radar image representing a position relationship of an object on a three-dimensional map composing the virtual three-dimensional space on the display unit, and a function for changing a shape of the visual field area according to a shape of the main screen in the display unit.
1. A game image display control program for allowing a computer to realize a function for displaying a video picture captured from a first visual point position in a virtual three-dimensional space as a main screen of a game on a display unit, and displaying a predetermined range where the virtual three-dimensional space is captured from a second visual point position and a visual field area, in which an area where the virtual three-dimensional space is captured from the first or a third visual point position at a predetermined azimuthal angle is projected in the predetermined range, as a radar image representing a position relationship of an object on a three-dimensional map composing the virtual three-dimensional space, comprising a function for changing a shape of the visual field area according to a shape of the main screen in the display unit. 2. The game image display control program according to claim 1, further comprising a function for changing the shape of the main screen according to a screen ratio of the display unit to change the shape of the visual field area accordingly. 3. The game image display control program according to claim 1, further comprising a function for changing the shape of the visual field area according to a screen ratio of the display unit independently from a change in the shape of the main screen. 4. The game image display control program according to claim 1, further comprising a function for capable of setting the shape of the main screen independently from a screen ratio of the display unit and changing the shape of the visual field area according to the set shape of the main screen. 5. The game image display control program according to claim 1, further comprising a function for changing the shape of the main screen according to game proceeding. 6. The game image display control program according to claim 1, wherein the visual field area is a pyramid shaped or a conical visual field area where the first or the third visual point position is an apex. 7. The game image display control program according to claim 1, wherein the visual field area is a quadrangular pyramid shaped or a conical visual field area where the first or the third visual point position is an apex, comprising a function for changing the shape of the main screen and the shape of the visual field area so that an aspect ratio of a bottom surface of the quadrangular pyramid matches with the screen ratio of the display unit. 8. The game image display control program according to claim 1, comprising a function having a virtual camera which photographs an area captured from the first or the third visual point position for adjusting a field angle of the virtual camera according to the shape of the main screen so as to change the shape of the visual field area. 9. The game image display control program according to claim 1, comprising a function having at least a mode where a ratio of a horizontal direction to a vertical direction of the screen of the display unit is 4:3 and a mode where the ratio is 16:9 for widening a visual field in the horizontal direction of the visual field area in the mode of 16:9 in comparison with the mode of 4:3. 10. The game image display control program according to claim 1, wherein the video picture to be displayed on the main screen is a video picture relating to the mobile object moving in the virtual three-dimensional space in response to a player's operation and a visual field direction of the video picture on the main screen can be freely rotationally moved to any directions in the virtual three-dimensional space with the first visual point position being a center independently from an advancing direction of the mobile object, comprising a function for controlling a rotation movement of the visual field area in conjunction with the rotational movement of the video picture on the main screen. 11. The game image display control program according to claim 1, wherein the video picture to be displayed on the main screen is a video picture relating to the mobile object moving in the virtual three-dimensional space in response to the player's operation, and an entire movable area of the mobile object or a periphery of the mobile object is displayed as the radar image. 12. The game image display control program according to claim 1, wherein the video picture to be displayed on the main screen is a video picture relating to the mobile object moving in the virtual three-dimensional space in response to the player's operation, and the third visual point position is a position of the mobile object or a position in its vicinity. 13. The game image display control program according to claim 1, wherein the video picture to be displayed on the main screen is a video picture relating to the mobile object moving in the virtual three-dimensional space in response to the player's operation, and the second visual point position is a position above the mobile object. 14. The game image display control program according to claim 1, wherein the video picture to be displayed on the main screen is a video picture relating to the mobile object moving in the virtual three-dimensional space in response to the player's operation, and a predetermined range where the virtual three-dimensional space is captured from the second visual point position is a range centering on the mobile object. 15. A game image display control program for allowing a computer to realize a function for displaying a video picture obtained by capturing a mobile object moving in a virtual three-dimensional space from a first visual point position as a main screen of a game on a display unit, a function for capturing a predetermined range centering on the mobile object in the virtual three-dimensional space and a predetermined object included in the predetermined range from a position above the mobile object and displaying the predetermined range and icons representing the mobile object and the object as a radar image on a part of the main screen of the game, and a function for displaying a visual field area, where an area in which the virtual three-dimensional space is captured from the first visual point position or from the position of the mobile object is projected in the predetermined range, on a radar screen, further comprising: a function for changing a shape of the main screen according to a shape of the display unit or game proceeding; and a function for changing a shape of the visual field area according to the shape of the main screen. 16. A game machine which is constituted so as to be capable of executing the game image control program according to claim 1. 17. A recording medium which is a readable by means of a computer and into which the game image control program according to claim 1 is recorded.
TECHNICAL FIELD The present invention relates to a game image display control program which has a function for displaying an image representing an arrangement relationship of specified objects on a map composing a virtual three-dimensional space as a radar image, a game machine, and a storage medium. The invention particularly relates to the game image display control program which changes a shape of a visual field area according to a shape of a game screen so as to display the radar image on arbitrary display devices with various screen ratio (aspect ratio), the game machine and the storage medium. BACKGROUND ART In game machines which realize computer games such as so-called action type games and role playing games, a leading character (player character) in a game image displayed on a screen of a display device is controlled according to an operation signal from an input device (controller pad) operated by a player, so that the story of the game proceeds. Particularly in recent years, according to improvement of hardware performance, a game image such that a player character acts in the virtual three-dimensional space is provided in a form of three-dimensional graphics, thereby heightening the presentation effect of the game. In three-dimensional graphics, a spatial position relationship of an object in a visual line direction is obtained from a visual point position in the virtual three-dimensional space based on three-dimensional data expressing the object, an image process such as a rendering process is executed, so that the object is expressed three-dimensionally. That is to say, in games utilizing three-dimensional graphics, a player character and another object captured from the visual point position are expressed three-dimensionally, and the visual point position and the visual line are moved according to operations by the player or game scenes. Game images in which the virtual three-dimensional space is expressed in such a manner are provided. Game machines, which provide game images where the virtual three-dimensional space is expressed from a specified camera angle in games such as action type games using a lot of three-dimensional graphics, provide the following game images, for example. In the game images, a character which moves in response to an operation by the planer is tracked to be photographed by a virtual camera arranged in an upper-backward position of the character. In the case where the thing which is present besides far background such as mist is expressed, an effect image which draws the landscape is synthesized with the far background and the character image to be displayed, so that various things which come into the visual field of the virtual camera are expressed, thereby providing the sense of reality. In the case where an object which moves in the virtual three-dimensional space is to be displayed, like an image which is tracked to be photographed by the virtual camera is displayed on a display unit of the display device. Since a size of a display area is, however, limited, only a range of the viewing angle where the virtual camera is the visual point is displayed. For this reason, a screen, on which the arrangement relationship of a specified object such as its current position and a relative position relationship between the specified object and another mobile object in a course map where a moving range is limited is shown as a pattern in a reduced-size graphic (hereinafter, radar image), as well as a main screen is displayed in order to understand a condition of a range which is not displayed in a range captured by the virtual camera (for example, see Patent Document 1). Further, the game machines which display radar images include the following game machines (for example, see Non-Patent Document 1). In this game machine, like a game where a player's battleplane is operated to attack an opponent's battleplane, a circular radar frame obtained by patterning a radar, for example, as well as a visual field image captured from the self battleplane is displayed on a display unit, a “visual field display” representing a portion actually displayed on a main screen is displayed as a radar image in a radar detection space, and player's sight is set on the opponent's battleplane in the radar image so as to attack the opponent's battleplane. At this time, on the radar image which represents the radar detection space, a character to be operated by the player is arranged on the center or lower-end center, and a position of the object is displayed as a small window represented by a light spot or a symbol with the character looking down the ground vertically. A fan shaped (or (inverted) triangular) section whose center (apex) shows the character to be operated by the player is displayed within the small window, so that a visual field portion is expressed. In recent years, the display devices include two types of display devices whose screen ratio (aspect ratio) is 4:3, namely, have a normal screen (standard screen) and 16:9, namely, have a wide screen. In image processing devices such as game machines which display virtual objects, however, even if the aspect ratio is different from the above aspect ratios, a player feels less discomfort at the screen unlike television broadcasting which provides an actual live image. For this reason, images are generally processed without taking the screen ratio into consideration. When, however, images on the standard screen created by the image processing devices such as the game machines are directly displayed on the wide screen, defects such as non-image portions on right and left portions occur. When the images on the standard screen are displayed on a wide-screen television or monitor device which has a function for converting the aspect ratio in a lateral direction and a vertical direction of a sampling signal, the lateral direction is widened or the vertical direction is reduced. For this reason, the images are extended laterally or the images are reduced vertically, and thus distorted images are displayed. In such display devices having the function for switching between the standard images and the wide images, image data, which are reduced or enlarged by the opposite scaling to the scaling in the display devices, are created to be output to the display devices, so that the images can be displayed with the original ratio. When, however, such images are displayed on the display devices having a wide-size screen which does not have the switching function, a defect such as an image distorted to an opposite direction occurs. The image processing devices which display the virtual objects such as game machines do not generally cope with various screen ratios, and even if they cope with the various ratios, defects occur in the display devices which do not have the function for switching between the wide-size screen and the standard screen in the image processing system which reduce or enlarge images with the scaling opposite to the scaling in the display devices. Particularly in the radar images where a predetermined area in the three-dimensional virtual space is expressed by reduced figure or the like, images in which the wide-screen display devices are taken into consideration are not processed, and even when the ratio of the image on the main screen is switched, the size of the visual field display of the radar portion is not changed. Further, in the form where the ratio is switched in the display device, a range which is actually in the visual field is different from the visual field display of the radar, a shape of the radar frame on the radar display portion is distorted, and the arrangement relationship of the object in the three-dimensional space to be displayed on the radar is not accurate. Conventionally, the radar image is displayed as a fan-shaped or inverted triangular plane representing the detection space, and display contents are fixed ones which are looked down vertically. A range which is actually in the visual field does not match with the visual field display of the radar, and the radar images which are obtained by capturing the visual field area in an arbitrary direction from the visual point position in the virtual three-dimensional space in conjunction with the game images cannot be displayed on the wide-size screen without trouble. The present invention is devised from the viewpoint of the above situation, and its object is to provide a game image display control program which is capable of allowing a range which is actually in a visual field to match with a visual field display of a radar even when a radar image is displayed on a display device with varied screen ratio, a game machine, and a storage medium. DISCLOSURE OF INVENTION The present invention relates to a game image display control program, a game machine, and a storage medium, and its object is achieved by a game image display control program for allowing a computer to realize a function for displaying a video picture captured from a first visual point position in a virtual three-dimensional space as a main screen of a game on a display unit, and displaying a predetermined range where the virtual three-dimensional space is captured from a second visual point position and a visual field area, in which an area where the virtual three-dimensional space is captured from the first or a third visual point position at a predetermined azimuthal angle is projected in the predetermined range, as a radar image representing a position relationship of an object on a three-dimensional map composing the virtual three-dimensional space, comprising a function for changing a shape of the visual field area according to a shape of the main screen in the display unit. Further, the object of the present invention is achieved more effectively by a function for changing the shape of the main screen according to a screen ratio of the display unit to change the shape of the visual field area accordingly; a function for changing the shape of the visual field area according to a screen ratio of the display unit independently from a change in the shape of the main screen; a function for capable of setting the shape of the main screen independently from a screen ratio of the display unit and changing the shape of the visual field area according to the set shape of the main screen; a function for changing the shape of the main screen according to game proceeding; that the visual field area is a pyramid shaped or a conical visual field area where the first or the third visual point position is an apex; that the visual field area is a quadrangular pyramid shaped or a conical visual field area where the first or the third visual point position is an apex, and a function for changing the shape of the main screen and the shape of the visual field area so that an aspect ratio of a bottom surface of the quadrangular pyramid matches with the screen ratio of the display unit; and a function having a virtual camera which photographs an area captured from the first or the third visual point position for adjusting a field angle of the virtual camera according to the shape of the main screen so as to change the shape of the visual field area. Further, the present invention is achieved more effectively by a function having at least a mode where a ratio of a horizontal direction to a vertical direction of the screen of the display unit is 4:3 and a mode where the ratio is 16:9 for widening a visual field in the horizontal direction of the visual field area in the mode of 16:9 in comparison with the mode of 4:3; that the video picture to be displayed on the main screen is a video picture relating to the mobile object moving in the virtual three-dimensional space in response to a player's operation and a visual field direction of the video picture on the main screen can be freely rotationally moved to any directions in the virtual three-dimensional space with the first visual point position being a center independently from an advancing direction of the mobile object and a function for controlling a rotation movement of the visual field area in conjunction with the rotational movement of the video picture on the main screen; that the video picture to be displayed on the main screen is a video picture relating to the mobile object moving in the virtual three-dimensional space in response to the player's operation, and an entire movable area of the mobile object or a periphery of the mobile object is displayed as the radar image; that the video picture to be displayed on the main screen is a video picture relating to the mobile object moving in the virtual three-dimensional space in response to the player's operation, and the third visual point position is a position of the mobile object or a position in its vicinity; that the video picture to be displayed on the main screen is a video picture relating to the mobile object moving in the virtual three-dimensional space in response to the player's operation, and the second visual point position is a position above the mobile object; and that the video picture to be displayed on the main screen is a video picture relating to the mobile object moving in the virtual three-dimensional space in response to the player's operation, and a predetermined range where the virtual three-dimensional space is captured from the second visual point position is a range centering on the mobile object. In another way, the present invention is achieved by a game image display control program for allowing a computer to realize a function for displaying a video picture obtained by capturing a mobile object moving in a virtual three-dimensional space from a first visual point position as a main screen of a game on a display unit, a function for capturing a predetermined range centering on the mobile object in the virtual three-dimensional space and a predetermined object included in the predetermined range from a position above the mobile object and displaying the predetermined range and icons representing the mobile object and the object as a radar image on a part of the main screen of the game, and a function for displaying a visual field area, where an area in which the virtual three-dimensional space is captured from the first visual point position or from the position of the mobile object is projected in the predetermined range, on a radar screen, comprising: a function for changing a shape of the main screen according to a shape of the display unit or game proceeding; and a function for changing a shape of the visual field area according to the shape of the main screen. Further, the present invention is achieved by a game machine which is constituted so as to be capable of executing any one of the above game image control programs. Further, the invention is achieved by a recording medium which is a readable by means of a computer and into which any one of the above game image control programs is recorded. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a block diagram illustrating one example of a constitution of an information processing device which realizes the present invention; FIG. 2 is a block diagram illustrating one example of a constitution of a main section of software which realizes an image processing function according to the present invention; FIGS. 3A and 3B are pattern diagrams for explaining a radar image display control system and a first display form according to the present invention; FIGS. 4A and 4B are pattern diagrams for explaining the radar image display control system and a second display form according to the present invention; FIG. 5 is a diagram illustrating a main screen of a game and a first example of the radar image in a standard mode; FIG. 6 is a diagram illustrating the main screen of the game and a second example of the radar image in the standard mode; FIG. 7 is a diagram illustrating the main screen of the game and a third example of the radar image in the standard mode; FIG. 8 is a diagram illustrating the main screen of the game and a fourth example of the radar image in the standard mode; FIG. 9 is a diagram illustrating a main screen of the game and a first example of the radar image in a wide-screen television mode; FIG. 10 is a diagram illustrating the main screen of the game and a second example of the radar image in the wide-screen television mode; FIG. 11 is a diagram illustrating the main screen of the game and a third example of the radar image in the wide-screen television mode; FIG. 12 is a diagram illustrating the main screen of the game and a fourth example of the radar image in the wide-screen television mode; FIG. 13 is a diagram illustrating the main screen of the game and a first example of the radar image in another display form; FIG. 14 is a diagram illustrating the main screen of the game and a second example of the radar image in another display mode; FIG. 15 is a diagram illustrating the main screen of the game and a third example of the radar image in another display mode; FIGS. 16A to 16C are pattern diagrams illustrating concrete examples in the case where a shape of a visual field area of the radar image is displayed three-dimensionally; and FIG. 17 is a flowchart for explaining an operation example of the image processing device relating to a radar image display process according to the present invention. BEST MODES FOR CARRYING OUT THE INVENTION Embodiments of the present invention are explained in detailed below with reference to the drawings. A game proceeds while a predetermined mobile object (hereinafter, player character), which moves in a virtual three-dimensional space in response to an operation input by an operator (hereinafter, player), is moving along a predetermined course in the virtual three-dimensional space where a moving area is limited like a car racecourse having a course frame or is freely moving in the virtual three-dimensional space where a moving area is not limited like cosmic space. A case where the present invention is applied to such computer games is explained as an example. A device which realizes an image processing method relating to a radar image in the virtual three-dimensional space according to the present invention may be an information processing device, which can execute and control a computer program, such as a home-use game machine, a personal computer, a mobile phone, an arcade game machine, and a simulation device. A multi-purpose constitution can be applied to its hardware constitution. FIG. 1 is a block diagram illustrating one example of a constitution of an information processing device which realizes the present invention (hereinafter, game machine). The game machine according to the present invention has a controller 10 that controls execution of a computer program and controls input/output with respect to peripheral equipment via an I/O interface 11, an input unit 20 that inputs operation information or the like of a player, a display unit 30 that displays an image thereon, a voice output unit 40 that outputs sound effects, voice and the like, and a recording medium 50 that records an application program, data and the like therein. As hardware, the controller 10 is composed of a control device such as CPU or MPU, the operation information input unit 20 is composed of an input device such as a control pad, joy stick or a keyboard, the display unit 30 is composed of a display device such as a liquid crystal display or CRT, and the voice output unit 40 is composed of a sound output device such as a speaker. In the present invention, types and a number of hardware are not limited to the above types and numbers. The recording medium 50 is an information storage medium that stores an image processing program and data of the present invention therein, a type and a location of the medium are not limited as long as CPU can control input/output into/from the recording medium 50. For example, a program which is recorded in a recording medium of a server on a network may be made to be cooperative with a program of the game machine so that a process relating to computer graphics is executed. A program may be read from a predetermined recording medium of the game machine (flexible disc, hard disc, CD-ROM, CD-R, DVD-ROM, DVD-RAM, DVD-R, PD disc, MD disc, MO disc, memory card or IC card), so that the process is independently executed by the game machine. The latter form is explained as an example. The image processing function of the present invention is realized by a computer program (hereinafter, program) executed by CPU, and this program is recorded in the predetermined recording medium 50 on the game machine. The present invention includes the form that a part of the image processing function is realized by hardware. FIG. 2 is a block diagram illustrating one example of a constitution of a main section of software which realizes the image processing function according to the present invention. Main components of the controller 10 are a game controller 110 that controls entire movement of a game, a main screen camera work controller 120 that controls camera work of a virtual camera for capturing an object in a virtual three-dimensional space from a first visual point position so as to photograph an image on the main screen of the game, and a main screen display controller 130 that creates image data of a video picture captured from the first visual point position (for example, slightly backward of a player character) in the virtual three-dimensional space by the virtual camera to display the image data as a main screen on the display unit 30. The main screen camera work controller 120 includes a function for changing a shape of the main screen of the game according to a shape of a display unit (screen ratio) or an proceeding condition of the game. The shape of the main screen to be displayed on the display unit 30 changes according to the screen ratio of the display device, for example, and a visual field from the virtual camera is changed into an arbitrary shape such as pyramid or circular cone according to the proceeding condition of the game. The main screen on which an area in the three-dimensional space is projected is formed by the main screen display controller 130 to be displayed on the display unit 30. The unit relating to the radar image process includes a radar image creating unit 130 that creates a predetermined range where the virtual three-dimensional space is captured from a second visual point position (for example, a position where a periphery of a player character is viewed from above) at a first azimuthal direction, and a visual field area on which an area, where the virtual three-dimensional space is captured from the first visual point position or a third visual point position (for example, the position of the player character) at a second azimuthal direction is projected in the predetermined range, as radar image, a visual field area changing unit 150 that changes the shape of the visual field area according to the shape of the main screen of the game on the display unit 30, and a radar display controller 160 that synthesizes the image on the main screen and the radar image by means of an image synthesizing unit 170 according to the proceeding condition of the game or a display instruction by the player to display the synthesized image on the display unit 30 or displays the radar image independently on a predetermined position of another display unit 30A. The visual field changing unit 150 has a function for changing the shape of the visual field area according to the screen ratio of the display unit independently from a change in the shape of the main screen, and a function for changing the shape of the visual field area according to the shape of the main screen set separately from the screen ratio of the display unit as well as a function for changing the shape of the visual field area of the radar image according to the shape of the main screen of the game. For example, in the case where the shape of the main screen is changed into a shape different from normal game according to a scene of the game, the visual field area changing unit 150 changes the shape of the visual field area according to the shape of the main screen, but can enlarge or reduce the visual field area according to the screen ratio of the display unit independently from the control according to the shape of the main screen. Further, the visual field area changing unit 150 can dynamically change the shape of the visual field area according to the shape of the main screen of the game set by a player or an instruction or the like from the game controller 110 in advance independently from the control according to the screen ratio. The radar image in this embodiment means an image representing an arrangement relationship of a specified object on a three-dimensional map composing the virtual three-dimensional space. As to the display form, a position relationship and a direction relationship (or one of them) between a mobile object and another object on the map are (is) displayed, only a position/direction relationship between the objects is displayed, and a schematic diagram of the map in this area as the object is displayed together with the mobile object and another object. As the display contents of the radar image, icons (in this embodiment, light spot) representing the player character, another opponent character, an object of impediment and the like are displayed as the radar image together with the schematic diagram of the map in the visual field area as the need arises on a part of the main screen (or display unit of another display device). At this time, the radar image creating unit 140 creates an image such as the icons representing the objects included in at least one (in this embodiment, the visual field area) of the two areas in the virtual three-dimensional space (the predetermined range and the visual field area projected on the predetermined range) captured from different visual point positions and azimuthal angles so as to display the created image. The radar image creating unit 140 creates an image of the reduced map, for example, as a radar detectable range, or an image representing the objects of characters, impediments and the like as well as the reduced diagram of the map included in the area (the predetermined range) so as to display the created image. At this time, the images are displayed with different colors or density so that the player can discriminate the area in the predetermined range and the visual field area or the objects in the areas. The objects and the like may be displayed so as to be scattered on a three-dimensional visual field area having a shape of pyramid, circular cone or the like, or they may be displayed only on a projected bottom surface. The main screen display controller 130 and the radar display controller 160 have a coordinate converting processor that converts the position of the object in the virtual three-dimensional space (three-dimensional coordinate) into a position on the screen (two-dimensional coordinate) and a drawing unit. In the case where the main screen is created, in this embodiment, display data for a two-dimensional screen is created from a three-dimensional model expressed by a plurality of polygons. The storage unit 180 is composed of a work memory 181 and a data memory 182, data relating to execution of application programs are stored therein. The data memory 182 stores player characters, background and information about fixed objects to be displayed in the virtual three-dimensional space as information of polygonal surface unit therein. Further the data memory stores screen data about the main screen, radar image and the like, various image data such as main screen, background image and radar image to be projected on the screen, screen ratio data for switching a visual field according to the screen ratio, various control data and the like therein. On the other hand, the work memory 181 stores camera work control data (parameters relating to the camera work of the virtual camera), position and direction data of the characters including the player character, a coordinate conversion formula for converting polygon data on a three-dimensional world coordinate into polygon data on a two-dimensional screen coordinate, display modes relating to the screen ratio (in this embodiment, a plurality of display modes according to the horizontal/vertical screen ratio such as a first mode where the screen ratio is 4:3 (hereinafter, “standard mode”) and a second mode where the screen ratio is 16:9 (hereinafter, “wide-screen television mode”)) and the like therein. The coordinate converting processor as the component of the main screen display controller 130 reads the information about the mobile object such as the player character and the background (in this embodiment, the polygon data about the three-dimensional model expressed by a plurality of polygons) and the related coordinate conversion formula from the data memory 182 so as to convert the coordinate of the polygon data. The coordinate converting processor further executes a coordinate converting process so that the polygon data on the three-dimensional coordinate whose coordinate is converted are projected on the screen. The radar display controller 160 creates a radar image based on the position information in the visual field of the objects in which the radar is projected on the screen from a visual point position of a second virtual camera (position and direction, or information about position and information) using a visual field from the visual point position of the second virtual camera as the radar image to be displayed. At this time, in the case where a radar frame representing a radar detection space or a course frame of a race game is displayed, objects in the frame are replaced by icons such as light spots, marks or colors (symbols which can specify the objects) so that the relative position of the objects in the frame can be discriminated easily in the reduced drawing, and the icons are arranged in the visual field area, so that the radar image is created. The drawing unit writes polygon data into an image output memory such as a graphic memory, and after writing all the polygon data, reads them, and synthesizes main screen data composed of background and a player character, effect image data and radar image data if necessary, so as to output the image data to the display unit 30. Information process in the virtual three-dimensional space according to the present invention is explained below. Three-dimensional information is secured as video picture information to be displayed on the display unit 30. That is to say, all positions and shapes of display objects relating to the a video picture to be displayed are specified by coordinates in the three-dimensional coordinate space. A visual point (virtual visual point) is set in an arbitrary position of the virtual three-dimensional space, and the video picture to be displayed on the display unit 30 is a visual scene obtained by projecting a space from the visual point position. The projection means to view the virtual three-dimensional space from the virtual camera, and the projection process is executed based on various parameters such as the visual point position and the azimuthal angle of the virtual camera, and visual field area. The visual point position of the virtual camera can be set in an arbitrary position in space. The visual point position is sequentially moved, so that the video picture displayed on the display unit 30 also changes gradually. At this time, a viewer of the display unit 30 feels like moving in the virtual three-dimensional space. Further, information about a light source can be also included in the virtual three-dimensional space. When the position of the light source is specified, shade is specified on information about objects to be displayed in the space. As to the camera work of the virtual camera for the main screen, the virtual three-dimensional space is projected from an arbitrary position such as a position separated from a mobile object to be tracked by a predetermined distance or a position of the player character like a manner that the mobile object which moves in response to an operation by the player is tracked. The parameters relating to the camera work of the virtual camera such as an object to be tracked, movement of the virtual camera, position and azimuthal angle of the virtual camera, and a distance between the player character and the virtual camera (zoom-up and zoom-out) are automatically changed according to the position of the player character in the virtual three-dimensional space and the scene of the game, and is changed by the operation by the player. For example, the direction and the position of the virtual camera automatically change according to the proceeding condition of the game, and change according to the direction and the position of the player character to be moved in response to the operation by the player, or an operation relating to the visual angle in right, left, up and down directions. Elements which change the parameters are determined based on the position of the player character, the scene of the game and the like. In this embodiment of the present invention, the visual field direction of a video picture on the main screen can be rotatively moved to any directions in the virtual three-dimensional space about the first visual point position as a center independently from the advancing direction of the mobile object which moves in the virtual three-dimensional space in response to the operation by the player. The radar image creating unit 140 creates an image in a visual field area which is projected in a predetermined range in a manner that the visual field area is rotationally moved in conjunction with the rotational movement of the video picture and is captured from that direction. The rotational movement is controlled based on the control information about the camera work in the main screen camera work controller 120, but a radar display camera work controller may be provided to control the rotational movement independently from the camera work on the main screen. There are some methods of expressing an object to be displayed in the virtual three-dimensional space. The typical two methods are a polygon process and a patch process. The polygon process is a method of structuring a three-dimensional space by means of plural polygons. That is to say, in this method, an object to be displayed is regarded as aggregate of plural polygonal plates and information is stored by polygon unit. On the other hand, the patch process is a method of structuring a three-dimensional space by means of plural curved surfaces. According to this method, a three-dimensional space composed of smooth curved surfaces can be structured easily, but its computing takes a longer time than the polygon process. As to the effect screen of the present invention, any one of the methods may be used. In this embodiment, as to the player character and the background, the three-dimensional space is expressed by the polygon process. The image process utilizing polygons is explained as an example. The portion relating to the virtual three-dimensional display is explained in detail. The coordinate converting processor 151 reads the information about the fixed object to be displayed relating to the background stored in the data memory 182, the position of the player character and the position of the visual point stored in the work memory 181, and the coordinate conversion formula relating to them, and converts the information about the fixed object to be displayed such as the background into coordinates based on the relative visual point position of the virtual camera with respect to the player character at that time. Further, the coordinate converting processor executes the coordinate converting process so that the polygon data on the converted three-dimensional coordinate is projected on the screen. The information obtained as a result is transmitted to the drawing unit, so that image data are created by using a degree of transparency, brightness, colors and the like as parameters. As a result, a three-dimensional video picture is projected on the display unit 30. The embodiment where the radar display camera work controller is provided to process the radar image is explained. In this embodiment, a radar image is created based on at least two areas in the virtual three-dimensional space captured from different visual point positions and azimuthal angles, but the camera work relating to the visual field area is explained here. As to the camera work of the second virtual camera (radar display virtual camera), a first visual point position (for example, an upper-backward position of the player character) or a third visual point position (for example, the position of the player character or a radar center position at which a target of shooting or the like is captured) is used as the visual point position of the second virtual camera, an image pickup area (a visual field area whose the shape is changed by the visual field area changing unit 150) such as a wide visual field captured from the entire movable area, a periphery of the mobile object or the visual point position is photographed from a predetermined direction according to the moving condition of the mobile object moving in the virtual three-dimensional space and the proceeding condition of the game. As the arrangement relationship of a specified object, a position relationship between the object of a self character and another object (another mobile object, impediment, whole or part of the map, and the like) is obtained based on three-dimensional position information representing the position (and the direction) of a player character (self mobile object) and another object in the visual field where the virtual three-dimensional space is overlooked from the second visual point position, for example. An image representing the position relationship is created as an image in the visual field area. At this time, the radar image creating unit 140 synthesizes an image for determining the standards such as a concentrical line and a cross line in a circular frame in the case of radar display where radar is patterned or an image representing a shape of a course map in the case of a map showing a course such as a driving course and a maze (an image in a predetermined range of the map) with the image in the visual field area so as to create a radar image. At this time, icons which present the position of the object such as a player's machine, an opponent character and an impediment included in the predetermined range or the position and the direction (simplified symbols such as light spots or marks) are displayed in that area. The display form of the radar image in the above constitution according to the present invention is explained below with reference to the pattern diagrams. In the present invention, a shape of visual field display in the virtual three-dimensional space is changed according to the shape of the game screen so that the range actually in the visual field matches with the visual field display of the radar. In FIGS. 3A and 3B, visual field areas 6B and 6B′ in the standard mode and the wide-screen television mode are shown by slanted lines. In this embodiment, as shown in FIG. 3A for example, a predetermined range 6A where the virtual three-dimensional space is captured from a second visual point position 5A at the first azimuthal angle (in this example, a circular range where a peripheral of a player character 1 is captured from above the player character 1), and a visual field area 6B where an area captured from the first visual point position of the main screen (for example, a backward position of the player character 1) or a third visual point position 5B at the second azimuthal angle is projected in a predetermined range 6A are displayed as a radar image 6. In this example, the circular range 6A in FIG. 3A where the periphery of the player character 1 is captured from the visual point position 5A above the player character 1 in a conical or cylindrical visual field, and the fan-shaped range 6B in FIG. 3A where a front portion in the position of the player character 1 as the visual point position 5B is captured in a conical visual field to be projected in the circular range 6A are displayed as the radar image 6. In the case of the wide-screen television mode, as shown in FIG. 3B, a field angle in a horizontal direction, for example, is increased to be 4/3 times larger than the visual field 6 in the standard mode, and is projected in the predetermined range 6A. An area 6B′ where the visual field area in the horizontal direction is increased according to the screen ratio of the display device (an area where the horizontal width of the visual field area is widened) is the visual field area. On the game screen, like a case of a rectangular display device having a circular display screen, the game screen is occasionally constituted so as to have a shape different from the screen shape of the display device. In this case, the visual field area has a conical shape in the case of the circular game screen, and a sectional shape of the visual field area has an enlarged circular or elliptic shape in the case of the wide-screen television mode. FIGS. 4A and 4B are pattern diagrams illustrating another display forms of the radar image. In this example, as shown in FIG. 4A, the visual field area has a pyramid shape (in this example, quadrangular pyramid), and an area captured at an azimuthal angle slanted with respect to the horizontal direction is projected in the predetermined range 6A so as to form the visual field area. The respective objects are displayed within the pyramid or on a pyramid-shaped bottom surface. In the case of the wide-screen television mode, the radar display controller 160 changes the shape of the visual field area 6B into 6B′ shown in FIG. 3B so that the quadrangular pyramid-shaped bottom surface to be the visual field area of the virtual camera matches with the screen ratio in the display device. More concretely, the visual field area changing unit 150 calculates visual field display 6y in the vertical direction (or visual field display 6x in the horizontal direction) based on a vertical field angle θy (or horizontal field angle θx) of the second virtual camera, for example, and calculates the visual field display 6x in the horizontal direction (or the visual field 6y in the vertical direction) based on the visual field display and the aspect ratio of the screen, so as to set the visual field display 6x and the visual field display 6y as the visual field display area. The radar image creating unit 140 creates the radar image from the visual field display area whose shape is changed. This case is applied to the case where the game screen is rectangular, and in the case where the game screen in the standard mode is circular, the shape of the visual field area is conical according to the circular shape of the game screen (the shape of the bottom surface is circular). In the case of the wide-screen television mode, the field angle in the horizontal direction is enlarged, so that the shape of the bottom surface is changed into an elliptic shape. The switching into the modes according to each screen ratio (in this example, the standard mode and the wide-screen television mode) can be automatically carried out by setting a selecting operation by the player or according to a signal or the like to be input from the display device. The visual field direction of the video picture on the main screen can be rotationally moved so that the player can look round in all directions in the virtual three-dimensional space with the first visual point position being the center independently from the advancing direction of the mobile object. The radar display controller 160 controls the rotational movement of the radar image in conjunction with the rotational movement on the main screen under the camera work of by means of the radar display camera work controller 140. That is to say, separately from the advancing direction of the mobile object (player's machine) to be operated by the player, the visual field direction can be rotationally moved (look around) with the player's machine being the center, for example. The visual field display portion in the radar display (or the display contents of the visual field display portion) are also rotationally moved to be displayed in conjunction with the video picture of the main screen. The visual field direction is rotationally moved according to the proceeding condition of the game, and the position and the direction of the mobile object as well as the operation by the player. FIGS. 5 to 8 illustrate concrete examples of the main screen of the game the radar image in the standard mode, and the relationship between the main screen of the game and the radar image is explained with reference to these drawings. FIG. 5 illustrates a screen example of a shooting game in the present invention, and a player character 1 which rides on a dragon can freely move in space by changing the advancing direction according to the operation by the player. Further, independently from the advancing direction, a firing range 6B where an opponent character is captured can be operated to any directions. This game proceeds in such a manner that an opponent character which flies in space or moves on the ground is captured in the firing range 6B and is destroyed. In this example, the quadrangular pyramid-shaped visual field area 6B (see FIG. 4) which covers from the visual point position, which is the position of the player character 1, to the rectangular surface is the firing range. In this case, as shown in an upper-right portion of FIG. 5, as the radar screen 6, for example, the periphery of the player character 1 and the opponent character included in its range are captured from the visual point position above the player character 1, and an image 6A in this range and the icons representing the dragon as the player's machine, the player character 1 and the opponent character (1a in FIG. 5 designates the icon of the opponent character) are displayed. The visual field area 6B (the firing range) where the area captured from the player character 1 (position of a weapon) is projected in the range, and the icon representing the opponent character included in the quadrangular pyramid-shaped area are displayed on the radar screen 6. As to the radar image 6 in this example, the player character 1 is displayed with its direction and position being fixed so that the advancing direction of the character 1 is always an up direction, whereas the visual field area 6B showing the firing range is rotationally moved about the player character 1 to be displayed. On the other hand, as shown in FIGS. 6 to 8, on the main screen, the visual point position is switched sequentially according to the change in the direction of the player character 1 in such a manner that the direction of the player character 1 is changed to the right side, the front side and the left side from the back side of the screen, and the visual field from the visual point position is displayed. In this example, in order to recognize the firing range (visual field area 6B) at one glance on the main screen, as shown in FIGS. 5 to 8, the player character 1 is photographed from the front side of the game screen, and the direction of the player character 1 is changed relatively with respect to the firing range direction so that the firing range 6B is displayed in a fixed manner on an approximately center portion on the back side of the game screen. As to the radar image 6, on the contrary to the main screen, the direction of the player character 1 is fixed, and the direction of the firing range (visual field area 6B) is changed relatively. FIGS. 9 to 12 illustrate concrete examples of the main screen of the game and the radar image in the wide-screen television mode correspondingly to FIGS. 5 to 8. In the case of the wide-screen television mode, as shown in the examples of FIGS. 9 to 12, the shape of the game screen is changed according to the screen ratio of the display unit (in this example, enlarged to the horizontal direction), and accordingly the shape of the visual field area 6B′ is changed. In this example, as to the firing range 6B′ to be displayed in the main screen of the game, the visual field (field angle) is enlarged according to the screen ratio of the display unit, but this portion may be fixed. FIG. 13 illustrates a screen example in the case where the shape of the main screen is changed into a shape different from that in the normal game according to the proceeding of the game. For example, in like a case where spot light display in a dark place is simulated, as shown in FIG. 13, a video picture which is captured in the conical visual field (in this example, a projection surface is elliptic) from the first visual point position in the virtual three-dimensional space is displayed. In this case, the visual field area 6B where the visual field area of the radar image is changed from its original shape (for example, quadrangular pyramid shape) into the conical shape is displayed as the radar image 6. For example, due to the processing of the game, in order to express that the visual field of the player is limited (in order to change the visual field area 6B according to passage of time and a moving position in the moving area in like a case where the player advances a dark place and a foggy place), the shape of the display screen is changed so that a range which is narrower than the normal range is occasionally displayed. This is achieved by controlling the image display so that an image on the portion out of the visual field is displayed with a color and a shape which are different from those of an image to be originally displayed when the normal display range is displayed on the display screen. For example, in FIG. 13, pixels of only black are displayed in a fixed manner on the outside of the circular visual field, so that the player cannot view the portion out of the visual field. For this reason, when the display image is created, the pixels on the portion corresponding to the outside of the visual field are replaced by black pixels, or after a normal display image is temporarily created to be displayed, a mask image which is constituted so that the display image transmits through only the visual field range (it has only black color, and an effect image or the like such as another color, rain or fog may be used according to requirements of representation in the game) is overlapped. In another method, a known image effect (blur, color change, etc.) which makes the visual field on the pixels out of the visual field impossible or difficult may be used. Further, in FIG. 13, the portion out of the visual field has only black color and thus visibility is disabled, but a semi-transparent mask image is superposed so that the visibility may be made to be difficult. Further, the visual field range is occasionally changed to be a closer range than the normal range due to representation of the game proceeding. For example, in order to express a foggy or dark situation, an effect is given to an object in a position separated from the visual point position by a not less than predetermined distance, its color is changed, or this object is not displayed, thereby disabling the visibility of the player on the normal display screen (in this case, an icon may be displayed on the radar screen). In this case, the image in the visual field range which is displayed on the radar screen is also deformed or reduced according to a display distance. For example in FIG. 3A, a radius of the fan shape in the visual field range 6B is reduced. In another manner, in FIG. 4A, the image is deformed so that a distance from the apex of the quadrangular pyramid on the visual field range 6B to the bottom surface becomes short. For example, when a maximum detection range of the normal radar includes a circumference portion shown by numeral 6 in FIG. 3, if the visual field range does not reach the circumferential portion according to the game proceeding, an arc of the visual field range image 6B is deformed so as to be separated to the inner side of the circumference of the circle 6 by a distance corresponding to the visual field range. FIGS. 14 and 15 illustrate screen examples in the case where the shape of the main screen is set without taking the screen ratio of the display unit into consideration. The shape of the main screen changes according to the game proceeding and the screen ratio of the display unit as mentioned above, but the shape can be set by another method. FIG. 14 illustrates the example where the main screen is displayed with ratio of 4:3 on a wide-screen television whose screen ratio is 16:9, and in this case, the main screen in FIG. 14 is displayed on the screen of the display device. In this example, the main screen of the game is displayed in a predetermined position (the screen center portion in FIG. 14), and right and left portions are black, namely, non-display portions. Areas 3 other than the main screen are, however, used as “a display portion not for the objects in the virtual space but for arbitrary game information” such as score or residual machines display portion or a radar display portion. FIG. 14 illustrates the example in the case where the main screen of the game is displayed with ratio of 16:9 on a television whose screen ratio is 4:3, and similarly areas 3 other than the main screen are used as non-display portions or display portions for game information. In these cases, the field angle in the visual field area of the radar image is adjusted according to these settings, and a portion of the visual field area 6B (6B′) is displayed on the radar screen. Like in FIGS. 13 and 14, the inside and the outside of the visual field range are distinguished as display and non-display portions (only black) on the display screen, a border between the inside and the outside of the visual field range is clarified, but actually the inside and the outside of the visual field are not always clearly distinguished, and its border is mostly vague. In order to express this situation, therefore, semi-transparent pixels of the mask image for the outside of the visual field range are displayed, for example, on the border portion between the inside and the outside of the visual field range, and thus the border does not have to be distinguished clearly. Further, the outside of the visual field range is not uniformly subject to the effect process such as coloring with simple color, but it is subject to the image process such that transparency of the portion close to the inside of the visual field range is heightened, and the transparency is lowered sequentially or gradually towards the outside of the visual field range. In another method, the outside of the visual field range is subject to the image process such that a stronger effect is given to the outside of the visual field range to an outward direction, so that the inside and the outside of the visual field range may be made to be vague. As a result, when the image whose visual field is limited is displayed, the more real image can be provided. In this case, also in the visual field display image on the radar image may be subject to such an image process that it does not have a clear shape like the visual field area 6B shown in FIG. 3 but its outline portion is blurred. In the concrete examples of the radar image shown in FIGS. 5 to 15, the shape of the visual field area 6B (6B′) is expressed by a fan shaped plane, but as shown in FIGS. 16A, 16B and 16C, it may be expressed by three-dimensional shapes such as a quadrangular pyramid shape, a conical shape and an elliptic conical shape. Further, the drawings illustrate the examples that the visual point position corresponding to the visual field area 6B and the visual point position corresponding to the predetermined range 6A are displayed in a fixed manner, but these positions can be changed arbitrarily in conjunction with the main screen of the game or independently from the main screen of the game. An operational example of the image processing device relating to the display process for the radar image according to the present invention is explained along the flowchart in FIG. 17. The shape of the visual field area of the radar image can be changed according to the screen ratio of the display unit independently from the change in the shape of the main screen as mentioned above or according to the shape of the main screen set independently from the screen ratio of the display unit. A case where the shape of the visual field area of the radar image is changed according to both the screen ratio of the display device and the shape of the game screen is explained as an example. The image processing device (in this example, the game machine) reads the camera work control data (current contents of the various parameters relating to the camera work of the virtual camera) from the work memory 181, and displays a virtual three-dimensional image (main screen) on the display unit 30 according to a current camera angle of the virtual camera for the game main screen. At this time, the shape of the main screen is changed to be displayed according to the shape of the display unit, or the game proceeding, or both of them (step S1). The player views the video picture of the main screen displayed on the display unit 4 and simultaneously moves the player character or changes the visual field direction of the player character by means of the input unit 20. Since the game controller 110 changes the position of the first virtual camera, the camera angle and the like according to the movement of the player character, it obtains the position and the direction of the character in the three-dimensional space after operation based on the operation information from the input unit 20 and the position/direction data of the current character, so as to update contents of the parameters relating to the camera work (step S2). A determination is made whether the radar image is displayed according to the game proceeding state and the player's display instruction (step S3). When the radar image is not displayed, the main screen data composed of the background, the player character and the like are read from the data memory 182 (step S4). The main screen display controller 130 executes the three-dimensional coordinate converting process at that camera angle (step S5), and outputs the virtual three-dimensional image of the main screen which is subject to the drawing process or the like to display it on the display unit 30. The sequence goes to step S1, and the above processes are repeated (step S6). On the other hand, when the determination is made at step S3 that the radar image is displayed, the field angle of the second virtual camera is adjusted according to the screen ratio of the display device, and the shape of the visual field area is changed in the visual field according to the shape of the game screen. The changing process for the shape of the visual field area according to the screen ratio is executed according to a mode which is set according to each screen ratio (in this example, the standard mode and the wide-screen television mode). In this embodiment, as mentioned above, the visual field display in the vertical direction (or horizontal direction) is calculated based on the vertical field angle (or horizontal field angle) of the second virtual camera, for example, and the visual field display in the horizontal direction (or vertical direction) is calculated based on the above visual field display and the aspect ratio of the screen. Any directions of the visual field display may be increased or decreased based on any field angles, but in the case of the wide-screen television mode, it is preferable that the image in the visual field whose horizontal width is wider than that in the standard mode is displayed as the radar image. Further, a volume of the visual field area or a ratio of the area of the display area may be converted according to the aspect ratio of the screen. In this flow, the visual field area is changed at this time for convenience, but the visual field area is automatically changed according to the switching of modes by setting by means of the player's selecting operation, or by a signal input from the display device. It is not necessary to change the visual field area very time, but the visual field area can be changed at the time when an operation signal or the like is input so that the mode can be switched even during the game (step S7). The predetermined range where the virtual three-dimensional space is captured from the second visual point position and the visual field area whose shape is changed (the visual field area where the area in which the virtual three-dimensional space is captured from the first or third visual point position at the changed field angle is projected to the predetermined range) are set as the radar image (step 8). For example, the reduced diagram of a three-dimensional map in the predetermined range is displayed, and the radar image such that the icons or the like, which represent the player character and the objects included in the predetermined range, are arranged in the visual field are is created (step S9). The main screen and the radar image are superposed or synthesized as separate windows to be output, or the radar image is output to another display device so as to be displayed on the display unit (step S10). The sequence goes to step S1, and the above processes are repeated. The above-mentioned embodiment explains the computer games which adopt a mobile object (moving image) which moves according to a player's operation or control by a computer (shooting games and simulation games in which a radar is displayed, racing games in which a course map whose moving area is limited is displayed, sports games in which a map of a sports stadium is displayed, role-playing games and adventure games such as Dungeon in which a moving map is displayed) as examples. The present invention, however, is not limited to them, and it can be applied to any games in which a radar image is displayed. Further, in a “navigation device” or the like which displays a moving condition or the like of an actual mobile object or the like using a detector for a three-dimensional coordinate position in actual space, the present invention can be applied also to devices which display that situation which is replaced by a virtual three-dimensional space. EFFECTS OF THE INVENTION According to the present invention, since the shape of the visual field area of the radar image is changed according to the shape of the game screen on which the visual field in the virtual three-dimensional space is projected, the range which is actually in the visual field can be matched with the visual field display of the radar. Further, the function for changing the shape of the main screen according to the screen ratio of the display unit to change the shape of the visual field area accordingly, or a function for changing the shape of the visual field area according to the screen ratio of the display unit independently from the change in the shape of the main screen are provided. For this reason, even if the main screen is output to the display device with different screen ratio, the position relationship between the object in the virtual three-dimensional space and another object, the reduced diagram of the map and the like can be displayed accurately. Further, since the position relationship of the object is shown on the three-dimensional map by using the visual field areas where the virtual three-dimensional space is captured from two different visual points, the position relationship on the periphery or the whole of the objects on the map can be expressed easily understandably in the three-dimensional space. INDUSTRIAL APPLICABILITY The present invention can be applied to the information processing device which displays an image representing an arrangement relationship of a specified object on a map composing a virtual three-dimensional space as a radar image. Particularly, the present invention can be applied effectively to computer games such as action games and role playing games in which a mobile object moves in a virtual three-dimensional space in response to an operation by a player. Further, in the case where a virtual space is captured as an actual space and three-dimensional position information in the actual space is input to be processed, the present invention can be applied to various devices which display an image for navigation as well as the devices which process the game image. <List of Reference Documents> Patent Document 1: Japanese Patent Application Laid-Open No. 6-91054 Non-Patent Document 1: “Mobile Suit Gundam F91 Formula War 0122 Official Guide Book”, Bandai Co., Ltd., Jul. 31, 1991, pp. 10- and 13 and 78-79
<SOH> BACKGROUND ART <EOH>In game machines which realize computer games such as so-called action type games and role playing games, a leading character (player character) in a game image displayed on a screen of a display device is controlled according to an operation signal from an input device (controller pad) operated by a player, so that the story of the game proceeds. Particularly in recent years, according to improvement of hardware performance, a game image such that a player character acts in the virtual three-dimensional space is provided in a form of three-dimensional graphics, thereby heightening the presentation effect of the game. In three-dimensional graphics, a spatial position relationship of an object in a visual line direction is obtained from a visual point position in the virtual three-dimensional space based on three-dimensional data expressing the object, an image process such as a rendering process is executed, so that the object is expressed three-dimensionally. That is to say, in games utilizing three-dimensional graphics, a player character and another object captured from the visual point position are expressed three-dimensionally, and the visual point position and the visual line are moved according to operations by the player or game scenes. Game images in which the virtual three-dimensional space is expressed in such a manner are provided. Game machines, which provide game images where the virtual three-dimensional space is expressed from a specified camera angle in games such as action type games using a lot of three-dimensional graphics, provide the following game images, for example. In the game images, a character which moves in response to an operation by the planer is tracked to be photographed by a virtual camera arranged in an upper-backward position of the character. In the case where the thing which is present besides far background such as mist is expressed, an effect image which draws the landscape is synthesized with the far background and the character image to be displayed, so that various things which come into the visual field of the virtual camera are expressed, thereby providing the sense of reality. In the case where an object which moves in the virtual three-dimensional space is to be displayed, like an image which is tracked to be photographed by the virtual camera is displayed on a display unit of the display device. Since a size of a display area is, however, limited, only a range of the viewing angle where the virtual camera is the visual point is displayed. For this reason, a screen, on which the arrangement relationship of a specified object such as its current position and a relative position relationship between the specified object and another mobile object in a course map where a moving range is limited is shown as a pattern in a reduced-size graphic (hereinafter, radar image), as well as a main screen is displayed in order to understand a condition of a range which is not displayed in a range captured by the virtual camera (for example, see Patent Document 1). Further, the game machines which display radar images include the following game machines (for example, see Non-Patent Document 1). In this game machine, like a game where a player's battleplane is operated to attack an opponent's battleplane, a circular radar frame obtained by patterning a radar, for example, as well as a visual field image captured from the self battleplane is displayed on a display unit, a “visual field display” representing a portion actually displayed on a main screen is displayed as a radar image in a radar detection space, and player's sight is set on the opponent's battleplane in the radar image so as to attack the opponent's battleplane. At this time, on the radar image which represents the radar detection space, a character to be operated by the player is arranged on the center or lower-end center, and a position of the object is displayed as a small window represented by a light spot or a symbol with the character looking down the ground vertically. A fan shaped (or (inverted) triangular) section whose center (apex) shows the character to be operated by the player is displayed within the small window, so that a visual field portion is expressed. In recent years, the display devices include two types of display devices whose screen ratio (aspect ratio) is 4:3, namely, have a normal screen (standard screen) and 16:9, namely, have a wide screen. In image processing devices such as game machines which display virtual objects, however, even if the aspect ratio is different from the above aspect ratios, a player feels less discomfort at the screen unlike television broadcasting which provides an actual live image. For this reason, images are generally processed without taking the screen ratio into consideration. When, however, images on the standard screen created by the image processing devices such as the game machines are directly displayed on the wide screen, defects such as non-image portions on right and left portions occur. When the images on the standard screen are displayed on a wide-screen television or monitor device which has a function for converting the aspect ratio in a lateral direction and a vertical direction of a sampling signal, the lateral direction is widened or the vertical direction is reduced. For this reason, the images are extended laterally or the images are reduced vertically, and thus distorted images are displayed. In such display devices having the function for switching between the standard images and the wide images, image data, which are reduced or enlarged by the opposite scaling to the scaling in the display devices, are created to be output to the display devices, so that the images can be displayed with the original ratio. When, however, such images are displayed on the display devices having a wide-size screen which does not have the switching function, a defect such as an image distorted to an opposite direction occurs. The image processing devices which display the virtual objects such as game machines do not generally cope with various screen ratios, and even if they cope with the various ratios, defects occur in the display devices which do not have the function for switching between the wide-size screen and the standard screen in the image processing system which reduce or enlarge images with the scaling opposite to the scaling in the display devices. Particularly in the radar images where a predetermined area in the three-dimensional virtual space is expressed by reduced figure or the like, images in which the wide-screen display devices are taken into consideration are not processed, and even when the ratio of the image on the main screen is switched, the size of the visual field display of the radar portion is not changed. Further, in the form where the ratio is switched in the display device, a range which is actually in the visual field is different from the visual field display of the radar, a shape of the radar frame on the radar display portion is distorted, and the arrangement relationship of the object in the three-dimensional space to be displayed on the radar is not accurate. Conventionally, the radar image is displayed as a fan-shaped or inverted triangular plane representing the detection space, and display contents are fixed ones which are looked down vertically. A range which is actually in the visual field does not match with the visual field display of the radar, and the radar images which are obtained by capturing the visual field area in an arbitrary direction from the visual point position in the virtual three-dimensional space in conjunction with the game images cannot be displayed on the wide-size screen without trouble. The present invention is devised from the viewpoint of the above situation, and its object is to provide a game image display control program which is capable of allowing a range which is actually in a visual field to match with a visual field display of a radar even when a radar image is displayed on a display device with varied screen ratio, a game machine, and a storage medium.
<SOH> BRIEF DESCRIPTION OF THE DRAWINGS <EOH>FIG. 1 is a block diagram illustrating one example of a constitution of an information processing device which realizes the present invention; FIG. 2 is a block diagram illustrating one example of a constitution of a main section of software which realizes an image processing function according to the present invention; FIGS. 3A and 3B are pattern diagrams for explaining a radar image display control system and a first display form according to the present invention; FIGS. 4A and 4B are pattern diagrams for explaining the radar image display control system and a second display form according to the present invention; FIG. 5 is a diagram illustrating a main screen of a game and a first example of the radar image in a standard mode; FIG. 6 is a diagram illustrating the main screen of the game and a second example of the radar image in the standard mode; FIG. 7 is a diagram illustrating the main screen of the game and a third example of the radar image in the standard mode; FIG. 8 is a diagram illustrating the main screen of the game and a fourth example of the radar image in the standard mode; FIG. 9 is a diagram illustrating a main screen of the game and a first example of the radar image in a wide-screen television mode; FIG. 10 is a diagram illustrating the main screen of the game and a second example of the radar image in the wide-screen television mode; FIG. 11 is a diagram illustrating the main screen of the game and a third example of the radar image in the wide-screen television mode; FIG. 12 is a diagram illustrating the main screen of the game and a fourth example of the radar image in the wide-screen television mode; FIG. 13 is a diagram illustrating the main screen of the game and a first example of the radar image in another display form; FIG. 14 is a diagram illustrating the main screen of the game and a second example of the radar image in another display mode; FIG. 15 is a diagram illustrating the main screen of the game and a third example of the radar image in another display mode; FIGS. 16A to 16 C are pattern diagrams illustrating concrete examples in the case where a shape of a visual field area of the radar image is displayed three-dimensionally; and FIG. 17 is a flowchart for explaining an operation example of the image processing device relating to a radar image display process according to the present invention. detailed-description description="Detailed Description" end="lead"?
20050518
20091110
20060223
76747.0
A63F1300
0
SAGER, MARK ALAN
GAME IMAGE DISPLAY CONTROL PROGRAM, GAME DEVICE, AND RECORDING MEDIUM
UNDISCOUNTED
0
ACCEPTED
A63F
2,005
10,535,564
ACCEPTED
Urine collector for female use
The invention relates to an improved urine collector for female use. The inventive collector comprises a body which is triangular in plan and which is made from an elastomer material. According to the invention, the body is equipped with: a first recess (3) which is disposed at the end of the peripheral flange (2) thereof, said recess (3) being defined by two lateral tongue elements; and a second recess (4). Moreover, a tubular projection (7) is provided in the lateral zone of said second recess. The aforementioned recess (4) also comprises a zone (8) which adopts the form of a bellows or fold.
1. an improved urine collector for female use, of the type made up of a body made from an elastomer material and adopting a shape that is triangular in plan and two of its three vertexes being rounded, the general body having a recess (4) or concave area, externally having a conduit (7) coupling to a flexible conduit, and having a valve (5) provided with a projection (6) emerging from zone (4), characterized in that there is a recess (3) at the end of the peripheral flange (2) defined by two lateral tongue elements, and in recess (4) and in coincidence with the side through which the tubular projection (7) emerges, the recess (4) has a zone (8) configured as a bellows or fold.
OBJECT OF THE INVENTION The present specification refers to a Utility Model application corresponding to an improved urine collector for female use, having the purpose of being configured as a body obtained from elastomer materials having a configuration suitable for being adapted to the outer perimetral zone of the urinary organ of a female user, having a tongue element provided with two projections between which there is a recessed zone allowing its adhesion on the perineum of the user, leaving the anus completely free, the tongue element being die-cut for the purpose of being effectively adapted on the irregularities of the skin and being able to be bent on the folds or on deformations which the surface of the skin may have, having on the end of the cavity adjacent to the collector element a series of folds defining the existence of a flexible zone, achieving that when the urine collector is connected to a cannula and a potential stretching occurs, the bellows is also stretched and the urine collector undergoes no pulling that may provoke the separation thereof from the body of the user. FIELD OF THE INVENTION This invention is applicable within the industry dedicated to the manufacture of urine collector elements, equipment and devices for temporarily or permanently bedridden patients. BACKGROUND OF THE INVENTION The applicant is aware of the current existence of a Utility Model filed in Spain with number 200200220 relating to a urine collector for female use. In accordance with the configuration thereof and without detracting from any of the substantial features of the invention, it has been verified that this collector protected in said Utility Model, in accordance with the shape of the tongue element, partially covers the anus in its application, and when a cannula is incorporated on the urine collector conduit, it may in turn cause the accidental pulling of the body of the collector, separating it from the fixing surface. DESCRIPTION OF THE INVENTION The improved urine collector for female use proposed by the invention has a general configuration that is notably suitable for preventing both the covering of the anus of the user and the pulling thereof should a cannula be fixed on the collector. More specifically, the improved urine collector for female use object of the invention is formed from a body made from an elastomer material adopting a plan shape similar to a triangle, a central recess being arranged on the narrower end for the purpose of passing over the anus or freeing it from being covered, remaining adhered to the perineum of the user. Said tongue element is die-cut so that this zone suitably adapts to the irregularities of the skin and at the same time can be bent on the folds or deformations that the skin may have. The invention is provided with a tubular projection of increasing width configured as the outlet or zone for the passing of the urine towards the direct collector thereof, to which end incorporated in the invention in the upper zone of the tubular projection is an area shaped like a non-rigid bellows or folds, achieving that when a cannula is connected on the collector, and specifically on the tubular zone, possible pulling is avoided, and if so required the bellows stretches, and accordingly the general collector cannot come loose from the zone for the fixing thereof on the body of the user. DESCRIPTION OF THE DRAWINGS To complement the description being made and for the purpose of helping to better understand the features of the invention, a set of drawings is attached to the present specification as an integral part thereof, wherein the following is shown with an illustrative and non-limiting character: FIG. 1 shows a plan view of the object of the invention corresponding to an improved urine collector for female use, the existence of the recess passing over the anus and allowing its fixing on the female perineum being seen in this graphic representation. FIG. 2 shows a side elevational view of the object shown in FIG. 1, wherein the existence of the bellows completely or partially preventing the collector from coming loose from the body of the user should a cannula be incorporated, which may cause pulling, can be seen. PREFERRED EMBODIMENT OF THE INVENTION In view of these figures, it can be observed how the improved urine collector (1) for female use is formed by a body (2) made from an elastomer material, having a perimetral configuration similar to a triangle and incorporating a recess (3) defined by two lateral tongue elements in coincidence with the narrower end, incorporating a hollow area (4) provided with a projection (5) and a valve (6) in the central zone, whereas on the opposite side it incorporates a tubular conduit (7) projecting from zone (4), and specifically from the hollow zone (2), the hollow zone (2) having a bellows-like configuration (8) in correspondence with the zone from which the projection (7) originates.
<SOH> BACKGROUND OF THE INVENTION <EOH>The applicant is aware of the current existence of a Utility Model filed in Spain with number 200200220 relating to a urine collector for female use. In accordance with the configuration thereof and without detracting from any of the substantial features of the invention, it has been verified that this collector protected in said Utility Model, in accordance with the shape of the tongue element, partially covers the anus in its application, and when a cannula is incorporated on the urine collector conduit, it may in turn cause the accidental pulling of the body of the collector, separating it from the fixing surface.
20050519
20070508
20060112
58800.0
A47K1100
0
KINDRED, KRISTIE MAHONE
URINE COLLECTOR FOR FEMALE USE
SMALL
0
ACCEPTED
A47K
2,005
10,535,780
ACCEPTED
Method of controlling cellular processes in plants
A method of controlling a genetically-modified plant, comprising (a) providing a genetically-modified plant, whereby cells of said genetically-modified plant contain a heterologous nucleic acid and whereby said genetically-modified plant is inactive with regard to a cellular process of interest, (b) switching on said cellular process of interest by directly introducing a polypeptide from a cell-free composition into cells containing said heterologous nucleic acid wherein said polypeptide and said heterologous nucleic acid are mutually adapted such that said polypeptide is capable of switching on said cellular process of interest.
1. A method of controlling a genetically-modified plant, comprising (a) providing a genetically-modified plant, whereby cells of said genetically-modified plant contain a heterologous nucleic acid and whereby said genetically-modified plant is inactive with regard to a cellular process of interest, and (b) switching on said cellular process of interest by directly introducing a polypeptide from a cell-free composition into cells containing said heterologous nucleic acid, wherein said polypeptide and said heterologous nucleic acid are mutually adapted such that said polypeptide is capable of switching on said cellular process of interest. 2. The method of claim 1, wherein said directly introducing of step (b) is done by particle bombardment, application of said polypeptide on at least a part of said plant, or by injecting a solution containing said polypeptide in tissue of said plant. 3. The method of claim 1, wherein said polypeptide comprises a membrane translocation sequence enabling the direct introduction of said polypeptide into cells containing said heterologous nucleic acid. 4. The method of claim 3, wherein said membrane translocation sequence is covalently bound to said polypeptide. 5. The method of claim 3, wherein said membrane translocation sequence is non-covalently bound to said polypeptide. 6. The method claim 1, wherein said switching on of said cellular process of interest comprises formation of a DNA, an RNA or a protein from said heterologous nucleic acid or involving said heterologous nucleic acid. 7. The method of claim 6, wherein cells of said genetically-modified plant contain an additional heterologous nucleic acid that is controlled by said DNA, said RNA, or said protein. 8. The method of claim 6, wherein said DNA, said RNA, or said protein is capable of spreading to other cells of said plant. 9. The method of claim 1, wherein said cellular process of interest comprises the formation of an expressible operon from said heterologous nucleic acid or from an RNA expression product thereof. 10. The method of claim 1, wherein said cellular process of interest comprises the formation of an expressible amplicon from said heterologous nucleic acid or from an RNA expression product thereof. 11. The method of claim 10, wherein said expressible amplicon is capable of expressing a gene of interest. 12. The method of claim 10, wherein said expressible amplicon is capable of cell-to-cell or systemic movement in said plant. 13. The method of claim 8, wherein said protein contains a protein portion endowing said protein with the capability of leaving a cell and entering other cells of said plant. 14. The method of claim 13, wherein said protein portion is selected from the following group: a viral movement protein, viral coat protein, plant or animal transcription factor, plant or animal peptide intercellular messenger, artificial peptide capable of endowing said protein with said capability. 15. The method of claim 13, wherein said protein is capable of controlling expression of said protein in cells containing said heterologous nucleic acid. 16. The method of claim 15, wherein said protein controls said additional heterologous nucleic acid. 17. The method of claim 16, wherein said cellular process of interest comprises formation of an RNA or protein expression product, an operon, or an amplicon from said additional heterologous nucleic acid. 18. The method of claim 6, wherein said protein and said polypeptide jointly generate a predetermined function switching on said cellular process of interest only when said protein and said polypeptide are jointly present. 19. The method of claim 18, wherein said protein and said polypeptide jointly generate said predetermined function by intein-mediated trans-splicing or by intein-mediated affinity interaction. 20. The method of claim 18, wherein said protein and said polypeptide jointly generate said predetermined function by affinity interation mediated by leucine zipper fragments fused to said polypeptide and to said protein. 21. The method of claim 18, wherein said protein and said polypeptide jointly generate said predetermined function by affinity interation mediated by dimerizer fragments fused to said polypeptide and to said protein. 22. The method of claim 21, wherein said affinity interatction is regulated by a dimerizer agent such as rapamycin or a rapamycin analog. 23. The method of claim 1, wherein said polypeptide is capable of switching on said cellular process of interest by (i) an enzymatic activity or by (ii) a binding affinity to said heterologous nucleic acid or to an expression product of said heterologous nucleic acid. 24. The method of claim 23, wherein said polypeptide has an enzymatic activity of an enzyme selected from the group consisting of a site-specific recombinase, a flippase, resolvase, an integrase, a transposase, a replicase, and a polymerase. 25. The method of claim 1, wherein said polypeptide is introduced in step (b) without introducing a nucleic acid coding for said polypeptide or for a part of said polypeptide capable of switching on said cellular process. 26. The method of claim 1, wherein said plant is a transgenic plant containing said heterologous nucleic acid stably integrated in the nuclear genome. 27. The method of claim 1, wherein said plant is a transgenic plant containing said heterologous nucleic acid stably integrated in the plastid genome. 28. The method of claim 1, wherein said plant is a higher crop plant. 29. A genetically-modified plant containing a heterologous nucleic acid in cells thereof, wherein said plant is inactive with regard to a cellular process of interest, wherein said heterologous nucleic acid is adapted such that said cellular process of interest can be switched on by directly introducing a polypeptide into cells containing said heterologous nucleic acid, wherein said polypeptide and said heterologous nucleic acid are mutually adapted such that said polypeptide is capable of switching on said cellular process of interest. 30. The genetically-modified plant of claim 29, wherein said polypeptide is from a cell-free composition. 31. A system of controlling a cellular process of interest in a genetically-modified plant, comprising a plant as defined in claim 29 and a polypeptide for switching on said cellular process of interest, whereby said plant and said polypeptide are mutually adapted such that said polypeptide is capable of switching on said cellular process of interest. 32. A plant obtained or obtainable by the method of claim 1. 33. A cell-free composition from the cells containing said polypeptide according to claim 1.
FIELD OF THE INVENTION The present invention relates to a method of controlling a cellular process of interest in a plant by an external signal like an externally applied polypeptide. The invention further relates to a transiently or stably genetically-modified plant adapted for said method and to a genetically-modified plant which has been controlled according to the method of the invention. Moreover, the present invention relates to a method of producing a product in a genetically-modified plant by controlling a cellular process of interest using an encrypted external signal. The process of the invention allows for the selective control of transgene expression in a transiently or stably genetically modified plant, whereby a cellular process of interest previously non-operable in the plant may be selectively switched on at any predetermined time. BACKGROUND OF THE INVENTION Controllable Transagene Expression Systems in Plants One of the major problems in plant biotechnology is the achievement of reliable control over transgene expression. Tight control over gene expression in plants is essential if a downstream product of transgene expression is growth inhibitory or toxic, like for example, biodegradable plastics (Nawrath, Poirier & Somerville, 1994, Proc. Natl. Acad. Sci., 91, 12760-12764; John & Keller, 1996, Proc. Natl. Acad. Sci., 93, 12768-12773; U.S. Pat. Nos. 6,103,956; 5,650,555) or protein toxins (U.S. Pat. No. 6,140,075). Existing technologies for controlling gene expression in plants, are usually based on tissue-specific and inducible promoters and practically all of them suffer from a basal expression activity even when uninduced, i.e. they are “leaky”. Tissue-specific promoters (U.S. Pat. No. 05,955,361; WO09828431) represent a powerful tool but their use is restricted to very specific areas of applications, e.g. for producing sterile plants (WO9839462) or expressing genes of interest in seeds (WO00068388; U.S. Pat. No. 05,608,152). Inducible promoters can be divided into two categories according to their induction conditions: those induced by abiotic factors (temperature, light, chemical substances) and those that can be induced by biotic factors, for example, pathogen or pest attack. Examples of the first category are heat-inducible (U.S. Pat. No. 05,187,287) and cold-inducible (U.S. Pat. No. 05,847,102) promoters, a copper-inducible system (Mett et al., 1993, Proc. Natl. Acad. Sci., 90, 4567-4571), steroid-inducible systems (Aoyama & Chua, 1997, Plant J., 11, 605-612; McNellis et al., 1998, Plant J., 14, 247-257; U.S. Pat. No. 06,063,985), an ethanol-inducible system (Caddick et al., 1997, Nature Biotech., 16, 177-180; WO09321334), and a tetracycline-inducible system (Weinmann et al., 1994, Plant J., 5, 559-569). One of the latest developments in the area of chemically inducible systems for plants is a chimaeric promoter that can be switched on by glucocorticoid dexamethasone and switched off by tetracycline (Bohner et al., 1999, Plant J., 19, 87-95). For a review on chemically inducible systems see: Zuo & Chua, (2000, Current Opin. Biotechnol., 11, 146-151). Other examples of inducible promoters are promoters which control the expression of patogenesis-related (PR) genes in plants. These promoters can be induced by treatment of a plant with salicylic acid, an important component of plant signaling pathways in response to pathogen attack, or other chemical compounds (benzo-1,2,3-thiadiazole or isonicotinic acid) which are capable of triggering PR gene expression (U.S. Pat. No. 05,942,662). There are reports of controllable transgene expression systems using viral RNA/RNA polymerase provided by viral infection (for example, see U.S. Pat. Nos. 6,093,554; 5,919,705). In these systems, a recombinant plant DNA sequence includes the nucleotide sequences from the viral genome recognized by viral RNA/RNA polymerase. The effectiveness of these systems is limited because of the low ability of viral polymerases to provide functions in trans, and their inability to control processes other than RNA amplification. Another way is to trigger a process of interest in a transgenic plant by using a genetically-modified virus which provides a heterologous nucleic acid encoding a switch for a biochemical process in a genetically-modified plant (WO02068664). The systems described above are of significant interest as opportunities of obtaining desired patterns of transgene expression, but they do not allow tight control over the expression patterns, as the inducing agents (copper) or their analogs (brassinosteroids in case of steroid-controllable system) can be present in plant tissues at levels sufficient to cause residual expression. Additionally, the use of antibiotics and steroids as chemical inducers is not desirable or economically unfeasible for large-scale applications. When using promoters of PR genes or viral RNA/RNA polymerases as control means for transgenes, the requirements of tight control over transgene expression are also not fulfilled, as casual pathogen infection or stress can cause expression. Tissue- or organ-specific promoters are restricted to very narrow areas of application, since they confine expression to a specific organ or stage of plant development, but do not allow the transgene to be switched on at will. Recombinant viral switches as described in WO02/068664 address all these problems, but do not guarantee tight environmental safety requirements, as the heterologous nucleic acid in the viral vector can recombine. There is an abundant literature including patent applications which describe the design of virus resistant plants by the expression of viral genes or mutated forms of viral RNA (e.g. U.S. Pat. Nos. 5,792,926; 6,040,496). However, there is an environmental risk associated with the use of such plants due to the possibility of forming novel viruses by recombination between the challenging virus and transgenic viral RNA or DNA (Adair & Kearney, 2000, Arch. Virol, 145, 1867-1883). Hooykaas and colleagues (2000, Science, 290, 979-982; WO01/89283) described the use of a translational fusion of Cre recombinase with vir gene fragments for Agrobacterium-mediated recombinase translocation into plant cells. Cre-mediated in planta recombination events resulted in a selectable phenotype. The translocation of Cre recombinase is the first use of a translocated protein as a switch to trigger a process of interest in plant cells. However, despite the translocation is not necessarily accompanied by DNA transfer, this approach does not guarantee high level safety, as the phytopathogenic genetically-modified microorganism (Agrobacterium) posesses a complete coding sequence of the switching protein Cre recombinase. Further, the process of interest can only be triggered in cells that receive the switching protein. If large ensembles of cell are to be treated, the ratio of cells receiving switching protein to the total number of cells becomes very small. The method of Hooykaas can therefore not be applied to entire plants. Instead, its usefulness is limited to cells in tissue culture or cell culture. It is therefore object of this invention to provide a method of switching on a cellular process of interest in entire plants. It is another object of the invention to provide an environmentally safe method of switching on a cellular process of interest in plants, whereby the cellular process may be selectively switched on at any predetermined time. It is another object of this invention to provide a method for producing a product in a transgenic plant, wherein the production of the product may be selectively switched on after the plant has grown to a desired stage, whereby the process is environmentally safe in that genetic material necessary for said cellular process and genetic material coding for the control function are not spread in the environment together. GENERAL DESCRIPTION OF THE INVENTION The above objects are achieved by a method of controlling a genetically-modified plant, comprising (a) providing a genetically-modified plant, whereby cells of said genetically-modified plant contain a heterologous nucleic acid and whereby said genetically-modified plant is inactive with regard to a cellular process of interest, (b) switching on said cellular process of interest by directly introducing a polypeptide from a cell-free composition into cells containing said heterologous nucleic acid, wherein said polypeptide and said heterologous nucleic acid are mutually adapted such that said polypeptide is capable of switching on said cellular process of interest. The invention also provides genetically-modified plants or parts thereof obtained or obtainable by the method of the invention. Preferred parts of said plants are leaves and seeds. Seeds are most preferred examples for parts of a plant. The invention also provides a genetically-modified plant containing a heterologous nucleic acid in cells thereof, wherein said plant is inactive with regard to a cellular process of interest, wherein said heterologous nucleic acid is adapted such that said cellular process of interest can be switched on by directly introducing a polypeptide into cells containing said heterologous nucleic acid, wherein said polypeptide and said heterologous nucleic acid are mutually adapted such that said polypeptide is capable of switching on said cellular process of interest. Further, the invention provides a system for controlling a cellular process of interest in a genetically-modified plant, comprising a plant as defined above and a polypeptide for switching on said cellular process of interest in the genetically-modified plant, whereby said plant and said polypeptide are mutually adapted such that said polypeptide is capable of switching on said cellular process of interest. The present invention allows to switch on a cellular process of interest in a plant by directly introducing a polypeptide into cells that contain said heterologous nucleic acid. Directly introducing said polypeptide means that said introducing does not comprise applying nucleic acids to said plant that code for said polypeptide or for a functional part of said polypeptide. A part of said polypeptide is functional if it is capable of switching on the cellular process of the invention. By said direct application of said polypeptide to said plant, a very high level of biological safety is achieved by the invention, since the plant does not come into contact with genetic material that could switch on said cellular process of interest. Instead, at least one necessary component for said cellular process is provided to the plant as a polypeptide without genetic material coding for said polypeptide. A major advantage of the invention is that genetic material necessary for the cellular process of interest and genetic material coding for said polypeptide cannot both be transferred to progeny of said plant or otherwise spread together in the environment. The method of Hooykaas (2000, Science, 290, 979-982; WO01/89283) allows switching on a cellular process of interest in plant cells, whereby a switching protein is introduced using pathogenic bacteria. As this method is limited to cell culture (laboratory scale), biological safety concerns due to the use of Agrobacteria that code for the switching protein do not arise. The present invention provides for the first time a method of controlling a cellular process of interest that is efficient in whole plants and that is at the same time environmentally safe even when used on a large scale like in a green-house or on a farm field. In step (a) of the method of the invention, a genetically-modified plant is provided. Higher plants, notably higher crop plants, are preferred. Said plant is genetically-modified in that cells of said plant contain a heterologous nucleic acid that is involved in switching on said cellular process of interest. In many cases, said heterologous nucleic acid may code for a protein to be expressed. Said plant provided in step (a) may be a transgenic plant, whereby most or all of the cells of said plant contain said heterologous nucleic acid stably integrated in the genome of said cells. Said heterologous nucleic acid may be stably integrated into the nuclear genome or in the genome of organelles like mitochondria or, preferably, plastids. Integration of said heterologous nucleic acid in the plastid genome is advantageous in terms of biological safety. The method of the invention is preferably carried out with transgenic plants. Alternatively, however, said plant may be transiently modified and/or said heterologous nucleic acid may be present in a fraction of cells but not in other cells. A heterologous nucleic acid in a transiently modified plant may be stably integrated in the genome of said fraction of cells or it may be present episomally. Incorporation of said heterologous nucleic acid in a fraction of cells of said plant may be achieved by transiently transfecting said organism e.g. using viral transfection or Agrobacterium-mediated transformation. In any case, the genetically-modified plant provided in step (a) is inactive with regard to the cellular process of interest before step (b) has been carried out. In step (b) of the method of the invention, said polypeptide is introduced from a cell-free composition into at least some of said cells containing said heterologous nucleic acid. If said plant is transgenic, said polypeptide may in principal be applied to any part or to any cells of the plant. If only a fraction of the cells of said plant contains said heterologous nucleic acid, said polypeptide is applied to the plant such that said polypeptide can reach cells containing said heterologous nucleic acid for switching on the cellular process of interest. As noted above, said polypeptide is directly introduced into cells of said plant from a cell-free composition. A cell-free composition does not contain viable cells that could replicate nucleic acids coding for said polypeptide. Preferably, said cell-free composition contains no viable cells. A cell-free composition may be a cell extract obtained by lysing cells (e.g. cells like bacterial cells used for expressing said polypeptide), provided there are no viable cells in said composition that could replicate nucleic acids coding for said polypeptide. Other examples of cell-free compositions are solutions, preferably buffered aqueous solutions, of said polypeptide or said polypeptide in solid or dry form, provided there are no viable cells as defined above. Directly introducing may be done by (i) particle (microprojectile) bombardment, (ii) application of said polypeptide on at least a part of said plant, or (iii) by injecting a solution containing said polypeptide in tissue of said plant. In methods (ii) and (iii), said polypeptide is typically contained in a liquid, preferably aqueous, cell-free composition (or solution) that is applied to parts of the plant. Such a composition may be applied e.g. by spraying said plant with said composition containing the polypeptide. Further, said composition may be injected according to (iii). For methods (ii) and (iii), said polypeptide preferably comprises a membrane translocation sequence (MTS) that enables entering of said polypeptide into cells of said plant. Said membrane translocation sequence may be covalently or non-covalently bound to said polypeptide. Preferably, it is covalently bound to said polypeptide. Said membrane translocation sequence may be a peptide that endows said polypeptide with the capability of crossing the plasma membrane of cells of said organism. Many such membrane translocation sequences are known in the art. Frequently, they comprise several basic amino acids, notably arginines. The size of membrane translocation sequences may vary largely, however, they may typically have 3 to 100 amino acids, preferably 5 to 60 amino acids. Said polypeptide may be produced by standard protein expression techniques e.g. in E. coli. Purification of said polypeptide after its expression is preferably done, notably removal or destruction of nucleic acids coding for said polypeptide. Nucleic acids may be removed or destroyed by hydrolysis, preferably catalysed by an enzyme like a (DNase) or a ribonuclease (RNase). Further or additionally, chromatographic techniques may be used for removing nucleic acids from said polypeptide. Said polypeptide may be applied to a plant e.g. by spraying said plant with a liquid composition, preferably an aqueous solution, containing said polypeptide. Preferably, measures are taken to facilitate entering of said polypeptide into cells of a plant, notably measures that allow crossing of the plant cell wall and/or the outer plant layer. An example of such measures is slight wounding of parts of the plant surface e.g. by mechanical scratching. Another example is the use of cellulose-degrading enzymes to weaken or perforate the plant cell wall. Switching on of the cellular process of interest (step (b)) requires directly introducing said polypeptide from a cell-free composition into cells that contain said heterologous nucleic acid. Said polypeptide and said heterologous nucleic acid are mutually adapted such that said polypeptide is capable of switching on said cellular process of interest. With respect to said cellular process of interest, there are no particular limitations and the invention is of very broad applicability. Said cellular process of interest may be or may comprise formation of a DNA, an RNA or a protein from said heterologous nucleic acid or involving said heterologous nucleic acid. There are numerous possibilities for achieving formation of said DNA, said RNA or said protein. Said polypeptide may for example comprise a segment having a binding activity to said heterologous nucleic acid, e.g. to a promoter. Said segment may then e.g. act as a transcription factor inducing transcription of said hetereologous nucleic acid, thus triggering formation of said RNA and or said protein. Preferably, said polypeptide has a segment having an enzymatic activity capable of triggering formation of said DNA, said RNA or said protein. Examples of such activities are DNA or RNA-modifying activities like the activity of a site-specific recombinase, flippase, resolvase, integrase, polymerase, or a transposase. Said enzymatic activity may modify said heterologous nucleic acid leading to expression of said protein e.g. by recombination. In an embodiment wherein said polypeptide has polymerase activity, said segment may be a DNA-dependent RNA polymerase that acts on a promoter of said heterologous nucleic acid. Said promoter is preferably not recognized by native polymerases of said plant. Examples of such promoter-polymerase systems are bacterial, viral, or bacteriophage promoter-polymerase systems like the T7 promoter-T7 polymerase. Moreover, said switching on of said cellular process of interest may comprise formation of a DNA, an RNA or a protein from said heterologous nucleic acid or involving said heterologous nucleic acid. As an example, the formation of an expressible operon from said heterologous nucleic acid or from an RNA expression product of said heterologous nucleic acid may be mentioned. A sequence portion of said heterologous nucleic acid (or of said additional nucleic acid described below) may be operably linkable to a transcription promoter by the action of said protein, which allows to switch on expression of a protein of interest or transcription of an RNA-viral amplicon from said additional heterologous nucleic acid, e.g. by operably linking a sequence encoding said protein of interest or an RNA amplicon with a promoter. There are several ways of reducing this embodiment to practice. One option is to separate, in said (additional) heterologous nucleic acid, the sequence encoding an RNA amplicon and a promoter by a sequence block that precludes an operable linkage therebetween. Said sequence block may be flanked by recombination sites such that said block can be cut out by a recombinase recognizing said recombination sites. Thereby, operable linkage for transcription of the sequence encoding an RNA amplicon can be established and expression may be switched on. Another option is to have a portion of a sequence necessary for transcription (e.g. a promoter or promoter portion) in flipped orientation and flanked by recombination sites. Providing a suitable recombinase (e.g. with said polypeptide) may flip said sequence portion back in correct orientation, whereby an operable linkage can be established. Further, said DNA, said RNA or said protein may be capable of spreading to other cells of said plant (e.g. a DNA or RNA viral vector). An important example of such a cellular process is the formation of an expressible amplicon from said heterologous nucleic acid or from an RNA expression product of said heterologous nucleic. Said amplicon is capable of amplifying within cells of its activation or formation (amplifying vector). Said amplicon may be an expressible amplicon that contains a gene of interest to be expressed in said cellular process of interest. Further, said amplicon may be capable of cell-to-cell or systemic movement in the plant of the invention. An amplicon may be based on a plant DNA or RNA virus. Plant RNA viruses like tobamoviruses are preferred. The amplification properties of said protein capable of spreading (see below) and said amplicon may behave synergistically, thus allowing an extremely strong cellular process of interest that spreads over significant parts of said plant (e.g. leading to extremely strong expression of a protein of interest from said amplicon). Engineering of amplicons based on Tobamoviruses is known in the art (see e.g. Dawson et al., 1989, Virology, 172, 285-293; Yusibov et al., 1999, Curr. Top. Microbiol. Immunol., 240, 81-94; for review, see “Genetic Engineering With Plant Viruses”, 1992, eds. Wilson and Davies, CRC Press, Inc.). In a major embodiment of the invention, said switching on of said cellular process of interest involves formation of a protein from said heterologous nucleic acid, whereby said protein is capable of spreading within the plant, i.e. capable of leaving a cell of its formation and entering other cells of said plant (such a protein is also referred to as “protein switch” herein). In other cells, said protein may switch on a cellular process of interest, notably by controlling an additional heterologous nucleic acid (see below). Said leaving a cell and entering other cells preferably comprises cell-to-cell-movement or systemic movement in said plant or in a part thereof. Said protein (also referred to herein as “protein switch”) preferably contains a protein portion enabling said leaving a cell and entering other cells of said protein switch. Said protein portion may be a domain of a viral movement protein or of a viral coat protein. Further, said protein portion may be a plant or an animal transcription factor, or a domain of a plant or animal transcription factor capable of cell-to-cell or systemic movement Further, said protein portion may be a plant or animal peptide intercellular messenger, or a domain of a plant or an animal peptide intercellular messenger. Moreover, said protein portion may be an artificial peptide capable of enabling cell-to-cell or systemic movement. Preferably, however, said protein portion is or comprises a viral movement protein or viral coat protein, or a domain of a viral movement or coat protein. When said protein capable of spreading enters other cells that contain said heterologous nucleic acid, it is preferably capable of switching on (inducing) expression of said protein from said heterologous nucleic acid. By making use of this protein (protein switch), the method of the invention allows to amplify and propagate the switching signal provided externally with said polypeptide in said plant. Particularly, if the number of cells initially reached by said polypeptide is small, the switching signal is efficiently carried to further cells in said plant. There are many ways how said protein can be made to control its own expression from said heterologous nucleic acid. These ways correspond to those that may be employed for said polypeptide of step (b) given above. Apart from the capability of controlling its own expression, the protein has preferably the capability of switching on a cellular process of interest. Although switching on of a cellular process is preferred, it is clear to those skilled in the art that the end result of a cellular process that was switched on may also be a suppression or a switching off of a process in cells of the plant. For being capable of switching on said cellular process of interest, said protein may have a segment that is capable of controlling said cellular process. Said segment may have a binding activity or an enzymatic activity that controls a nucleic acid (notably said additional heterologous nucleic acid) necessary for said cellular process of interest. In the method of the invention, said switching on of said cellular process may be achieved analogously to the control of its own expression from said heterologous nucleic acid. For this purpose, said protein may have a segment for controlling said cellular process and a segment for causing said expression of said protein, whereby the control mechanisms of said two segments may be different. Preferably, the two control mechanisms are similar or identical, wherein one segment of said protein may be sufficient for switching on said cellular process and for controlling the expression of said protein. Thus, for simplicity, said protein contains most preferably said one segment and a portion endowing said protein with the capability of leaving a cell and entering other cells of said plant. In the invention, said polypeptide of the invention can have the same switching function as said protein switch, e.g. have the same enzymatic activities as said protein switch. Said polypeptide is applied externally and can switch on a cellular process of interest in cells it enters. Said protein switch is produced inside cells of said genetically-modified plant, preferably in response to the switching function of said polypeptide. Said protein switch can in turn, after its production in cells of said plant, switch on a cellular process of interest in cells where it is produced and/or in other cells of said plant. If said polypeptide and said protein switch exert their switching function by the same of a related enzymatic activity, they may differ in that said polypeptide preferably has a membrane translocation sequence, whereas said protein switch preferably has a protein portion endowing said protein switch with the capability of leaving a cell and entering other cells. Said cellular process of interest may require, as mentioned above, the presence of an additional heterologous nucleic acid in cells of said plant where said cellular process is to be controlled. Said additional heterologous nucleic acid may be present in all cells or in a fraction of cells of said plant. It may be stably incorporated in nuclear or organellar genomes of cells of said organism. What has been said regarding said heterologous nucleic acid of the invention generally applies also to said additional heterologous nucleic acid. Preferably, said plant is transgenic regarding said additional heterologous nucleic acid and regarding said heterologous nucleic acid. Said additional heterologous nucleic acid will e.g. be made use of, if said heterologous nucleic acid is used for forming a protein capable of spreading in the plant. The spreading protein may then switch on a cellular process of interest encoded in said additional heterologous nucleic. FIG. 8 illustrates such an embodiment. The cellular process of interest that may be switched on from said additional heterologous nucleic corresponds to those mentioned in connection with said heterologous nucleic acid. In a further important embodiment of this invention, a protein expressed from said heterologous nucleic acid and said directly introduced polypeptide jointly generate a predetermined function leading to switching on said cellular process of interest only when said protein and said polypeptide are jointly present (cf. FIG. 3). Preferably, said protein and said polypeptide jointly generate said predetermined function by intein-mediated trans-splicing or by intein-mediated affinity interaction. Said predetermined function may then switch on the cellular process of the invention. Said predetermined function may e.g. be a binding activity or an enzymatic activity that may act on said addtonal heterologous nucleic acid similar as described above for said protein. An important advantage of this embodiment is that the plant provided in step (a) that is genetically-modified with a heterologous nucleic acid does not contain all components required for switching on said cellular process of the invention. Thus, said plant cannot transfer genetic information for a functional cellular process or interest to progeny or to other organisms. The cellular process of interest that was switched on as described herein does, however, not have to affect the entire plant. Instead, said cellular process of interest may be limited to a part of said plant like leaves or seeds. A cellular process of interest in seeds may be the production of a protein of interest in seeds, whereby the protein of interest can be easily harvested by conventional methods and stored in said seeds. Preferably, however, the cellular process of interest affects substantial parts of said plant. The part of a plant where said cellular process is switched on depends inter alia on the place(s) of application of said polypeptide. Generally, said cellular process of interest may be strongest in the vicinity of the place of application of said polypeptide and may decrease with increasing distance from said place. Said decrease may in general be anisotropic and depend on the structure of the tissue of said plant where said polypeptide was applied. If, for example, a cellular process of interest is to be switched on (e.g. expression of a gene of interest is to be switched on) and said polypeptide is applied to a fraction of a leaf of the plant, said cellular process of interest typically occurs within said fraction of said leaf and in the vicinity of said fraction of said leaf. Preferably, said cellular process of interest occurs in the major part of said leaf. More preferably, said cellular process of interest occurs also in the shoot and in other leaves. Most preferably, said cellular process of interest occurs in the major part of said plant. The extent of said cellular process of interest (e.g. expression of a gene of interest) may vary within said plant e.g. with the cell type or tissue type. Obviously, application of said polypeptide is normally not limited to a single point on the surface of a plant. Preferably, said polypeptide is applied to several parts of said plant (see further below). The cellular process according to the invention may comprise or give rise to a whole biochemical cascade of interest like a multi-step biosynthetic pathway in cells of the plant. The cellular process or biochemical cascade of interest is not operable in the plant prior to exposure to said polypeptide. The method of the invention may provide control over a cellular process or biochemical cascade of interest with a hitherto unattainable technical precision and environmental safety. Thereby, novel applications in biotechnology in general, specifically in plant biotechnology, are available for solving problems which cannot be solved by conventional technologies like basal transgene expression activity in a plant, particularly when producing toxic substances or biodegradable polymers. Moreover, the precise control according to the invention allows to grow a transgenic plant to a desired stage where, for example, the plant is best suited for performing the cellular process of interest without burdening the plant with a basal expression activity slowing down the growth of the plant. Once the plant is ready for efficiently performing the cellular process of interest, the process of interest may be switched on and performed with high efficiency. Accordingly, the method of the invention allows to safely decouple the growth phase and the production phase of a multicellular organism, specifically a transgenic plant. Moreover, it is possible to design multi-component systems for multiple cellular processes or biochemical cascades of interest, whereby one or more desired processes or cascades can be selectively switched on. DESCRIPTION OF THE FIGURES FIG. 1 is a scheme of the method according to the invention. FIG. 2 is a schematic representation of a method according to the invention, wherein the polypeptide is an active (functional) protein (AB), C designates a heterologous DNA and its expression products (RNA or protein). RNA is indicated by having bound ribosomes. In the cell of a plant, the active protein (AB) can interact (1) with said heterologous nucleic acid, (2) with RNA expression products, or (3) with a protein expression product of said heterologous nucleic acid, for switching on a cellular process of interest. FIG. 3 is a schematic representation of a method according to the invention, wherein said polypeptide is a non-functional protein (AB) which after direct introduction into the plant cell is converted to an active form A′B′ under the influence of a factor encoded by a heterologous nucleic acid C. D indicates an additional heterologous nucleic acid (or RNA or protein expression products thereof) that is targeted by the protein A′B′, thus switching on a cellular process of interest. Said conversion to the active form A′B′ may e.g. take place by an enzymatic activity of an expression product of C or by intein-mediated trans-splicing. FIG. 4 is a scheme showing embodiments for generating an active protein switch from inactive protein fragments in a plant cell. A: generation of an active protein switch by intein-mediated trans-splicing of protein fragments. B: generation of an active protein switch by affinity binding of protein fragments. FIG. 5 is a scheme showing assembly of a functional protein (AB) from non-functional protein fragments A and B by intein-mediated trans-splicing (FIG. 5A) or affinity interaction (FIG. 5B). Fragment A is the polypeptide of the invention that is imported into the cell. Fragment B is internally expressed from a heterologous nucleic acid. FIG. 6 is a general scheme showing switching on a cellular process of interest via a protein-switch that is capable of intercellular trafficking and causing its own expression in other cells. PS stands for protein switch, TP stands for a trafficking protein capable of intercellular trafficking (i.e. leaving a cell and entering other cells), PS:TP stands for a PS-TP fusion protein, hNA stands for an additional heterologous nucleic acid. (A) depicts a heterologous nucleic acid encoding PS:TP and an additional heterologous nucleic acid hNA. No external polypeptide is introduced, thus the protein switch is not expressed and no cellular process of interest is switched on. (B) an external (cell-permeable) polypeptide is introduced causing expression of the protein-switch PS:TP. The protein switch can control a cellular process by acting on hNA in the cell of its expression. Further, the protein switch can leave the cell that was triggered by said externally introduced polypeptide and enter other cells. In other cells, the protein switch can induce its own expression and also control the cellular process by acting on hNA. (C) depicts a heterologous nucleic acid encoding two protein switches: PS1 and PS2. Expression of PS1 is caused by an externally applied signal (the polypeptide of the invention), leading to PS1:TP. As above, PS1:TP can spread to other cells and activate expression of PS2. PS2 in turn can control a cellular process by acting on hNA. FIG. 7 depicts in (A) the construct pICHGFPinv containing a non-functional TMV-based provector and in (B) a functional derivative of said construct resulting from integrase-mediated recombination. Arrows at the bottom indicate RNAs and subgenomic (sg) RNAs including their orientation that can be formed from the construct shown in (B). sgp stands for subgenomic promoter. FIG. 8 shows schematically a method according to the invention, wherein a cell-permeable polypeptide (MTS:recombinase) triggers recombination events within targeted cells, leading to the formation of a protein switch capable of intercellular trafficking (recombinase:TP) from a heterologous nucleic acid (the construct coding for recombinase:TP). The protein switch can further trigger recombination events leading to rearrangement of a plant virus-based pro-vector (an additional heterologous nucleic acid according to the invention) resulting in expression of a gene of interest (GOI). MTS: membrane translocating sequence; TP: protein capable of intercellular trafficking; SM: selectable marker; RS: recombination site recognized by site-specific DNA recombinase/integrase; ter1 and ter2: transcription termination regions; PROM: promoter active in plants; RdRp: viral RNA-dependent RNA polymerase; MP: movement protein; 3′NTR: 3′ non-translated region of plant RNA virus. Arrows show the orientation of coding and regulatory sequences. FIG. 9 shows vectors for producing integrase phiC31 proteins fused to membrane translocating signals (MTS). The vectors pICH13180 and pICH13190 contain the 5′ end of a TMV-based vector with an MTS of choice and are designed for site-specific recombination-mediated assembly with a vector (pICH13591) containing a 3′ end of a TMV-based vector coding for the integrase phiC31 with nuclear localisabon signal (NLS) at its C-terminal end. DETAILED DESCRIPTION OF THE INVENTION At the basis of this invention is the use of a polypeptide capable of entering cells of a plant, leading to switching on a cellular process of interest without delivery of nucleic acids encoding said polypeptide or a functional part of said polypeptide into said cells. Preferably, said switching on a cellular process of interest comprises forming a protein that is capable of causing its own expression. The general principle of the method according to the invention is schematically shown in FIGS. 1 to 9. Choice of Protein for “Switch” Function The same switching functions that are described herein for said protein switch may also be used for the switching function of said polypeptide and vice versa. There are countless numbers of cellular processes of interest which can be irreversibly triggered by said protein of the invention (protein switch). The protein switch (marked as AB in FIG. 2) can e.g. control the expression of a transgene of interest (designated C in FIG. 2) in many different ways. For example, it can trigger DNA recombination or transcription, RNA processing or translation, protein post-translational modifications (FIG. 2) etc. In addition, the protein switch can be activated by said polypeptide upon delivery into the plant cell and after that be able to function as a switch (FIG. 3). Obviously, the choice of the protein switch depends on the design/choice of the cellular process to be controlled in said plant. Said cellular process can be controlled, notably switched on, by nucleic add rearrangement or modification in cells wherein said protein is present or in cells that are invaded by said protein. In such case, the protein switch may comprise a DNA or RNA modifying enzyme like a site-specific endonuclease, a recombinase, a methylase, an integrase, a transposase, a polymerase etc. Other embodiments contemplated in this invention include triggering reactions such as DNA restriction and/or DNA replication. An example of a biochemical cascade that can be triggered by restriction is a two-component system wherein a DNA sequence containing an origin of replication and being integrated into a nuclear genome is specifically excised and converted into an autosomally replicating plasmid by a rare-cutting restriction enzyme serving as protein switch, thus triggering the cascade. There are numerous reactions that affect RNA molecules that may be used as efficient triggering device for the cellular process according to the present invention. These include, inter alia, reactions such as RNA replication, reverse transcription, editing, silencing, or translation. There is abundant prior art describing in detail how, for example, a site-specific recombinase, integrase or transposase can trigger a process of interest by DNA excision, inversion or insertion in cells, notably in plant cells (Zuo, Moller & Chua, 2001, Nat Biotech., 19, 157-161; Hoff, Schnorr & Mundy, 2001, Plant Mol. Biol., 45, 41-49; U.S. Pat. No. 5,225,341; WO9911807; WO9925855; U.S. Pat. Nos. 5,925,808; 6,110,736 WO0140492; WO 0136595). Site-specific recombinases/integrases from bacteriophages and yeasts are widely used for manipulating DNA in vitro and in plants and animals. Preferred recombinases-recombination sites for the use in this invention are the following: Cre recombinase-LoxP recombination site, FLP recombinase-FRT recombination sites, R recombinase-RS recombination sites, phage C31 integrase recognising attP/attB sites etc. Transposons are widely used for the discovery of gene function in plants. Preferred transposon systems for use in the present invention include Ac/Ds, En/Spm, transposons belonging to the “mariner” family, etc. Heterologous transcription factors and RNA polymerases may also be used in a protein switch according to the invention. For example, the delivery of T7 polymerase into cells of a plant carrying a transgene under the control of the T7 promoter may induce the expression of such a transgene. The expression of a plant transgene (e.g. the additional heterologous nucleic acid of the invention) that is under control of a bacteriophage promoter (e.g. T3, T7, SP6, K11) with the corresponding DNA/RNA polymerase delivered into cells of a plant may be another efficient approach for the development of protein switches contemplated in this invention. Another useful approach may be the use of heterologous or chimaeric or other artificial promoters which require heterologous or engineered transcription factors for their activation. Heterologous transcription factors also can be used in order to induce expression of the transgene of interest under control of said transcription factor-recognizable promoter. Examples of such transcription factors are inter alia yeast metalloresponsive ACE1 transcription factor binding specific sequences in the yeast MT (metallothionein) promoter (Meft et al., 1993, Proc. Natl. Acad. Sci., 90, 4567-4571), different chimaeric transcription factors having a sequence-specific DNA-binding domain and an activation domain like a transcription factor having a fusion six-zink finger protein 2C7 and herpes simplex virus VP16 transcription factor activation domain (Ordiz, Barbas & Beachy, 2002, Proc. Natl. Acad. Sci. USA, 99, 13290-13295), a transcription factor having a full length 434 repressor and the C-terminal 80 amino acids of VP16 transcriptional activator (Wilde et al., 1994, Plant Mol. Biol., 24, 381-388), a transcription factor used in steroid-inducible systems (Aoyama & Chua, 1997, Plant J., 11, 605-612; McNellis et al., 1998, Plant J., 14, 247-257; U.S. Pat. No. 06,063,985) or a tetracycline-inducible system (Weinmann et al., 1994, Plant J., 5, 559-569). In some cases, the existing inducible systems for transgene expression may be used. Alternatively, heterologous transcription factors may be modified such that no activating ligand-inducer will be required to drive the transcription factor into the active state. Chimaeric transcription factors would be of advantage for the use in this invention, as they allow to combine highly sequence-specific DNA binding domains and highly efficient activation domains, thus allowing a maximum desired effect after delivery of such a factor into the plant cell. Another protein switch contemplated under the invention may rely on posttranslational modification of one or more expression product(s) of a heterologous nucleic acid, which may lead to the activation of the expression product. There are many possible implementations of such protein switches that could operate by controlling steps such as polypeptide folding, oligomer formation, removal of targeting signals, conversion of a pro-enzyme into an enzyme, blocking enzymatic activity, etc. For example, delivery of a site-specific protease into cells of a plant may trigger a cellular process of interest if a genetically-engineered host specifically cleaves a pro-enzyme, thus converting it into an active enzyme, if a product is targeted to a particular cellular compartment because of the host's ability to cleave or modify a targeting motif, or if a product is specifically mobilised due to the removal of a specific binding sequence. Cleavage of a translational fusion protein can be achieved via a peptide sequence recognized by a viral site-specific protease or via a catalytic peptide (Dolja et al., 1992, Proc. Natl. Acad. Sci. USA, 89, 10208-10212; Gopinath et al., 2000, Virology, 267, 159-173; U.S. Pat. Nos. 5,162,601; 5,766,885; 5,491,076). Other examples of site-specific proteases applicable to this invention are mammalian enterokinases, for example, human enterokinase light chain which recognizes the sequence DDDK-I (Kitamoto et al., 1994, Proc. Natl. Acad. Sci., 91, 7588-7592), and specifically cleaves Lys-Ile bonds; viral proteases, like Hc-Pro (Carrington J C & Herndon K L, 1992, Virology, 187, 308-315) which catalyzes proteolysis between the Gly-Gly dipeptide but requires 4 amino acids for the recognition of the cleavage site; site-specific protease of Semliki Forest Virus (Vasiljeva et al., 2001, J Biol. Chem., 276, 30786-30793); and proteases involved in polyubiquitin processing, ubiquitin-carboxy-terminal hydrolases (Osava et al., 2001, Biochem Biophys Res Commun., 283, 627-633). Directly Introducing Said Polypeptide into Cells of a Plant a) Microprojectile Bombardment (Particle Bombardment) Different methods can be used for directly introducing (direct delivery) said polypeptide into cells of said plant. Among the simplest ones is the direct delivery with the help of mechanical interaction with plant tissue. For example, microprojectile bombardment of polypeptide-coated particles can deliver said polypeptide into the plant cell. The protocol can be similar to those described for DNA delivery in plant transformation protocols (U.S. Pat. No. 05,100,792; EP 00444882B1; EP 00434616B1). However, instead of DNA, said polypeptide may be used for coating the particles. There is a description of a biolistic process that uses particle coating methods which are reasonably gentle for preserving the activity of said polypeptide (Sanford, Smith & Russell, 1993, Methods in Enzymol., 217, 483-509). In principle, other plant transformation methods can also be used e.g. microinjection (WO 09209696; WO 09400583A1; EP 175966B1), or liposome-mediated delivery (for review see: Fraley & Papahadiopoulos, 1982, Curr. Top. Microbiol. Immunol., 96,171-191). b) Use of Membrane Translocation Amino Acid Sequences The polypeptide of interest can be applied externally to target cells of said plant using a covalent fusion or non-covalent interaction with a membrane translocating sequence. Many examples of membrane translocating sequences (MTS), natural and synthetic, are known in the art. They are widely used as fusions with peptide drugs and therapeutic proteins in order to increase their cell membrane permeability. An MTS may be a simple amino acid repeat, for example a cationic peptide containing eleven arginines RRRRRRRRRRR (Matsushita et al., 2001, J. Neurosci., 21, 6000-6007). Another cationic MTS is a 27 amino acid long transportan (GWTLNSAGYL LGKINLKALA ALAKKIL) (Pooga et al., 1998, FASEB J., 12, 67-77). It is very likely that such peptides, for their penetration of the cell, exploit the asymmetry of the cellular plasma membrane where the lipid monolayer facing the cytoplasm contains anionic phospholipids (Buckland & Wilton, 2000, Biochim. Biophys. Acta/Mol. Cell. Biol. Of Lipids, 1483, 199-216). Certain proteins also contain subunits that enable their active translocation across the plasma membrane into cells. To such domains belongs the basic domain of HIV-1 Tat49-57 (RKKRRQRRR) (Wender et al., 2000, Proc. Natl. Acad. Sci. USA, 97, 13003-13008), Antennapedia43-58 (RQIKIWFQNR RMKWKK) (Derossi et al., 1994, J. Biol. Chem., 269, 10444-10450), the Kaposi Fibroblast Growth Factor MTS (MVALLPAVL LALLAP) (Lin et al., 1995, J. Biol. Chem., 270, 14255-14258); the VP22 MTS (Bennet, Dulby & Guy, 2002, Nat. Biotechnol., 20, 20; Lai et al., 2000, Proc. Natl. Acad. Sci. USA, 97, 11297-302); homeodomains from the Drosophila melanogaster Fushi-tarazu and Engrailed proteins (Han et al., 2000, Mol Cells 10, 728-732). It was shown that all these positively charged MTSs are able to achieve cell entry by themselves and as fusions with other proteins like GFP (Zhao et al., 2001, J. Immunol. Methods, 254, 137-145; Han et al., 2000, Mol Cells, 10, 728-732), Cre recombinase (Peitz et al., 2002, Proc. Natl. Acad. Sci. USA, 4489-4494) in an energy-independent manner. However, the fusion is not necessarily required for protein transport into the cell. A 21-residue peptide carrier Pep-1 was designed (KETWWETWWTEWSQPKKKRKV) which is able to form complexes by mean of non-covalent hydrophobic interactions with different types of proteins, like GFP, b-Gal, or full-length specific antibodies. These complexes are able to efficiently penetrate cell membranes (Morris et al., 2001, Nature Biotechnol., 19, 1173-1176). The list of MTS can be continued and, in general, any synthetic or naturally occurring arginine-rich peptide can serve for practicing this invention (Futaki et al., 2001, J. Biol. Chem., 276, 5836-5840). As there is no essential structural difference between plant and animal cell membranes affecting their general architecture and physico-chemical properties, said fusions of MTS with said polypeptide of the invention can also be efficiently used for penetrating plant cells. However, unlike animal cells, plant cells possess a tough cell wall (Varner & Linn, 1989, Cell, 56, 231-239; Minorsky, 2002, Plant Physiol., 128, 345-53). This obstacle can be overcome by using simple techniques. For example, injection of a (e.g. crude) protein extract containing said polypeptide having an MTS into a plant apoplast facilitates translocation of said polypeptide into the plant cells. Another approach to overcome the cell wall and to reach the cell membrane of plant cells can be the application of cellulytic enzymes many of which are commercially available. Once added to a composition containing said polypeptide, said enzymes help to remove or weaken the cell wall, but will leave the cell membrane intact and exposed for penetration by said polypeptide containing said MTS. Said cellulytic enzymes from bacteria and molds have been commercially available at industrial scale for a long time and are widely used (e.g. “Onozuka” R-10 enzyme preparation of Trichoderma harzianum, etc.) in plant cell tissue culture for obtaining plant protoplasts (Sidorov &Gleba, 1979, Tsitologia, 21, 441-446; Gleba & Gleba, 1978, Tsitol Genet, 12, 458-469; Ghosh et al., 1994, J. Biotechnol., 32, 1-10; Boyer, Zaccomer & Haenni, 1993, J. Gen. Virol, 74, 1911-1917; Hilbricht, Salamini & Bartels, 2002, Plant J., 31, 293-303). The approach of using cellulytic enzymes has potential for large scale applications of this invention. A mixture of cellulytic enzymes with a cell-permeable polypeptide can be sprayed over the genetically-modified plants or over parts thereof. Cellulases can make cell membranes accessible for membrane permeable polypeptides. Upon translocation into the cell, said polypeptide may trigger said cellular process of interest and the expression of said protein within the plant. In addition to the above delivery methods for said polypeptide, efficient spreading of a protein switch inside the plant is preferably used for amplification purposes within said plant. Further, to make the overall method safe, strict control over the heterologous nucleic acid is required. In order to address these issues it is proposed herein to use a “split genes” (or “split proteins”) approach for controlling the segregation of a transgene encoding the protein switch. In this embodiment, an active (functional) protein switch is assembled either by intein-mediated protein trans-splicing (FIG. 4-A and FIG. 5-A) or by affinity interaction (FIG. 4-B and FIG. 5-B). In this case, the protein switch is not encoded by a continuous DNA sequence and its use may be much better controlled. Such an active protein switch may e.g. be assembled from said polypeptide and a protein expressed in cells of said plant (e.g. from the heterologous nucleic acid) by intein-mediated protein trans-splicing or by affinity interaction. The protein expressed from said heterologous nucleic acid and said polypeptide may jointly generate a predetermined function leading to switching on said cellular process of interest only when the protein and said polypeptide are jointly present. The protein expressed from said heterologous nucleic acid may e.g. be constitutively expressed, whereby the process of interest can be switched by applying said polypeptide. Alternatively, the protein expressed from said heterologous nucleic acid may be under the control of a regulated promoter (e.g. a chemically inducible promoter), which allows a “double” control of the process of interest, namely by induction of the regulated promoter and the introduction of said polypeptide. Importantly, these embodiments have an exceptional biological safety. Intein-mediated protein trans-splicing and affinity interaction are described next. Intein-mediated trans-splicing of proteins with restoration of their activity is known in the prior art and is described in detail in many publications. Protein affinity interaction and/or trans-splicing can be achieved by using engineered inteins (FIG. 4-A). Inteins were first identified as protein sequences embedded in-frame within protein precursor and excised during protein maturation process (Perler et al., 1994, Nucleic Acids Res., 22, 1125-1127; Perler, F. B., 1998, Cell, 92, 14). All information and catalytic groups necessary to perform a self-splicing reaction reside in the intein and two flanking amino acids. The chemical mechanism of protein splicing is described in detail by Perler and colleagues (1997, Curr. Opin. Chem. Biol., 1, 292-299) and by Shao & Kent (1997, Chem. Biol., 4, 187-194). Inteins usually consist of N- and C-terminal splicing regions and a central homing endonuclease region or small linker region. Over 100 inteins are known so far that are distributed among the nuclear and organellar genomes of different organisms including eukaryotes, archaebacteria and eubacteria (http://www.neb.com/neb/inteins.html). It was shown that inteins are capable of trans-splicing. The removal of the central homing endonuclease region does not have any effect on intein self-splicing. This made possible the design of trans-splicing systems, in which the N-terminal and C-terminal fragments of an intein are co-expressed as separate fragments and, when fused to exteins (protein fragments that are ligated together with the help of the intein), can perform trans-splicing in vivo (Shingledecker et al., 1998, Gene, 207, 187-195). It was also demonstrated with N- and C-terminal segments of the Mycobacterium tuberculosis RecA intein, that protein trans-splicing can take place in vitro (Mills et al., 1998, Proc. Natl. Acad. Sci. USA, 95, 3543-3548). This phenomenon was also identified for the DnaE protein of Synechocystis sp. strain PCC6803 (Wu et al., 1998, Proc. Natl. Acad. Sci. USA, 95, 9226-9231). Two different genes located more than 700 Kb.p. apart on opposite DNA strands encode this protein. It was also shown that two intein sequences encoded by those genes reconstitute a split mini-intein and are able to mediate protein trans-splicing activity when tested in Escherichia coli cells. An intein of the same origin (DnaE intein from Synechocystis sp. strain PCC6803) was used to produce functional herbicide-resistant acetolactate synthase II from two unlinked fragments (Sun et al., 2001, Appl. Environ. Microbiol., 67, 1025-29) and 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS) (Chen et al., 2001, Gene, 263, 3948) in E. coli. Trans-splicing of protein fragments (including covalent bond formation between exteins) is not necessarily required to restore the original function of the split protein. In many cases, affinity interaction between protein parts without peptide bond formation is sufficient to restore protein function (FIG. 4-B). This approach is most successful (as in case of intein-mediated trans-splicing) with proteins having two or more functional domains. In this case, the domains can be separated from each other by splitting the coding sequence between two transcription vectors and can be brought together by protein-mediated affinity interactions (FIG. 5-B). Protein domains can interact without the necessity to use interacting inteins. There is an example of reconstituting activity of the IS10 transposase consisting of two structural domains connected by a proteolysis-sensitive linker region (Kwon, Chalmers & Kleckner, 1995, Proc. Natl. Acad. Sci. USA, 92, 8234-8238). Each of the domains separately is unable to provide the transposase function. When added together, however, they are able to provide for transpositions even without being connected by a linker region. There are many other examples of the reconstitution of functional proteins from isolated fragments without peptide bond formation. The efficient assembly of a functional insulin receptor binding site was achieved by simple mixing of non-functional fragments (Kristensen et al., 2002, J. Biol. Chem., 277, 18340-18345). Reconstitution of active proteins by simple mixing of two inactive peptide fragments was shown for leucine dehydrogenase (Oikawa et al., 2001, Biochem. Biophys. Res. Commun., 280, 1177-1182), Ca2+-binding protein calbindin D28k (Berggard et al., 2000, Protein Sci., 9, 2094-2108; Berggard et al., 2001, Biochemistry, 40, 1257-1264), Arabidopsis developmental regulator COP1 (Stacey et al., 2000, Plant Physiol., 124, 979-990), diopamine D receptor (Scarselli et al., 2000, Eur. J. Pharmacol, 397, 291-296), microplasminogen (De Los Santos, Wang & Reich, 1997, Ciba Found. Symp., 212, 76-83) and many others. Leucine zipper domains are of special interest for forming protein heterodimers once fused to a protein of interest (Riecker & Hu, 2000, Methods Enzymol., 328, 282-296; Liu et al., 2001, Curr. Protein Pept. Sci., 2, 107-121). An interesting example is the control of protein-protein interactions with a small molecule. For example, Cre recombinase was engineered in such a way that, when split in two inactive fragments, was able to restore 100% of its recombinase activity in the presence of the small molecule rapamycin that triggered activity complementation by heterodimerization between two inactive fragments (Jullien et al., 2003, Nucleic Acids Res., 31, e131). Rapamycin and, preferably non-toxic, analogues can also be used for conditional protein splicing, where they trigger a trans-splicing reaction (Mootz et al., 2003, J. Am. Chem. Soc., 125, 10561-10569). Similar approaches for regulation of protein-protein interactions with the help of small molecules, such as rapamycin or rapamycin analogues, are described in several papers (Amara et al., 1997, Proc. Natl. Acad. Sci. USA., 94, 10618-10623; Pollock et al., 2000, Proc. Natl. Acad. Sci. USA., 97, 13221-13226; Pollock et al., 2002, Nat. Biotechnol., 20, 729-733). Many other chemical dimerizers such as dexamethasone and methotrexate, can be used for assembling active homo- or heterodimers from inactive protein fragments (for review see: Pollock & Clackson, 2002, Curr. Opin. Biotechnol., 13, 459-467). Affinity interactions can be efficiently engineered by using naturally occurring interacting protein domains or by identifying such domains with the help of two-hybrid (Fields & Son, 1989, Nature, 340, 245-246; Chien et al., 1991, Proc. Natl. Acad. Sci. USA, 88, 9578-9582; Yeast Protocol Handbook, Clontech Laboratories, Inc., 2000) or phage display systems. For example, phage display may be used to select a 5-12-mer oligopeptide with high affinity to a protein fragment of interest. Several such systems are now commercially available. Phage display is a selection technique in which a short variable 5-12-mer oligopeptide is inserted into a coat protein of bacteriophage. The sequence encoding this variable oligopeptide is included in the corresponding gene of the bacteriophage coat protein. Usually, a 7-mer phage display library has at least 109 independent clones bearing different combinations of 7-mer amino acids in variable oligopeptides. Phage display has been used to create affinity complexes between bacteriophage and a protein of interest, allowing rapid identification of peptide ligands for a given target protein by an in vitro selection process called “panning” (Parmley, Smith, 1988, Gene 73, 305-318; Cortese et al., 1995, Curr. Opin. Biotechnol., 6, 73-80). The phage-protein complex created after the panning procedure can be dissociated and a phage with affinity to a target protein can be amplified. Usually, one needs three panning cycles to get bacteriophage with high affinity. After three rounds, individual clones can be characterized by sequencing of variable region in genomic DNA. Said system can be efficiently adopted for identifying short interacting oligopeptides and using them as affinity tags in order to bring together protein fragments. Another approach includes the use of naturally occurring interacting domains like leucine-rich repeats (Kobe & Deisenhofer, 1994, Trends Biochem Sci., 19, 415-421; Kobe & Kajava, 2001, Curr. Opin. Struct. Biol., 11, 725-732), zinc finger (Grossley, Merika & Orkin, 1995, Mol. Cell. Biol., 15, 2448-2456), ankyrin repeats (Thompson, Brown & McKnight, 1991, Science, 253, 762-768), chromo domains (Paro & Hogness, 1991, Proc. Natl. Acad. Sci. USA, 88, 263-267; Singh et al., 1991, Nucleic Acids Res., 19, 789-793) and many others involved in protein-protein interactions. However, the possibility of involving not only the engineered protein fragments containing the motive fusions in protein-protein interactions, but also endogenous proteins can be taken into account. Involving protein-protein interactions for switching on a cellular process of interest like gene expression has inter alia the following advantages: Firstly, the system may be rendered highly specific, as the function of interest is a result of a highly specific protein-protein or protein-nucleic acid interaction, which is characterized by zero-level uninduced state and absence of non-specific leakiness. This is in contrast to prior art systems such as switches based on small molecules that are inherently less specific and invariably show a certain degree of leakiness. Secondly, said protein switch or a fragment thereof (or said polypeptide or a fragment thereof can be directly delivered into cells of a plant without a nucleic acid vector encoding said polypeptide, thus allowing precise dosage of said polypeptide. This makes direct delivery of said protein switch (or said polypeptide) into cells of a plant comparable with the use of small molecules for triggering a required process in cells. Thirdly, the system is inherently environmentally safer than prior art systems that contain full genetic information for the protein of interest (either in a form of linear nucleic acid or fragments of said nucleic acid), since it allows that the organism in question does not contain the full genetic information necessary for the expression of a protein of interest. According to the central dogma of molecular biology, biological systems cannot reverse translate proteins to nucleic acids. Thus, the ‘reverse engineering’ of the genetic information sufficient for expression of a functional trait by a living organism is impossible. Fourthly, the system provides a specific lock that could be used to prohibit unauthorized use of the system. The use of said polypeptide as a component of a crude protein extract from organism expressing said polypeptide or said polypeptide fragment makes it practically very difficult to identify the active component of said extract. Spread of the Protein Switch within a Plant for Triggering a Cellular Process of Interest Here, an approach for overcoming the problem of the low number of cells of a plant that can be reached by the externally-applied polypeptide is provided: said polypeptide may lead to the formation of an intracellular protein-switch molecule capable of cell-to-cell or systemic movement. Moreover, said polypeptide may lead to or may cause the formation of a virus-based vector (amplicon) expressing a gene of interest or a part thereof and being capable of cell-to cell or systemic movement in said plant. In these approaches, the movement of either viral vectors- or protein-switch molecules or both can lead to the spread of a cellular process and/or biochemical cascade over significant parts of said plant and even all over the genetically-modified plant. In Example 1 of this invention, the protein-switch contains an integrase phiC31 to convert a precursor vector of a viral vector into the viral vector. The viral vector is capable of amplification, cell-to-cell and systemic movement. Integrase-mediated recombination between attP and attB sites of pICHGFPinv (FIG. 7-A) leads to the inversion of a DNA fragment flanked by said sites and formation of a viral vector capable of amplification and expression of gene of a interest (GFP) (FIG. 7-B). This may be achieved as the result of placing viral components (3′NTR-3′non-translated region; CP—coat protein) necessary for vector amplification and systemic transport in sense orientation relative to a promoter active in the plant in question like the actin 2 promoter in this example. Thus, together with other viral vector components (e.g. RdRp and CP) it may form a cDNA which upon actin 2 promoter-driven transcription forms an RNA viral vector capable of amplification, cell-to-cell and systemic movement. Optionally, said vector can be further modified by removing the CP (coat protein) gene. Such a vector lacking the CP gene will still be capable of cell-to-cell movement. The construction of plant virus-based expression systems for the expression of non-viral genes in plants has been described in several papers (Dawson et al., 1989, Virology, 172, 285-293; Brisson et al., 1986, Methods in Enzymology, 118, 659; MacFarlane & Popovich, 2000, Virology, 267, 29-35; Gopinath et al., 2000, Virology, 267, 159-173; Voinnet et al., 1999, Proc. Natl. Acad. Sci. USA, 96, 14147-14152) and reviews (Porta & Lomonossoff, 1996, Mol. Biotechnol., 5, 209-221; Yusibov et al., 1999, Curr. Top. Microbiol. Immunol., 240, 81-94) and can be easily performed by those skilled in the art. Viral vector-based expression systems offer a significantly higher yield of a transgene product compared to plant nuclear transgenes. For example, the level of a transgenically encoded protein can reach 5-10% of the total cellular plant protein content when expressed from a viral vector (Kumagai et al., 2000, Gene, 245, 169-174; Shivprasad et al., 1999, Virology, 255, 312-323). RNA viruses are the most suitable as they offer a higher expression level compared to DNA viruses. There are several published patents which describe viral vectors suitable for systemic expression of transgenic material in plants (U.S. Pat. Nos. 5,316,931; 5,589,367; 5,866,785). In general, these vectors can express a foreign gene as a translational fusion with a viral protein (U.S. Pat. Nos. 5,491,076; 5,977,438), from an additional subgenomic promoter (U.S. Pat. Nos. 5,466,788; 5,670,353; 5,866,785), or from polycistronic viral RNA using IRES (internal ribosome entry site) elements for independent protein translation (German Patent Application DE 10049587). The first approach—translational fusion of a recombinant protein with a viral structural protein (Hamamoto et al., 1993, BioTechnology, 11, 930-932; Gopinath et al., 2000, Virology, 267, 159-173; JP6169789; U.S. Pat. No. 5,977,438) gives significant yield of a recombinant protein product. However, the usefulness of this approach is limited, as the recombinant protein cannot be easily separated from the viral one. An alternative of this approach employs a translational fusion via a peptide sequence recognized by a viral site-specific protease or via a catalytic peptide (Dolja et al., 1992, Proc. Natl. Acad. Sci. USA, 89, 10208-10212; Gopinath et al., 2000, Virology, 267, 159-173; U.S. Pat. Nos. 5,162,601; 5,766,885; 5,491,076). Expression processes utilizing viral vectors built on heterologous subgenomic promoters provide the highest level of protein production to date (U.S. Pat. No. 5,316,931). The most serious disadvantage of viral vectors and many others is their limited capacity with regard to the size of DNA to be amplified. Usually, stable constructs accommodate inserts of not more than one kb. In some areas of plant functional genomics this may not be such a serious limitation, as G. della-Cioppa et al. (WO993651) described the use of TMV-based viral vectors to express plant cDNA libraries with the purpose of silencing endogenous genes. Two-component amplification systems which make use of helper viruses may offer a slightly better capacity (U.S. Pat. No. 5,889,191). Other systems based on expression cassettes that are stably integrated into the plant genome contain the strong 35S promoter driving the expression of viral vector based amplicons. These systems usually are subject to post-transcriptional gene silencing (PTGS) (Angell & Baulcombe, 1997, EMBO J., 16, 3675-3684). The use of PTGS suppressors is necessary to overcome such silencing (WO0138512). It requires to perform crosses between plants carrying the silenced amplicon and plants carrying the source of PTGS suppressor (Mallory et al., 2002, Nature Biotechnol, 20, 622-625) for achieving large scale production of a protein of interest with the help of such system. Evidently, such a system has no flexibility and no tight control over transgene expression and is restricted to the production of proteins which do not compromise plant growth and development. Our approach allows to overcome the limitations of the above-described viral vector systems, specifically their limited capacity for the size of the gene to be expressed and the lack of flexibility in controlling the expression. In our invention, the viral vector precursor (also referred to as provector) is preferably present in each cell of the transgenic plant. In the case of expression of large genes (above 1 Kb), protein-switch movement is preferred over viral vector movement. Viral vectors can efficiently amplify in cells and the size of the insert of a viral vector mostly affects the ability for cell-to-cell and systemic movement. Therefore, providing a moveable protein switch capable of activating a viral vector to many cells or even to all cells of the host plant will solve the above-mentioned problem. Additionally, to provide a system with an efficient switching function that is able to turn on the amplification of such a viral vector in most if not all cells of the host plant, protein switches capable of cell-to-cell/systemic movement are used in the present invention. To this end, the protein switch may contain a protein portion that renders said protein capable of cell-to-cell and/or systemic movement. Examples of such protein portions capable to intercellular trafficking are known in prior art. There is evidence that plant transcription factors, defence-related proteins and viral proteins can traffic through plasmodesmata (for review see: Jackson & Hake, 1997, Curr. Opin. Genet. Dev., 7, 495-500; Ding, B. 1998, Plant Mol. Biol., 38, 279-310; Jorgensen R A., 2000, Sci STKE, 58, PE2; Golz & Hudson, 2002, Plant Cell, 14, S277-S288). It was shown that a fusion of 3a movement protein of Cucumber mosaic virus with GFP can traffic out via plasmodesmata to neighboring cells (Itaya et al., 2002, Plant Cell, 14, 2071-2083). Such fusions also showed movement through phloem from transgenic rootstock into non-transgenic scion. The movement protein of tobacco mosaic virus (TMV), P30, traffics between cells through plasmodesmata and, by affecting plasmodesmata size, facilitates the movement of many other large macromolecules not specified for such movement (Citovsky et al., 1999, Phil. Trans. R Soc. London B Biol Sci., 354, 637-443; Ding, Itaya & Woo, 1999, Int Rev. Cytol., 190, 251-316). The P30:GFP fusion showed movement between the cells independent of physiological conditions, while the non-targeted GFP diffusion through plasmodesmata at large depends of physiological state of the plant cells (Crawford & Zambryski, 2001, Plant Physiol, 125, 1802-1812). The fusion of GFP with transcription factor knotted1 also showed the ability for intercellular trafficking. The GFP:KN1 fusion protein demonstarted movement from internal tissues of the leaf to the epidermis, between epidermal cells and into the shoot apical meristem of tobacco plant (Kim et al., 2002, Proc. Natl. Acad. Sci. USA, 99, 4103-4108). Plasmodesmata play an important role in such trafficking and its physiologigal stage and structure are important for the efficiency of such trafficking. For example, simple plasmodesmata allow the nonspecific trafficking of proteins in developing tobacco leaves, while the branched ones do not (Oparka et al., 1999, Cell, 98, 5-8). Allowing trafficking of macromolecules including proteins appears to be a normal function of plasmodesmata, which was made use of by plant viruses for their cell-to-cell spread (Fujiwara et al., 1993, Plant Cell, 5, 1783-1794). In general, it is evident that plasmodesmata and the phloem play an important role in the transport and delivery of information macromolecules (proteins and nucleic acids) (Ruiz-Medrano et al., 2001, Curr. Opin. Plant Biol., 4, 202-209). Phloem sap proteins from Cucurbita maxima and Ricinum communis have the capacity of cell-to-cell trafficking through plasmodesmata (Balachandran et al., 1997, Proc. Natl. Acad. Sci. USA., 94, 14150-14155). FIG. 8 shows schematically possibilities of achieving intercellular movement of the protein switch of the invention. An externally-delivered protein switch (i.e. said polypeptide) and the protein switch synthesised within a cell can be fusions of the same or different protein segments to translocating or trafficking signals. In our example (FIG. 8), the same protein segment, e.g. a recombinase is fused either with a membrane translocating signal (MTS) for cell membrane permeability to form said polypeptide of the invention, or with a protein portion (TP) providing for intercellular trafficking to form said protein switch. It is very likely that for small proteins (like GFP and smaller), fusion to TP might not be necessary, as they may be capable of highly efficient cell-to-cell movement by simple diffusion. However, for larger protein switches, fusion with a TP or an active fragment thereof is advantageous. It is evident that among all proteins involved in intercellular trafficking, viral proteins are studied the best. They are the most preferred candidates to be included in a protein switch. As is shown in FIG. 8, an externally delivered polypeptide may trigger the expression of a transgene encoding a protein switch having the same enzymatic activity, but that is capable of intercellular trafficking (recombinase:TP). Said protein switch capable of trafficking may trigger protein switch expression in all affected cells, what represents a chain reaction. Availability of said protein switch in the cell is a prerequisite for triggering the expression of a gene of interest (GOI) in cells by DNA rearrangement, causing viral vector-based amlicon formation. The size of the gene of interest expressed from such an amplicon is not a limiting factor for efficient GOI expression, since amplicon stability and cell-to-cell movement are not necessary in this system: the viral provector may be present in each plant cell and the spreading of the protein-switch may trigger the expression of the gene of interest in each of these cells. Preferably, however, spreading of the amplicon contributes to efficient GOI expression. The ultimate purpose of the protein switch system contemplated herein is an operational control of a cellular process of interest or a cascade of biochemical reactions of interest in a plant production system. A biochemical cascade is a chain of biochemical reactions in a host production system that ultimately yields a specific product, effect, or trait of interest. The approaches described herein, in addition to being versatile and leakage-proof, provide an efficient production control method. The two-component process described above is in essence a “key-lock” system, whereby a company can efficiently control access to production by selling the protein-switch component. Preferred plants for the use in this invention include any plant species with preference given to agronomically and horticulturally important species. Common crop plants for the use in present invention include alfalfa, barley, beans, canola, cowpeas, cotton, corn, clover, lotus, lentils, lupine, millet, oats, peas, peanuts, rice, rye, sweet clover, sunflower, sweetpea, soybean, sorghum triticale, yam beans, velvet beans, vetch, wheat, wisteria, and nut plants. The plant species preferred for practicing of this invention are including but not restricted to: representatives of Gramineae, Compositeae, Solanaceae and Rosaceae, whereby Solanaceae are preferred. Additionally, preferred species for use the invention, as well as those specified above, plants from the genera: Arabidopsis, Agrosts, Allium, Antirrhinum, Apium, Arachis, Asparagus, Atropa, Avena, Bambusa, Brassica, Bromus, Browaalia, Camellia, Cannabis, Capsicum, Cicer, Chenopodium, Chichorium, Citrus, Coffea, Coix, Cucumis, Curcubita, Cynodon, Dactylis, Datura, Daucus, Digitalis, Dioscorea, Elaeis, Eleusine, Festuca, Fragaria, Geranium, Glycine, Helianthus, Heterocallis, Hevea, Hordeum, Hyoscyamus, Ipomoea, Lactuca, Lens, Lilium, Linum, Lolium, Lotus, Lycopersicon, Majorana, Malus, Mangifera, Manihot, Medicago, Nemesia, Nicotiana, Onobrychis, Oryza, Panicum, Pelargonium, Pennisetum, Petunia, Pisum, Phaseolus, Phleum, Poa, Prunus, Ranunculus, Raphanus, Ribes, Ricinus, Rubus, Saccharum, Salpiglossis, Secale, Senecio, Setaria, Sinapis, Solanum, Sorghum, Stenotaphrum, Theobroma, Trifolium, Trigonella, Triticum, Vicia, Vigna, Vitis, Zea, and the Olyreae, the Pharoideae and many others. Within the scope of this invention the plant species, which are not included into the food or feed chain are specifically preferred for pharmaceutical and technical proteins production. Among them, Nicotiana species are the most preferred, as the species easy to transform and cultivate with well developed expression vectors (especially viral vectors) systems. Genes of interest, their fragments (functional or non-functional) and their artificial derivatives that can be expressed as the cellular process of interest and isolated using the present invention include, but are not limited to: starch modifying enzymes (starch synthase, starch phosphorylation enzyme, debranching enzyme, starch branching enzyme, starch branching enzyme II, granule bound starch synthase), sucrose phosphate synthase, sucrose phosphorylase, polygalacturonase, polyfructan sucrase, ADP glucose pyrophosphorylase, cyclodextrin glycosyltransferase, fructosyl transferase, glycogen synthase, pectin esterase, aprotinin, avidin, bacterial levansucrase, E. coli glgA protein, MAPK4 and orthologues, nitrogen assimilation/methabolism enzyme, glutamine synthase, plant osmotin, 2S albumin, thaumatin, site-specific recombinase/integrase (FLP, Cre, R recombinase, Int, SSVI Integrase R, Integrase phiC31, or an active fragment or variant thereof), isopentenyl transferase, Sca M5 (soybean calmodulin), coleopteran type toxin or an insecticidally active fragment, ubiquitin conjugating enzyme (E2) fusion proteins, enzymes that metabolise lipids, amino acids, sugars, nucleic acids and polysaccharides, superoxide dismutase, inactive proenzyme form of a protease, plant protein toxins, traits altering fiber in fiber producing plants, Coleopteran active toxin from Bacillus thuringiensis (Bt2 toxin, insecticidal crystal protein (ICP), CryiC toxin, delta endotoxin, polyopeptide toxin, protoxin etc.), insect specific toxin AalT, cellulose degrading enzymes, E1 cellulase from Acidothermus celluloticus, lignin modifying enzymes, cinnamoyl alcohol dehydrogenase, trehalose-6-phosphate synthase, enzymes of cytokinin metabolic pathway, HMG-CoA reductase, E. coli inorganic pyrophosphatase, seed storage protein, Erwinia herbicola lycopen synthase, ACC oxidase, pTOM36 encoded protein, phytase, ketohydrolase, acetoacetyl CoA reductase, PHB (polyhydroxybutanoate) synthase, acyl carrier protein, napin, EA9, non-higher plant phytoene synthase, pTOM5 encoded protein, ETR (ethylene receptor), plastidic pyruvate phosphate dikinase, nematode-inducible transmembrane pore protein, trait enhancing photosynthetic or plastid function of the plant cell, stilbene synthase, an enzyme capable of hydroxylating phenols, catechol dioxygenase, catechol 2,3-dioxygenase, chloromuconate cycloisomerase, anthranilate synthase, Brassica AGL15 protein, fructose 1,6-biphosphatase (FBPase), AMV RNA3, PVY replicase, PLRV replicase, potyvirus coat protein, CMV coat protein, TMV coat protein, luteovirus replicase, MDMV messenger RNA, mutant geminiviral replicase, Umbellularia californica C12:0 preferring acyl-ACP thioesterase, plant C10 or C12:0 preferring acyl-ACP thioesterase, C14:0 preferring acyl-ACP thioesterase (luxD), plant synthase factor A, plant synthase factor B, D6-desaturase, protein having an enzymatic activity in the peroxysomal b-oxidation of fatty acids in plant cells, acyl-CoA oxidase, 3-ketoacyl-CoA thiolase, lipase, maize acetyl-CoA-carboxylase, 5-enolpyruvylshikimate-3-phosphate synthase (EPSP), phosphinothricin acetyl transferase (BAR, PAT), CP4 protein, ACC deaminase, protein having posttranslational cleavage site, DHPS gene conferring sulfonamide resistance, bacterial nitrilase, 2,4D monooxygenase, acetolactate synthase or acetohydroxyacid synthase (ALS, AHAS), polygalacturonase, Taq polymerase, bacterial nitrilase, many other enzymes of bacterial or phage including restriction endonucleases, methylases, DNA and RNA ligases, DNA and RNA polymerases, reverse trascryptases, nucleases (Dnases and RNAses), phosphatases, transferases etc. Our invention also can be used for the purpose of molecular farming and purification of commercially valuable and pharmaceutically important proteins including industrial enzymes (cellulases, lipases, proteases, phytases etc.) and fibrous proteins (collagen, spider silk protein, etc.). Any human or animal health protein can be expressed and purified using described in our invention approach. Examples of such proteins of interest include inter alia immune response proteins (monoclonal antibodies, single chain antibodies, T cell receptors etc.), antigens including those derived from pathogenic microorganisms, colony stimulating factors, relaxins, polypeptide hormones including somatotropin (HGH) and proinsulin, cytokines and their receptors, interferons, growth factors and coagulation factors, enzymatically active lysosomal enzyme, fibrinolytic polypeptides, blood clotting factors, trypsinogen, a1-antitrypsin (MT), human serum albumin, glucocerebrosidases, native cholera toxin B as well as function-conservative proteins like fusions, mutant versions and synthetic derivatives of the above proteins. EXAMPLE 1 Use of Site-Specific DNA Recombination Trigerred by Protein-Switch to Assemble Amplifying Vector from Provector Parts Stably Integrated into the Plant Genome Binary vector pICHFPinv (FIG. 7) carrying T-DNA with two provector parts was designed using standard molecular biology techniques (Maniatis et al., 1982, Molecular cloning: a Laboratory Manual. Cold Spring Harbor Laboratory, New York). The descriptions of provector elements and basic principles of their construction and functionin are described in details in patent application PCT/EP02/03476 (WO02088369) and in DE 101 21 283. The vector carries transformation marker (NPTII gene), the 5′end of TMV preceded by the plant promoter of the arabidopsis actin 2 gene (An et al., 1996, Plant J., 10, 107-121) and contains an RNA dependent RNA polymerase (RdRp) and movement protein (MP) followed by a subgenomic promoter. The vector also contains 3′ end of provector containing a gene of interest (GFP), viral coat protein (CP) providing for the systemic movement and 3′-nontranslated region of viral vector (3′NTR). The 3′ provector together with two transcription termination signals is flanked by recombination sites recognised by phage integrase phiC31 (Thomason, Calendar & Ow, 2001, Mol. Genet. Genomics, 265, 1031-1038). Transgenic Nicotiana benthamiana plants containing T-DNA of pICHGFPinv were obtained by Agrobacterium-mediated transformation of leaf discs as described by Horsch et al., (1985, Science, 227, 129-131). Leaf discs were incubated for 30 min with Agrobacterium strain GV3101 transformed with the construct of interest. After three days of incubation on medium (MS-medium 0.1 mgA NM, 1 mg/l BAP) without selective agent, selection of transformants was performed on the same MS-medium supplemented with 100 mg/L Kanamycin. In ordero reduce the growth of Agrobacterium, the medium was also supplemented with 300 mg/L carbenicilin and 300 mg/L cefataxime. Regenerants were incubated on selective MS-medium without hormones supplemented with the same concentration of the selective agents to induce the rooting. The presence of the transgene in segregating T2-populations was confirmed by PCR-analysis. In order to produce a cell-permeable integrase or recombinase fused to the membrane translocation signal (MTS) of choice, the set of constructs for provector system (WO02088369) was made (see FIG. 9) according to standard molecular biology techniques. The integrase phiC31 was produced in N. benthamiana leaves, said integrase was fused to MTS of HIV-Tat48-60 (Wender et al., 2000, Proc. Natl. Acad. Sci. USA, 97, 13003-13008) or Kaposi Fibroblast Growth Factor (FGF) MTS (Lin et al., 1995, J. Biol. Chem., 270, 14255-14258). The crude protein extract from infected N. benthamiana leaves was used for treatment of transgenic plants transformed with T-DNA of pICHGFPinv. In order to facilitate the penetration of the plant cell wall, an addition of cellulytic enzymes to crude protein extract containing the integrase, was used in some experiments. The 0.001% cellulase Onozuka R-10 (Serva) was used to increase the efficiency of the MTS-integrase fusion delivery into the plant cell. Exposure of transgenic plant leaves to cell-permeable integrase causes site-specific recombination between attP and attB sites. Such recombination leads to the reversion of 3′ provector, thus creating a complete cDNA of a viral amplicon under the control of the actin 2 promoter (FIG. 7, B). The TMV-based RNA amplicon expressing GFP is able for cell-to-cell and systemic movement The GFP expression in N. benthamiana plants can be easily detected using UV lamp or analyzing plant tissue under LEICA stereo fluorescent microscope system (excitation at 450-490 nm, emission at 500-550 nm). The sGFP used in our experiments can be excited by blue and UV-light.
<SOH> BACKGROUND OF THE INVENTION <EOH>Controllable Transagene Expression Systems in Plants One of the major problems in plant biotechnology is the achievement of reliable control over transgene expression. Tight control over gene expression in plants is essential if a downstream product of transgene expression is growth inhibitory or toxic, like for example, biodegradable plastics (Nawrath, Poirier & Somerville, 1994 , Proc. Natl. Acad. Sci., 91, 12760-12764; John & Keller, 1996 , Proc. Natl. Acad. Sci., 93, 12768-12773; U.S. Pat. Nos. 6,103,956; 5,650,555) or protein toxins (U.S. Pat. No. 6,140,075). Existing technologies for controlling gene expression in plants, are usually based on tissue-specific and inducible promoters and practically all of them suffer from a basal expression activity even when uninduced, i.e. they are “leaky”. Tissue-specific promoters (U.S. Pat. No. 05,955,361; WO09828431) represent a powerful tool but their use is restricted to very specific areas of applications, e.g. for producing sterile plants (WO9839462) or expressing genes of interest in seeds (WO00068388; U.S. Pat. No. 05,608,152). Inducible promoters can be divided into two categories according to their induction conditions: those induced by abiotic factors (temperature, light, chemical substances) and those that can be induced by biotic factors, for example, pathogen or pest attack. Examples of the first category are heat-inducible (U.S. Pat. No. 05,187,287) and cold-inducible (U.S. Pat. No. 05,847,102) promoters, a copper-inducible system (Mett et al., 1993 , Proc. Natl. Acad. Sci., 90, 4567-4571), steroid-inducible systems (Aoyama & Chua, 1997 , Plant J., 11, 605-612; McNellis et al., 1998 , Plant J., 14, 247-257; U.S. Pat. No. 06,063,985), an ethanol-inducible system (Caddick et al., 1997 , Nature Biotech., 16, 177-180; WO09321334), and a tetracycline-inducible system (Weinmann et al., 1994 , Plant J., 5, 559-569). One of the latest developments in the area of chemically inducible systems for plants is a chimaeric promoter that can be switched on by glucocorticoid dexamethasone and switched off by tetracycline (Bohner et al., 1999 , Plant J., 19, 87-95). For a review on chemically inducible systems see: Zuo & Chua, (2000 , Current Opin. Biotechnol., 11, 146-151). Other examples of inducible promoters are promoters which control the expression of patogenesis-related (PR) genes in plants. These promoters can be induced by treatment of a plant with salicylic acid, an important component of plant signaling pathways in response to pathogen attack, or other chemical compounds (benzo-1,2,3-thiadiazole or isonicotinic acid) which are capable of triggering PR gene expression (U.S. Pat. No. 05,942,662). There are reports of controllable transgene expression systems using viral RNA/RNA polymerase provided by viral infection (for example, see U.S. Pat. Nos. 6,093,554; 5,919,705). In these systems, a recombinant plant DNA sequence includes the nucleotide sequences from the viral genome recognized by viral RNA/RNA polymerase. The effectiveness of these systems is limited because of the low ability of viral polymerases to provide functions in trans, and their inability to control processes other than RNA amplification. Another way is to trigger a process of interest in a transgenic plant by using a genetically-modified virus which provides a heterologous nucleic acid encoding a switch for a biochemical process in a genetically-modified plant (WO02068664). The systems described above are of significant interest as opportunities of obtaining desired patterns of transgene expression, but they do not allow tight control over the expression patterns, as the inducing agents (copper) or their analogs (brassinosteroids in case of steroid-controllable system) can be present in plant tissues at levels sufficient to cause residual expression. Additionally, the use of antibiotics and steroids as chemical inducers is not desirable or economically unfeasible for large-scale applications. When using promoters of PR genes or viral RNA/RNA polymerases as control means for transgenes, the requirements of tight control over transgene expression are also not fulfilled, as casual pathogen infection or stress can cause expression. Tissue- or organ-specific promoters are restricted to very narrow areas of application, since they confine expression to a specific organ or stage of plant development, but do not allow the transgene to be switched on at will. Recombinant viral switches as described in WO02/068664 address all these problems, but do not guarantee tight environmental safety requirements, as the heterologous nucleic acid in the viral vector can recombine. There is an abundant literature including patent applications which describe the design of virus resistant plants by the expression of viral genes or mutated forms of viral RNA (e.g. U.S. Pat. Nos. 5,792,926; 6,040,496). However, there is an environmental risk associated with the use of such plants due to the possibility of forming novel viruses by recombination between the challenging virus and transgenic viral RNA or DNA (Adair & Kearney, 2000 , Arch. Virol, 145, 1867-1883). Hooykaas and colleagues (2000 , Science, 290, 979-982; WO01/89283) described the use of a translational fusion of Cre recombinase with vir gene fragments for Agrobacterium -mediated recombinase translocation into plant cells. Cre-mediated in planta recombination events resulted in a selectable phenotype. The translocation of Cre recombinase is the first use of a translocated protein as a switch to trigger a process of interest in plant cells. However, despite the translocation is not necessarily accompanied by DNA transfer, this approach does not guarantee high level safety, as the phytopathogenic genetically-modified microorganism ( Agrobacterium ) posesses a complete coding sequence of the switching protein Cre recombinase. Further, the process of interest can only be triggered in cells that receive the switching protein. If large ensembles of cell are to be treated, the ratio of cells receiving switching protein to the total number of cells becomes very small. The method of Hooykaas can therefore not be applied to entire plants. Instead, its usefulness is limited to cells in tissue culture or cell culture. It is therefore object of this invention to provide a method of switching on a cellular process of interest in entire plants. It is another object of the invention to provide an environmentally safe method of switching on a cellular process of interest in plants, whereby the cellular process may be selectively switched on at any predetermined time. It is another object of this invention to provide a method for producing a product in a transgenic plant, wherein the production of the product may be selectively switched on after the plant has grown to a desired stage, whereby the process is environmentally safe in that genetic material necessary for said cellular process and genetic material coding for the control function are not spread in the environment together.
20050622
20111108
20060202
80789.0
A01H100
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PAGE, BRENT T
METHOD OF CONTROLLING CELLULAR PROCESSES IN PLANTS
UNDISCOUNTED
0
ACCEPTED
A01H
2,005
10,535,810
ACCEPTED
Continuous steam generator with circulating atmospheric fluidised-bed combustion
A continuous steam generator with a circulating atmospheric fludized-bed chamber is defined by encircling walls essentially on all sides, comprised of gas-permeable tubular walls provided with essentially vertical tubes, and comprises at least one funnel in its lower region. The turbulence combustion chamber has at one essentially vertically arranged heating surface provided with vertical tubes, said heating surface comprises of a welded tube-web-tube combination, and a water/steam working medium flows through the tubes of the encircling walls and the heating surface. All of the tubes of the encircling walls and the heating surface are embodied as evaporator heating surfaces and are mounted in parallel for the circulation of the entire working medium to be evaporated. In addition, all of the tubes of the encircling walls have an inner smooth surface, and the heating surface extends between the bottom of the combustion chamber or the upper edge of the funnel, and the top of the combustion chamber.
1. A continuous steam generator having a circulating atmospheric fluidized-bed firing system, having a fluidized-bed combustion chamber, in which the fluidized-bed combustion chamber is essentially defined on all sides by enclosing walls, having gas-tight tubular walls essentially comprising vertical tubes and in the lower area at least one funnel, and the fluidized-bed combustion chamber is embodied with at least one essentially vertically disposed heating surface equipped with vertical tubes, whereby the heating surface is comprised of a welded tube-web-tube combination, and whereby the tubes of the enclosing walls and the heating surface have a water/steam working medium passing through them, wherein all tubes of the enclosing walls and the heating surface are configured as an evaporator heating surface, and they are connected in parallel so that all of the working medium that is to be evaporated can pass through them, all tubes of the enclosing walls are configured with a tube surface area that is smooth on the inside, and the heating surface extends between the bottom of the combustion chamber or the top of the funnel edge and the combustion chamber cover. 2. The continuous steam generator of claim 1, wherein the flow of working media through the tubes of the enclosing walls and of the heating surface is accomplished without the aid of intermediate collectors. 3. The continuous steam generator of claim 1, wherein the heating surface can be heated on both sides. 4. The continuous steam generator of claim 3, wherein the inner surfaces of the tubes of the heating surface have a single- or multiple-pitch helical internal ribbing. 5. The continuous steam generator of claim 1, wherein the heating surface is configured so that it can be heated from one side. 6. The continuous steam generator of claim 5, wherein the inner surfaces of the tubes of the heating surface have a smooth surface. 7. The continuous steam generator of claim 5, wherein the heating surface has a box-shaped cross section with a width and a depth and on the peripheral side comprises an inner space that is closed around its circumference. 8. The continuous steam generator of claim 1, wherein the cross section of the box-shaped heating surface is configured to have at least three-corners or to be round. 9. The continuous steam generator of claim 1, wherein the cross section of the box-shaped heating surface is configured to be rectangular. 10. The continuous steam generator of claim 7, wherein the tubes of the box-shaped heating surface, which are provided with a fireproof covering in the combustion chamber funnel area are bent out into the area of the inner space in the transition area between the covered and non-covered heating surface area, and the front edges of the fireproof covering and of the non-covered area of the heating surface are configured so that they align in the vertical direction. 11. The continuous heat generator of claim 1, wherein the tubes of the enclosing walls essentially have equal heated lengths. 12. The continuous heat generator of claim 1, wherein the tubes of the heating surface essentially have the same heated length as the tubes of the surrounding walls. 13. The continuous steam generator of claim 2, wherein the heating surface can be heated on both sides. 14. The continuous steam generator of claim 13, wherein the inner surfaces of the tubes of the heating surface have a single- or multiple-pitch helical internal ribbing. 15. The continuous steam generator of claim 2, wherein the heating surface is configured so that it can be heated from one side. 16. The continuous steam generator of claim 15, wherein the inner surfaces of the tubes of the heating surface have a smooth surface. 17. The continuous steam generator of claim 6, wherein the heating surface has a box-shaped cross section with a width and a depth and on the peripheral side comprises an inner space that is closed around its circumference. 18. The continuous steam generator of claim 2, wherein the cross section of the box-shaped heating surface is configured to have at least three-corners or to be round. 19. The continuous steam generator of claim 3, wherein the cross section of the box-shaped heating surface is configured to have at least three-corners or to be round. 20. The continuous steam generator of claim 4, wherein the cross section of the box-shaped heating surface is configured to have at least three-corners or to be round.
The invention relates to a continuous steam generator having a circulating atmospheric fluidized-bed firing system. In addition to natural circulation and forced circulation steam generators, forced continuous steam generators and continuous steam generators used to generate electrical energy by burning, for example, fossil fuels are known. The latter steam generators are used in particular in modern and/or large electrical power plants. In them, the heat released during the combustion of fuel in the combustion chamber of the continuous steam generator is transferred to heating surfaces of the continuous steam generator. These heating surfaces have a working medium flowing by them, and they consist of, for example, combustion chamber-enclosing walls, radiating and/or convective heating surfaces. The working medium is part of a water/steam loop in a steam turbine in which it gives off the thermal energy that it has absorbed. Such continuous steam generators, in which the working medium is preheated, evaporated, superheated, and, in some cases, temporarily superheated, in a single passage through the steam generator, have been known for a long time and are optionally equipped with burners to burn fossil fuels. A conventional, coal-dust-fired continuous steam generator has been disclosed in the publication “Zwangdurchlaufkessel für Gleitdruckbetrieb mit vertikaler Brennkammerberohrung” [forced continuous boiler for sliding-pressure operation with vertical combustion chamber tubing], VGB Kraftwerkstechnik 64, no. 4, April 1984, H. Juzi, A. Salem, and W. Stocker. As a rule, the combustion chamber-enclosing walls of the continuous steam generator are made of welded pipe-web-pipe evaporator heating surfaces. In order to ensure that the enclosing pipe walls are adequately cooled, either sloped smooth pipes (in other words pipes having smooth inner walls that extend at an angle within the enclosing pipe walls), internally ribbed vertical pipes or downcoming/riser pipe systems are used (in other words, the enclosing pipe walls are divided into a plurality of wall sections through which the fluid flows, one after another; see also FIG. 2c of the publication cited above). In recent years, continuous steam generators having circulating fluidized-bed firing systems (CFBFSs) have been designed. As is the case with all power plant systems fired by fossil fuels, an attempt is made to reduce the emissions resulted from combustion in order to protect the environment. This can be done by increasing the power plant's process efficiency combined with a reduction in the amount of fossil fuel used. A portion of the increase in efficiency is accomplished by generating steam at high steam parameters (high steam pressures and temperatures). In order for the power plant units to operate efficiently within a wide load range, the steam generators are operating with sliding pressure. In order to meet various requirements (a constant high steam temperature, sliding steam pressure, rapid rates of load changes), only the forced continuous steam generating systems referred to above may be used. For reasons relating to erosion, the combustion chamber-enclosing walls of continuous steam generators having circulating fluidized-bed firing systems cannot be positioned at a slope or angle, as is the case with conventional coal-dust-fired continuous steam generators, but rather they must have vertical tubes. Therefore, the circulating fluidized-bed firing systems were mainly combined with evaporator systems that work on the principle of natural circulation or forced circulation operation and are therefore equipped with vertically tubular enclosing walls. A small number of circulating fluidized-bed firing systems also generate steam by means of forced-circulation systems, however as a downcoming/riser pipe system with low vapor pressures (for example, the Moabit power plant). Plans have already been made for using CFBFSs-equipped forced continuous steam generators in the pressure range from 100 to 300 bar so that they will operate more efficiently—in other words, with less fuel. Because of the necessity of forming combustion chamber-enclosing walls from vertical evaporator tubes, tubes that have ribs on their inner sides were proposed for cooling the evaporator walls (see publication cited above). In the transition from naturally circulating steam generators to (supercritical) forced continuous steam generations operating at high steam parameters (typically 250 to 300 bar, 560 to 620° C.) in the power range from 300 to 600 MWel, the following problems and disadvantages occur in the prior art: CFBFSs continuous steam generators that are operated with sub-critical steam pressures use more fuel in comparison with supercritical steam pressures with the same steam generator output, therefore causing more hazardous emissions. In contrast to sloped tubes, vertical-tube-equipped forced continuous steam generators have the disadvantage that the number of tubes with a given combustion chamber geometry is larger and that the mass flow density (which is a measure of working medium flow in kg per m2 flow cross-sectional area and per second) decreases per tube. In order, nevertheless, to ensure that the tubes are adequately cooled, tubes having internal ribs are used, or the individual walls of the combustion chamber-enclosing walls have serial fluid flow. Distributing the entire evaporator flow to a plurality of walls connected in series has a number of disadvantages: 1) The individual walls must be connected by means of downcoming tubes 2) When the evaporator flow is redistributed, demixing processes occur (different steam contents), which manifest themselves at the evaporator outlet as temperature aberrations, which can result in cracks in the walls as a result of thermal expansion being prevented. 3) Higher pressure loss because of higher mass flow density. Tubes with internal ribs have higher pressure losses due to friction and have the disadvantage that special manufacturing techniques are required and that the effort and expense needed to join the part surfaces is greater. The object of the invention is therefore to provide a continuous steam generator having a circulating atmospheric fluidized-bed firing system in which the aforesaid disadvantages are avoided and/or the following criteria are met. Use of more economical and more environmentally friendly continuous steam generators equipped with CFBFSs in the power range from approximately 300 to 600 MWel, and in a pressure range of approximately 100 to 300 bar. Achieving efficient combustion chamber design for such a continuous steam generator incorporating additional heating surfaces installed inside or, optionally, outside the combustion chamber. The object of the invention referred to above is accomplished by the characterizing elements of patent Claim 1. Preferred embodiments of the invention are found in the dependent claims. The solution of the invention provides a continuous steam generator having a circulating atmospheric fluidized-bed firing system that has the following advantages: As a result of combining the combustion chamber-enclosing walls and additional heating surfaces located in the combustion chamber as evaporation heating surfaces and causing the working medium to flow through these evaporator heating surfaces in parallel, the fluidized-bed combustion chamber and, thus, also the continuous steam generator can be configured to be much lower in terms of its design scope and therefore to be more cost effective. There are economic advantages of using smooth tubes-in other words tubes that have smooth interior surfaces—in the enclosing walls of the continuous steam generator, since they are less expensive than internally-ribbed tubes and also since no specially manufactured parts are required. Numerous manufacturers produce a great variety of smooth tubes, which is not the case with internally-ribbed tubes. Using smooth tubes in the enclosing walls of the continuous steam generator results in a lower pressure loss in the evaporator heating surface compared to an evaporator heating surface made with tubes having internal ribs. The parallel flow of fluid through the enclosing walls and the additional heating surfaces disposed in the fluidized-bed chamber produce economic advantages, since it is not necessary to install intermediate collectors (blending or pressure-compensation collectors). Assembling the heating surfaces made from smooth tubes is more economical (no modification of the internal ribbing is necessary, thus less tubing wasted in assembly). The length or height of the vertical heating surfaces that are also located in the fluidized-bed combustion chamber is modified to match the height and construction (different funnels in the lower area of the combustion chamber) of the fluidized-bed combustion chamber. This leads to advantages in the assembly of the heating surfaces, since they can be efficiently integrated into the combustion chamber base or into the upper edge of the funnel, as well as the combustion chamber cover. The heating surfaces that are also located in the fluidized-bed combustion chambers can be designed as heating surfaces that are heated on one side and welded together to form boxes, or as bulkhead heating surfaces that are heated on two sides. The desired mass flow density that is necessary in order to compensate mass flow and heating differences and to achieve nearly the same outlet temperatures is accomplished through the integration of additional heating surfaces. The combustion chamber dimensions (cross section, height) and the integrated heating surfaces are dimensioned in such a way that the effective heat flow densities permit the use of vertical smooth pipes in the enclosing walls when mass flow densities are small. As a result of the use of heating surfaces that are heated on both sides, said heating surfaces may be designed in a simple but advantageous manner by making flat bulkhead heating surfaces from a pipe-web-pipe combination. In a preferred embodiment the tubes of these bulkhead heating surfaces have an internal ribbing which, with lower mass flow densities and the higher heating (because the heating is two-sided) reliably cool the heating surfaces. In this case the tubes of the enclosing walls can remain smooth tubes. In one preferred embodiment, the heating surface of the invention is heated on one side and the heating surface that is heated on one side is designed with smooth tubes in a preferred embodiment. In this way, as already described for the smooth tubes in the enclosing wall, an essential economic advantage is achieved, since smooth tubes are essentially less expensive, easier to install, and have a lower pressure loss due to friction. In a preferred embodiment of the heating surface that is heated on one side, said heating surface is configured as a box-shaped heating surface having a box-shaped cross section. Because of the box-shaped design, the heating surface has a high degree of stability that permits combustion chambers of relatively large continuous steam generators be equipped with heating surfaces. In a further, preferred embodiment the cross section of the box-shaped heating surface is designed to be rectangular. In order to achieve uniform heating of the working medium within the tubes in the enclosing walls, it is advantageous that said tubes essentially have the same heated length. In order to transfer the same effect to the tubes in the heating surfaces, it is also advantageous for the tubes in the heating surfaces to have the same heated length as the tubes in the enclosing walls. Examples of the invention are explained in greater detail below on the basis of the drawing and the description. The drawing shows: FIG. 1 a schematic diagram of a continuous steam generator having a circulating atmospheric fluidized-bed firing system in a longitudinal section, FIG. 2 a schematic diagram of a fluidized-bed combustion chamber of a fluidized-bed continuous steam generator having a combustion chamber funnel showing in a longitudinal cross section, FIG. 3 as in FIG. 2, a fluidized-bed combustion chamber having two combustion chamber funnels (“pant leg”) shown in a longitudinal cross section, FIG. 4 schematic diagram of a combustion chamber of a fluidized-bed continuous steam generator (having one combustion chamber funnel shown in cross section per Section A-A, of FIG. 2, rotated by 90°, FIG. 5 schematic diagram of a combustion chamber of a fluidized-bed continuous steam generator (with two combustion chamber funnels) in the cross section indicated as Section B-B in FIG. 3, section rotated 90° C., FIG. 6 schematic cross section of an alternative box-shaped heating surface (box bulkhead) of Detail C and FIGS. 4 and 5, FIG. 7 schematic diagram of a box-shaped heating surface with a vertically aligning transition from the fireproof exterior covering to the upper membrane tubular wall in a longitudinal section, corresponds to Section A-A in FIG. 8, FIG. 8 schematic cross section of a box-shaped heating surface shown in Section C-C of FIG. 9, FIG. 9 schematic longitudinal section of a box-shaped heating surface as shown in Section B-B of FIG. 8. In the continuous steam generators fired with fossil fuel in conventional power plants, in the prior art, the working medium, normally water/steam, is essentially preheated, vaporized, superheated, and optionally temporarily superheated in one pass through the steam turbine loop. The continuous steam generator including the appurtenant firing system is described below. FIG. 1 shows a schematic diagram of a continuous steam generator 1 having a circulating fluidized-bed firing system 2 (CFBFS) for burning coal or other combustible materials. The material that is to be burned is transported through the feed line 10 into the fluidized-bed combustion chamber or fluidized-combustion chamber 3 of the continuous steam generator 1 having a CFBFS. In order to construct the fluidized-bed and to burn the material being fed in in combustion chamber 3, a fluidization gas is directed through the feed line 11, normally the fluidized-combustion chamber 3. The fluidization gas is generally air, which therefore is used as the oxidizing agent for the combustion. The exhaust gas or flue gas that results from the combustion and the solids entrained by the exhaust gas (inert material, ash particles, and non-combusted materials) are transported out of the combustion chamber 3 in the upper area via opening 12, and they are fed via an exhaust gas line 13 to a precipitator, generally a centrifugal precipitator or cyclone precipitator 14. In the precipitator 14, the solids present in the exhaust gas are largely separating off and returned back to the combustion chamber 3 via the return line 15. The largely purified exhaust gas is fed via the exhaust gas line 16 to a second exhaust gas 17 stack in which at least one economizer heating surface 18, at least one superheater heating surface 19, and possibly at least one intermediate superheater surface 20 is provided for further use or for the acceptance of the exhaust gas heat. The cross section of combustion chamber 3 generally has a rectangular shape. However, it can also be round or have a different shape. FIGS. 2 to 5 show in a longitudinal section as well as in a transverse section the rectangularly formed and essentially vertically disposed fluidized-bed chamber 3 of a continuous steam generator 1. The combustion chamber 3 is essentially enclosed on all sides by the enclosing walls 4, whereby the enclosing wall 4 seen from the bottom toward the top comprises the combustion chamber bottom 4.1, the combustion chamber side walls 4.2, and the combustion chamber top 4.3. The combustion chamber floor 4.1 is generally configured as a nozzle plate through which the fluidization gas is brought in. FIG. 2 shows a combustion chamber 3 having a simple funnel 6 in the lower area of the combustion chamber. On the other hand, FIG. 3 is a combustion chamber 3 having a dual funnel 7, a so-called “pant leg” design. The combustion chamber enclosing walls 4 are configured as heating surfaces through which the working medium flows, and said heating surfaces are made of gas-tight membrane walls. Such membrane walls can be assembled by means of gas-tight welding of a combination of tube-web-tube. As a rule, the tube-web-tube combination comprises tubes 5 whose exteriors are smooth and which are each connected by means of separate webs 21. However, it is also possible that finned tubes, whose outer wall is already equipped with webs and which are connected to each other, can be used. The present invention relates to a continuous steam generator 1 having a circulating fluidized-bed firing system 2 characterized by a high output (approximately 300 to 600 MWel) and high steam parameters (about 250 to 300 bar pressure and 560 to 620° C.). In order to obtain an efficient combustion chamber design in this performance range, additional heating surfaces 8 must also be installed. For thermal technology reasons (uniform heat absorption) said additional heating surfaces 8 are preferably disposed within the combustion chamber 3. The continuous steam generator 1 of the invention having a CFBFS 2 required that all tubes 5, 9 in the enclosing wall 4 and the heating surfaces 8 lying within combustion chamber 3 be embodied as an evaporator heating surface, and that they be connected in parallel for the flow of the entire working medium that is to be evaporated, that all tubes 5 in the enclosing walls 4 be equipped with a pipe surface area that is smooth on the inside, and that the heating surfaces 8 extend between the combustion chamber base 4.1 or funnel upper edge 24 and the combustion chamber cover 4.3. By connecting the heating surfaces 8 and the heating surface of the enclosing wall 4 of the continuous steam generator 1 in parallel, as well as by using both heating surfaces as an evaporator heating surface, one achieves the advantage that, by modifying the number of heating surfaces 8, the combustion chamber 3 can be designed to be efficient. In other words, using this measure, one is able to optimize the combustion chamber dimensions; above all the height of the combustion chamber (the distance between the bottom of the combustion chamber and the top), can be reduced significantly by including the heating surfaces 8. Additionally, the effective heat flux densities within the fluidized-bed combustion chamber 3 of the continuous steam generator 1 of the invention increase to permit tubes that have a smooth interior surface to be used for the tubes 5 of the enclosing walls 4 despite the reduced working medium mass flow densities of about 400 to 1200 kg/m2s. Because of the reduced working medium mass flow densities, an improved natural circulation characteristic is achieved within the evaporator heating surface, which means that in the case of potential local excess heating, the working medium flow rate also increases here, so that safe tube cooling is ensured. The use of tubes 5 having a smooth inner surface, also referred to for short as smooth tubes, has a number of advantages over tubes having inner ribs such as are used with low mass flow densities. For one thing, smooth tubes are significantly less expensive than internally ribbed tubes; moreover, they have shorter delivery times, can be supplied in substantially more different sizes, and are generally more available, since internally ribbed tubes usually are merely available as custom manufactured parts; furthermore, smooth pipes are significantly easier to deal with in assembly. Moreover, smooth tubes have a significantly lower working medium pressure loss due to friction compared with internally ribbed tubes, which has a positive effect on the uniform distribution of the working medium among the individual tubes 5, as well as a reduction of the feed pump capacity of continuous steam generator 1. In order to increase the continuous steam generator process efficiency and, thus, to reduce the hazardous emissions that are caused by the steam generator firing system and that are released into the atmosphere, continuous steam generators 1 are being operated with increasing frequency in the supercritical range-in other words, at a steam pressure of over 220 bar as well as in sliding pressure between the supercritical and subcritical pressure (the operating pressure of the steam generator slides within the load range of the continuous steam generator—for example, between 20 to 100% load). In the case of a continuous steam generator operating pressure of, for example, 270 bar at full load, the steam generator reaches the critical pressure range at a partial load of about 70% and is operated subcritically below this partial load—in other words, in the partial load range roughly below 70% a 2-phase mixture occurs in the evaporator during the evaporating process. The solution in accordance with the invention referred to above ensures that within the vaporization heating surface (enclosing walls 4 and heating surfaces 8) no demixing of the steam and water occurs. This is further supported by the advantageous configuration-of the continuous steam generator 1 of the invention because the flow of working medium through tubes 5, 9 of the enclosing walls 4 and the heating surfaces 8 takes place without the assistance of intermediate collectors. The additional heating surfaces 8 used in the fluidized-bed combustion chamber 3 are so-called bulkhead heating surfaces. Bulkhead heating surfaces are self-contained plate-like heating surfaces (in other words, the individual tubes 9 that are located next to each other are connected to each other by means of webs 22—a welded tube-web-tube combination-to form a bulkhead), in contrast to bundle-type heating surfaces, which are designed in an open configuration (in other words, the individual tubes located next to each other are not connected to each other by means of webs). The heating surfaces 8 are essentially disposed vertically within the combustion chamber 3, and the tubes 9 contained therein also extend in an essentially vertical direction. In accordance with the invention, and depending on the combustion chamber design, the heating surfaces 8 either extend between the combustion chamber base 4.1 or between the upper edge of the funnel 24 and the combustion chamber cover 4.3. In this way, they, together with the enclosing wall 4, can be fully used to achieve parallel flow of the entire working medium that is to be vaporized. Thus, the heating surfaces 8 begin in the lower area of the fluidized-bed combustion chamber 3, essentially at the combustion chamber base or at the funnel lower edge 4.1 in a combustion chamber 3 having a funnel 6 (FIG. 2) and a central position of the heating surfaces 8 within the combustion chamber 3 or on the funnel upper edge 24 in a combustion chamber 3 having two funnels 7 (FIG. 3) as well as a centered arrangement of the heating surfaces, and it terminates [sic: they terminate] in the upper area of the fluidized-bed chamber 3 essentially at the combustion chamber cover 4.3. In order to attach the individual heating surfaces 8, said surfaces may, for example, be welded together with the combustion chamber base 4.1 or the upper edge of the funnel 24 and the combustion chamber cover 4.3. If more than two funnels are to be provided in the lower area of the combustion chamber 3, the heating surfaces 8 can be integrated into the design in the logically corresponding manner. The parallel feeding of the heating surfaces as well as of the enclosing wall 4 is carried out by collectors (not shown) by means of which the working medium that is to be vaporized is fed from below to the aforesaid heating surfaces. If the heating surfaces 8 with a combustion chamber 3 having two funnels 7 as shown in FIG. 3 do not begin until the upper edge of the funnel or at the yoke of the funnel 24, said heating surfaces 8 can be supplied with working medium via the funnel enclosing walls 4. A separate parallel feeding of the heating surfaces 8 is also possible. The heating surfaces 8 may be heated on one or two sides. In the case of heating surfaces that are heated on two sides or in the case of bulkhead heating surfaces 8, it is advantageous to configure the heating surfaces 8 with tubes 9 that have internal ribs in order to ensure reliable cooling of the tube 9 in the partial load range of the continuous steam generator 1 and in order to prevent the boiling crises or DNBs (departures from nucleate boiling) and drying or dry out in the evaporator tube, something which could occur as a result of the additional heating of the heating surface 8 from both sides. One advantageous embodiment of the solution in accordance with the invention provides for heating the heating surfaces 8 disposed inside the fluidized-bed combustion chamber 3 on one side. FIG. 6 shows a preferred embodiment of a heating surface 8 heated on one side. This heating surface 8 comprised an inner space 23 on the periphery side, and it is designed in a box shape, which is why the heating surface 8 is also called a box-shaped heating surface or a box bulkhead(s) 8 in the further description. FIG. 6 shows a preferred embodiment of the box-shaped heating surface 8 having a rectangular cross section. The box bulkhead 8 of FIG. 6 has four side walls consisting of welded membrane tube walls that are welded together at the corners, and the membrane tube walls are formed of tubes 9 and webs 22. This results in a box having a tube-web-tube design or combination that is welded together to be gas tight. Instead of the rectangular design of the box-shaped heating surface 8 shown on the cross-sectional side in FIG. 6, said heating surface can also be designed with a different cross section—for example, it can be n-cornered (at least three-cornered), round, etc. In other words, in this case the inner space 23 that is enclosed by the box-shaped heating surface 8 has an n-cornered or round cross section. Because of the vertical arrangement of the heating surfaces 8 and thus also of the tubes 9 as well as the vertical tubes 5 of the enclosing walls 4, the tubes 5, 9 provide as few possible locations for corrosive attack as possible to the upward flowing stream of gas and particles that is present in the combustion chamber 3. In order to protect the tubes 5, 9 in the lower area of the combustion chamber or in the funnel area 6, 7 from the high transverse or turbulence flows of the stream of gas and particles in the fluidized-bed, said tubes are provided with a fire-proof covering 25. A preferred embodiment of the invention in FIGS. 7 to 9 provides the following: The tubes 9 of the heating surface 8, which is provided with a fire-proof covering 25, and which is located in the combustion chamber funnel area 6, 7, are bent inward in the transition area 26 between the covered and the non-covered heating surface area 27 and in the area of the inner space 23, and the front edges of the fireproof covering 25 and of the non-covered areas 27 of the heating surfaces 8 are configured in a vertical direction aligned with each other. This measure prevents erosion attack points to form in the transition area 26 on the tubes 9 for turbulent flows of the gas and particle stream. As a result of the fireproof covering 25 of the tubes 5, 9 in the funnel area 6, 7 the lengths of the tubes 5, 9 are essentially equally heated within the combustion chamber 3. The box-shaped heating surfaces 8, that extend across a length L and across their cross-section across a width B and a depth T, and in the preferred embodiment they have dimensions of approximately 1.4 to 4.0 m across the width B, approximately 0.1 to 1.0 m across the depth T, and approximately 20 to 50 m across the length L. This also permits the combustion chambers 3 of larger continuous steam generators 1 to be properly equipped. The tubes 9 used for the box-shaped heating surfaces 8 possess diameters between 20 mm and 70 mm in a preferred embodiment. The manufacturing of the box-shaped heating surfaces 8 can be accomplished using the same conventional materials and manufacturing techniques that are used to manufacture steam generators. LIST OF REFERENCE NUMBERS 1 Continuous steam generator 2 Circulating fluidized-bed firing system 3 Fluidized-bed combustion chamber 4 Enclosing walls 4.1 Combustion chamber bottom or funnel lower edge 4.2 Combustion chamber side wall 4.3 Combustion chamber top 5 Tube 6 Funnel, single-leg 7 Funnel, pant-leg 8 Heating surface 9 Tube 10 Fuel feed 11 Fluidization gas feed 12 Flue gas opening or outlet 13 Exhaust gas line 14 Centrifugal precipitator 15 Return line 16 Exhaust gas line 17 Second flue gas stack 18 Eco heating surface 19 Superheater heating surface 20 Temporarily superheated heating surface 21 Web in enclosing wall 22 Web in heating surface 23 Innerspace 24 Funnel upper edge 25 Heat-proof covering 26 Transition area 27 Uncovered area of the heating surface
20051011
20080219
20060615
59019.0
F23C1000
0
WILSON, GREGORY A
CONTINUOUS STEAM GENERATOR WITH CIRCULATING ATMOSPHERIC FLUIDISED-BED COMBUSTION
UNDISCOUNTED
0
ACCEPTED
F23C
2,005
10,536,025
ACCEPTED
Semiconductor device, wiring substrate, and method for manufacturing wiring substrate
The reliabilities of a wiring substrate and a semiconductor apparatus are improved by reducing the internal stress caused by the difference of thermal expansion coefficients between a base substrate and a semiconductor chip. A wiring layer (5) is provided on one surface of a silicon base (3). An electrode as the uppermost layer of the wiring layer (5) is provided with an external bonding bump (7). A through-electrode (4) is formed in the base (3) for electrically connecting the wiring layer (5) and an electrode terminal. The electrode terminal on the chip mounting surface is bonded to an electrode terminal of a semiconductor chip (1) by an internal bonding bump (6). The thermal expansion coefficient of the silicon base (3) is equivalent to that of the semiconductor chip (1) and not more than that of the wiring layer (5).
1. A semiconductor apparatus in which a semiconductor chip is mounted on a wiring substrate with Flip-Chip, wherein the wiring substrate comprising: a base substrate; a wiring layer having an insulating layer and a wiring formed on a wiring layer formation surface which is one surface of the base substrate; an electrode formed on a chip mounting surface which is a backside of the wiring layer formation surface of the base substrate; and a through-electrode formed on the base substrate electrically connecting the wiring layer formed on the wiring layer formation surface and the electrode formed on the chip mounting surface, wherein a thermal expansion coefficient of the base substrate is equal to a thermal expansion coefficient of the semiconductor chip, or less than a thermal expansion coefficient of the wiring layer, wherein the semiconductor chip is bonded to the chip mounting surface with face-down. 2. A semiconductor apparatus according to claim 1, wherein a material of the base substrate is any one of a silicon, a ceramic, and a photosensitive glass. 3. A semiconductor apparatus according to claim 1, wherein a reinforcing frame is stuck at least on a part of outer part of the chip mounting position of the chip mounting surface. 4. A semiconductor apparatus according to claim 3, wherein a thermal expansion coefficient of the reinforcing frame is equal to the thermal expansion coefficient of the semiconductor chip, or less than the thermal expansion coefficient of the wiring layer. 5. A semiconductor apparatus according to claim 1, wherein a thickness of the base substrate, at least a part of outer part of the semiconductor chip mounting position at the chip mounting surface, is thicker than the semiconductor chip mounting position at the chip mounting surface. 6. A semiconductor apparatus according to claim 1, wherein a functional element is formed on at least any one of the wiring layer formation surface and the wiring layer. 7. A semiconductor apparatus according to claim 1, wherein the thermal expansion coefficient of the semiconductor chip is smaller than a thermal expansion coefficient of the wiring layer. 8. A wiring substrate which mounts a semiconductor chip with Flip-Chip, wherein the wiring substrate comprising: a base substrate; a wiring layer having an insulating layer and a wiring formed on a wiring layer formation surface which is one surface of the base substrate; an electrode formed on a chip mounting surface which is a backside of the wiring layer formation surface of the base substrate; and a through-electrode formed on the base substrate electrically connecting the wiring layer formed on the wiring layer formation surface and the electrode formed on the chip mounting surface, wherein a thermal expansion coefficient of the base substrate is equal to a thermal expansion coefficient of the semiconductor chip, or less than a thermal expansion coefficient of the wiring layer, 9. A wiring substrate according to claim 8, wherein a material of the base substrate is any one of a silicon, a ceramic, and a photosensitive glass. 10. A wiring substrate according to claim 8, wherein a reinforcing frame is stuck at least on a part of outer part of the chip mounting position of the chip mounting surface. 11. A wiring substrate according to claim 10, wherein a thermal expansion coefficient of the reinforcing frame is equal to the thermal expansion coefficient of the semiconductor chip, or less than the thermal expansion coefficient of the wiring layer. 12. A wiring substrate according to claim 8, wherein a thickness of the base substrate, at least a part of outer part of the semiconductor chip mounting position at the chip mounting surface, is thicker than the semiconductor chip mounting position at the chip mounting surface. 13. A wiring substrate according to claim 8, wherein a functional element is formed on at least any one of the wiring layer formation surface and the wiring layer. 14. A wiring substrate according to claim 8, wherein the thermal expansion coefficient of the semiconductor chip is smaller than a thermal expansion coefficient of the wiring layer. 15. A method for manufacturing a wiring substrate which comprises a base substrate and a wiring layer having an insulating layer and a wiring formed on a wiring layer formation surface, which is one surface of the base substrate, and mounts a semiconductor chip with Flip-Chip, the method comprising steps of: forming a half-through-hole from the wiring layer formation surface of the base substrate; forming a first electrode on the wiring layer formation surface by burying the half-through-hole with an electrically conductive material; forming the wiring layer on the wiring layer formation surface; and forming a second electrode for mounting the semiconductor chip by exposing the half-through-hole through thinning the base substrate from a backside of the wiring layer formation surface. 16. A method for manufacturing a wiring substrate according to claim 15, further comprising a step of: thinning the base substrate by maintaining a step between at least one part of outer part of a semiconductor chip mounting position and the other part of the semiconductor chip mounting position, by making a work amount smaller at least at the one part of outer part of the semiconductor chip mounting position than the other part of the semiconductor chip mounting position. 17. A method for manufacturing a wiring substrate according to claim 15, further comprising a step of: forming a functional element at a process forming the wiring layer. 18. A method for manufacturing a wiring substrate which comprises a base substrate and a wiring layer formed on a wiring layer formation surface, which is one surface of the base substrate, and mounts a semiconductor chip with Flip-Chip, the method comprising steps of: forming the wiring layer on the wiring layer formation surface of the base substrate; forming a through-hole which penetrates only the base substrate from a backside of the wiring layer formation surface of the base substrate; and forming an electrode for mounting the semiconductor chip at the backside of the wiring layer formation surface by burying the through-hole with an electrically conductive material. 19. A method for manufacturing a wiring substrate according to claim 18, further comprising a step of: thinning the base substrate by maintaining a step between at least one part of outer part of a semiconductor chip mounting position and other part of the semiconductor chip mounting position, by making a work amount smaller at least at the one part of outer part of the semiconductor chip mounting position than the other part of the semiconductor chip mounting position. 20. A method for manufacturing a wiring substrate according to claim 18, further comprising a step of: forming a functional element at a process forming the wiring layer.
FIELD OF THE INVENTION The present invention relates to a semiconductor apparatus, a wiring substrate for the semiconductor apparatus and a method for manufacturing the wiring substrate, and, more particularly to a Flip-Chip type semiconductor apparatus which is a face-down type, the wiring substrate for the Flip-Chip type semiconductor apparatus and a manufacturing method for the wiring substrate. BACKGROUND OF THE INVENTION All of patents, patent applications, patent publications, scientific articles and the like, which will hereinafter be cited or identified in the present application, will hereby be incorporated by references in their entirety in order to describe more fully the state of the art, to which the present invention pertains. Recently, for improving mounting density of a semiconductor package, shrinkage, miniaturization, and pin-multiplication of the package has been progressed. Aligning electrode terminal in the area is an effective technology against the shrinkage and pin-multiplication, while maintaining a wide pitch between electrode terminals. In the second mounting for bonding the semiconductor package and a motherboard, this technology means a Ball Grid Array type of semiconductor packaging technology which bonds the electrode to the motherboard with solder bumps arranged on an interposer substrate. On the other hand, in the first mounting for bonding a semiconductor chip and the interposer substrate, this means a Flip-Chip bonding technology for bonding the both by area aligning, for example, the solder bumps or gold bumps on a functional surface of the semiconductor chip. FIG. 1 is a cross sectional view showing a structure of conventional semiconductor apparatus. A semiconductor apparatus, which uses the packaging technology like the above and the Flip-Chip bonding technology, is a Flip-Chip Ball Grid Array (FCBGA) shown in FIG. 1. This has advantages for the shrinkage, miniaturization, and pin-multiplication of the package, as well as having a low wiring resistance compared with a wire bonding type of semiconductor package which bonds the semiconductor chip and the interposer substrate with a gold wire, thereby suitable for high speed operation. Therefore, an increase of the technology application is being expected. A material of the interposer substrate is divided into a resin material and a ceramic material. The resin material having advantages in manufacturing cost and in electrical characteristics has been mainly used. An example using the Flip-Chip bonding technology has been disclosed in Japanese Laid-Open Patent Publication No. 08-167630, in which a structure forming a wiring in a polymer material having a low thermal expansion coefficient close to that of silicon, and bonding a chip and the wiring with a through-hole is shown. Since a mounting area of this structure is decreased compared with the wire bonding, as well as shortening a bonding distance, and by using a material having a thermal expansion coefficient close to that of silicon, a thermal stress is also relaxed. Up to now, a development of LSI has been carried out based on a scaling rule, in which if a dimension of a transistor is shrunk by 1/k, the density of the LSI becomes k2 times and an operation speed becomes k times. With a progress of the shrinkage and a demand for high speed operation, so-called, RC delay due to increase in a wiring resistance (R) and a capacitance (C) between wirings (hereinafter, referred to as wiring capacitance) has become not negligible. Therefore, employments of Cu as a wiring material for decreasing the wiring resistance and a low dielectric film (Low-k film) for an interlayer dielectric film for decreasing the wiring capacitance are supposed to be promising. In addition, for stable operation of LSI at high frequency region, a stabilization of power voltage and an arrangement of decoupling capacitor against a high frequency noise are essential. Therefore, a capacitor apparatus, which has a large capacitance formed on a silicon having a through-hole, or on a substrate composed of insulating film containing silicon, or on a sapphire substrate, and a module mounting the capacitor apparatus have been proposed. This is disclosed in Japanese Laid-Open Patent Publication No. 2002-008942. In addition, because of high-scale integration of LSI and progress of pin-multiplication due to development of System-On-Chip technology configuring a system by forming, for example, various functional elements and memories on a single chip, a semiconductor chip still has a tendency to grow in size even after compensating contribution of the shrinkage and miniaturization by the electrode area alignment of the Flip-Chip. However, according to the conventional technology, in the structure of Flip-Chip type of semiconductor apparatus shown in FIG. 1, when a resin substrate is used for the interposer substrate, a linear expansion coefficient of the resin substrate is around 15 ppm/C in contract with 2.6 ppm/C of that of semiconductor chip of which base material is mainly silicon. The difference is large, thereby causing a large internal stress within the semiconductor apparatus by the difference of thermal expansion coefficient between them. Currently, the reliability of the semiconductor apparatus is maintained by filling a resin in a space at bonding part between the semiconductor chip and the interposer substrate. However, by increase in internal stress due to growing in size of semiconductor chip according to increase of the number of external terminal in a future, it is predicted to become difficult to maintain the reliability. In the above-described Japanese Laid-Open Patent Publication No. 2002-008942, the semiconductor chip is bonded on an organic layer forming a capacitor. Then, the issue of thermal stress concentration due to the difference of the expansion coefficient has not been solved. In addition, including the bonding structure disclosed in Japanese Laid-Open Patent Publication No. 167630, the reliability of package mounted on the interposer substrate, of which thermal expansion coefficient is matched to that of silicon, is decreased due to an internal stress caused by the difference of thermal expansion coefficient when the package is mounted on a motherboard. Furthermore, a dielectric constant of Low-k film, which is being supposed to be applied as a countermeasure for the RC delay, is decreased by doping, for example, fluorine, hydrogen, and organics in a silicon oxide (SiO2) film, or making the material porous. Then, it is well known that the Low-k film is fragile compared with a conventional interlayer dielectric film such as silicon oxide film. This means a decrease in allowable limit of the internal stress caused by the difference of linear expansion coefficient between the semiconductor chip and the interposer substrate, and may cause a reliability issue when the shrinkage and pin-multiplication are further progressed in a future. Moreover, recently, there is a tendency to replace a Tin-Lead solder, which has conventionally been used so far for the solder material, with a Lead-free solder. Electronics industries have a plan to abolish completely a solder containing Lead. The Lead-free solder, in which Tin is a base material, has a substantially small stress relaxation effect compared with the Tin-Lead solder, which has a stress relaxation effect to decrease a stress generated at the bonding part through composition change of solder itself. Accordingly, the internal stress increases, and may cause a reliability issue when the shrinkage and pin-multiplication are further progressed in a future. DISCLOSURE OF THE INVENTION It is therefore an object of the present invention to provide a semiconductor apparatus which is free from the above issues. It is another object of the present invention to provide a semiconductor apparatus, in which an internal stress caused by the difference of thermal expansion coefficients in a wiring substrate is decreased, thereby increasing the reliability and capable of responding to further shrinkage and pin-multiplication. It is a further object of the present invention to provide a wiring substrate of semiconductor apparatus which is free from the above issues. It is a still further object of the present invention to provide a wiring substrate of semiconductor apparatus, in which an internal stress caused by the difference of thermal expansion coefficients in a wiring substrate is decreased, thereby increasing the reliability and capable of responding to further shrinkage and pin-multiplication. It is a yet further object of the present invention to provide a method for manufacturing a wiring substrate of semiconductor apparatus which is free from the above issues. It is an additional object of the present invention to provide a method for manufacturing a wiring substrate of semiconductor apparatus, in which an internal stress caused by the difference of thermal expansion coefficients in a wiring substrate is decreased, thereby increasing the reliability and capable of responding to further shrinkage and pin-multiplication. According to a first aspect of the present invention, the present invention provides a semiconductor apparatus in which a semiconductor chip is mounted on a wiring substrate with Flip-Chip, wherein the wiring substrate comprising: a base substrate; a wiring layer having an insulating layer and a wiring formed on a wiring layer formation surface which is one surface of the base substrate; an electrode formed on a chip mounting surface which is a backside of the wiring layer formation surface of the base substrate; and a through-electrode formed on the base substrate electrically connecting the wiring layer formed on the wiring layer formation surface and the electrode formed on the chip mounting surface, wherein a thermal expansion coefficient of the base substrate is equal to a thermal expansion coefficient of the semiconductor chip, or less than a thermal expansion coefficient of the wiring layer, wherein the semiconductor chip is bonded to the chip mounting surface with face-down. In addition, it is favorable that the thermal expansion coefficient of the semiconductor chip is smaller than that of the wiring layer. With the present configuration, since the semiconductor chip is mounted on the base substrate of the wiring substrate, the difference of thermal expansion between the semiconductor chip and the base substrate is suppressed. Therefore, a bonding reliability between the semiconductor chip and the wiring substrate is improved. When the present configuration is mounted on a motherboard substrate, since the wiring layer of the wiring substrate faces to the motherboard substrate and the wiring layer thereof exists between the motherboard substrate and the base substrate, a stress of the wiring layer caused by the difference of thermal expansion between the motherboard substrate and the base substrate can be relaxed, thereby resulting in increase of electric bonding reliability. In the explanation, a motherboard was used as an example for explaining a substrate on which the wiring substrate of the present invention is mounted, but not limited to the motherboard. Any substrate, on which the wiring substrate of the present invention is mounted and which is different from the base substrate, may be possible. In the present embodiment, a support means a substrate which is different from the base substrate, and on which the wiring substrate of the present invention is mounted. The base substrate may be any one of a silicon, a ceramic, and a photosensitive glass. A reinforcing frame may be stuck at least on a part of outer part of the chip mounting position of the chip mounting surface. In addition, it is favorable that the thermal expansion coefficient of the reinforcing frame is equal to the thermal expansion coefficient of the semiconductor chip, or less than that of the wiring layer. A thickness of the base substrate, at least one part of outer part of the semiconductor chip mounting position at the chip mounting surface, may be thicker than the other part of the semiconductor chip mounting position at the chip mounting surface. A functional element may be formed on at least any one of the wiring layer formation surface and the wiring layer. According to a second aspect of the present invention, the present invention provides a wiring substrate which mounts a semiconductor chip with Flip-Chip, wherein the wiring substrate comprising: a base substrate; a wiring layer having an insulating layer and a wiring formed on a wiring layer formation surface which is one surface of the base substrate; an electrode formed on a chip mounting surface which is a backside of the wiring layer formation surface of the base substrate; and a through-electrode formed on the base substrate electrically connecting the wiring layer formed on the wiring layer formation surface and the electrode formed on the chip mounting surface, wherein a thermal expansion coefficient of the base substrate is equal to a thermal expansion coefficient of the semiconductor chip, or less than a thermal expansion coefficient of the wiring layer. It is favorable that the thermal expansion coefficient of the semiconductor chip is smaller than that of the wiring layer. With the present configuration, the above-described advantages are obtained for the semiconductor apparatus according to the first aspect of the present invention. A material of the base substrate may be composed of any one of a silicon, a ceramic, and a photosensitive glass. A reinforcing frame may be stuck at least on a part of outer part of the chip mounting position of the chip mounting surface. It is favorable that a thermal expansion coefficient of the reinforcing frame is equal to that of the semiconductor chip, or less than that of the wiring layer. A thickness of the base substrate, at least one part of outer part of the semiconductor chip mounting position at the chip mounting surface, may be thicker than the other part of the semiconductor chip mounting position at the chip mounting surface. A functional element may be formed on at least any one of the wiring layer formation surface and the wiring layer. According to a third aspect of the present invention, the present invention provides a method for manufacturing a wiring substrate which comprises a base substrate and a wiring layer having an insulating layer and a wiring formed on a wiring layer formation surface, which is one surface of the base substrate, and mounts a semiconductor chip with Flip-Chip, the method comprising steps of: forming a half-through-hole from the wiring layer formation surface of the base substrate; forming a first electrode on the wiring layer formation surface by burying the half-through-hole with an electrically conductive material; forming the wiring layer on wiring layer formation surface; and forming a second electrode for mounting the semiconductor chip by exposing the half-through-hole through thinning the base substrate from a backside of the wiring layer formation surface. The method for manufacturing a wiring substrate may further comprise a step of thinning the base substrate by maintaining a step between at least one part of outer part of a semiconductor chip mounting position and other part of the semiconductor chip mounting position, by making a work amount smaller at least at the one part of outer part of the semiconductor chip mounting position than the other part of semiconductor chip mounting position. The method for manufacturing a wiring substrate may further comprise a process of forming a functional element at a process which forms the wiring layer. According to a fourth aspect of the present invention, the present invention provides a method for manufacturing a wiring substrate which comprises a base substrate and a wiring layer formed on a wiring layer formation surface, which is one surface of the base substrate, and mounts a semiconductor chip with Flip-Chip, the method comprising steps of: forming the wiring layer on wiring layer formation surface of the base substrate; forming a through-hole which penetrates only the base substrate from a backside of the wiring layer formation surface of the base substrate; forming an electrode for mounting the semiconductor chip at the backside of the wiring layer formation surface by burying the through-hole with an electrically conductive material. The method for manufacturing a wiring substrate may further comprise a step of thinning the base substrate by keeping a step between at least one part of outer part of a semiconductor chip mounting position and the other part of semiconductor chip mounting position, by making a work amount smaller at least at the one part of outer part of the semiconductor chip mounting position than the other part of semiconductor chip mounting position. The method for manufacturing a wiring substrate may further comprise a process of forming a functional element at a process which forms the wiring layer. According to the aspects of the first to the fourth embodiments explained in the above, in the semiconductor apparatus, the wiring substrate, and the method for manufacturing the wiring substrate, since the semiconductor chip is bonded to the base substrate of the wiring substrate which has a thermal expansion coefficient close to that of the semiconductor chip, an internal stress caused by mismatch of the thermal expansion coefficient between them is substantially decreased. In addition, a change of an internal stress caused by mounting the semiconductor apparatus on a motherboard and by temperature change under operating circumstances is also decreased, thereby resulting in increase in the reliability. Accordingly, it becomes possible to overcome a decrease of allowance level of the internal stress due to, for example, growing in size of semiconductor chip according to increase in the number of external terminal, due to application of fragile Low-k film to the interlayer dielectric film, and due to a decrease of stress relaxation by using an environmentally-friendly lead-free solder. In addition, since the wiring layer of the wiring substrate is formed on a rigid base substrate, it is suitable for forming a fine wiring pattern. Furthermore, since most of manufacturing processes of the semiconductor apparatus can be implemented with a wafer, a high production efficiency is achieved, and thereby resulting in a low cost manufacturing. Further, a stress is caused by the difference of thermal expansion coefficient between the base substrate and a resin material used for the interlayer dielectric film substantially occupying the wiring layer, which is formed at a backside of the chip mounting surface of the wiring substrate. However, by sticking a reinforcing frame partially or entirely to the outer part of the mounting position of the semiconductor chip at the chip mounting surface, the rigidity of the base substrate is maintained even if the thickness of base substrate at the semiconductor chip mounting position is substantially thinned. As a result, it becomes possible to improve the mountability and the reliability by suppressing warpage of the wiring substrate. Moreover, a stress is caused by the difference of thermal expansion coefficient between the base substrate and a resin material used for the interlayer dielectric film substantially occupying the wiring layer, which is formed at a backside of the chip mounting surface of the wiring substrate. However, by increasing the thickness partially or entirely of the outer part of the mounting position of the semiconductor chip at the chip mounting surface, the rigidity of the base substrate is maintained even if the thickness of base substrate at semiconductor chip mounting position is substantially thinned. As a result, it becomes possible to increase the mountability and the reliability by suppressing warpage of the wiring substrate, as well as increasing simplicity of the process by simultaneous formation of the surrounding step when the base substrate is thinned. Then, the cost can be down. In addition, by disposing, for example, a capacitor, a resistor, and a inductor on the surface of base substrate for forming a wiring layer, or in the wiring layer, an optimum arrangement of functional elements, for example, the capacitor, the resistor and the inductor, is achieved at each optimum position in the wiring substrate. As a result, improvements of high frequency characteristics and a high performance can be achieved. Shrinkage of the mounting area and an increase of design freedom are also achieved. Furthermore, by stacking the wiring layer on the base substrate which has a small thermal expansion coefficient and a high rigidity, it becomes possible to form a fine wiring pattern compared with the case where the wiring layer is stacked on a resin-based base material. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross sectional view showing a structure of conventional semiconductor apparatus. FIG. 2A is a cross sectional view showing a structure of first example of semiconductor apparatus in the first embodiment of the present invention. FIG. 2B is a cross sectional view showing a structure of second example of semiconductor apparatus in the first embodiment of the present invention. FIG. 2C is a cross sectional view showing a structure of third example of semiconductor apparatus in the first embodiment of the present invention. FIG. 3A to 3F are cross sectional views of a wiring substrate at each process of a method for manufacturing the wiring substrate of the semiconductor apparatus in the first embodiment of the present invention. FIG. 4 is a cross sectional view showing a structure of semiconductor apparatus in the second embodiment of the present invention. FIG. 5A to 5E are cross sectional views of a wiring substrate at each process of a method for manufacturing the wiring substrate of the semiconductor apparatus in the third embodiment of the present invention. FIG. 6 is a cross sectional view showing a structure of semiconductor apparatus in the fourth embodiment of the present invention. FIG. 7A to 7D are cross sectional views of a semiconductor apparatus at each assembly process after Flip-Chip bonding process of the semiconductor apparatus in the fourth embodiment of the present invention. PREFERRED EMBODIMENTS OF THE PRESENT INVENTION First Embodiment Embodiments of the present invention will be explained in detail by referring to figures. FIG. 2A is a cross sectional view showing a structure of a first example of a semiconductor apparatus in the first embodiment of the present invention. FIG. 2B is a cross sectional view showing a structure of a second example of a semiconductor apparatus in the first embodiment of the present invention. FIG. 2C is a cross sectional view showing a structure of a third example of a semiconductor apparatus in the first embodiment of the present invention. FIGS. 3A to 3F are cross sectional views of a wiring substrate at each process of a method for manufacturing the wiring substrate of the semiconductor apparatus in the first embodiment of the present invention. In the first embodiment, as shown in FIG. 2A, a single or plural wiring layers 5 is formed on one side of base substrate 3 which is composed of silicon as a wiring substrate 2, and on an electrode at the top layer of wiring layer 5, bump 7 for external bonding is formed. In base substrate 3, through-electrode 4 is formed for electrically connecting wiring substrate 5 and an electrode terminal on the other side of base substrate 3 on which wiring layer 5 is not formed (hereinafter, referred to as chip mounting surface). The electrode terminal on the chip mounting surface and semiconductor chip 1 are electrically and mechanically bonded with internal bonding bump 6 which is composed of, for example, Tin-Lead solder. A thermal expansion coefficient of base substrate 3, which is composed of silicon, is substantially equal to that of semiconductor chip 1 and less than that of wiring layer 5. Then, a stress caused by the difference of thermal expansion coefficient between semiconductor chip 1 and base substrate 3 is substantially small. Therefore, as shown in FIG. 2A, it is not always necessary to bury a space between semiconductor chip 1 and wiring substrate 2 with mold compound such as an epoxy-based resin for partially supporting a bonding strength between them. As shown in FIG. 2B, it may be possible to bury the space between semiconductor chip 1 and wiring substrate 2 with mold compound 8 without putting overstress to the bonding part. It may also be possible, as shown in FIG. 2C, to bury only a perimeter of semiconductor chip 1 with mold compound 8. Next, a method for manufacturing the wiring substrate in a first embodiment will be explained by referring to FIGS. 3A to 3F. As shown in FIG. 3A, after forming a silicon oxide film (SiO2 film) of insulating layer 11a on a silicon wafer of base substrate 3, insulating layer 11a is bored by pattering a predetermined hole position with photolithography. Then, a half-through-hole of 110 μm in depth is formed with reactive ion etching (RIE). A diameter of the half-through-hole was set at 80 μm. A distance between the holes was 150 μm. The RIE is a method for removing the oxide through reactions of radical atom in the reactive gas plasma. It is possible to conduct anisotropic etching with RIE like dry etching. Next, as shown in FIG. 3B, a TEOS (Si(OC2H5)4) film of insulating layer 11b is formed on a surface of the half-through-hole with plasma CVD, followed by a cupper (Cu) film formation of a plating seed layer with sputtering. When a film is formed by CVD on whole surface of a hole which has a substantially deep depth as the present structure, it is difficult to form the film on a side wall of the hole due to a shape of the hole thereof. Therefore, the TEOS film, which has good step coverage from the beginning of film formation, was selected as insulating layer 11b. After that, the half-through-hole was filled with conductor 12 of Cu with plating of a damoscene method, and chemical-mechanical polished (CMP) for planarization of conductor 12. Other than the damoscene method, a method filling the conductor with CVD is also possible. Other than the metal, an electrically conductive resin may also be usable for the conductor. Next, as shown in FIG. 3C, after patterning the CMP treated Cu film at upper layer with etching, wiring layer 5 is formed with a buildup method for forming a multilayer wiring layer by sequentially repeating formation of interlayer dielectric film 14, formation of a via hole, desmear treatment, and formation of wiring 13. In FIG. 3C, an example of wiring layer with three levels is shown, but not limited to three levels. An increase in operation speed can be expected by fabricating functional apparatus, for example, a capacitor, a resistor, and an inductor during formation of wiring layer 5. For example, a decoupling capacitor function can be obtained by inserting a parallel plate capacitor formed by sandwiching ferroelectric material, which is formed as a part of interlayer dielectric film 14, with a power line and a ground line within wiring layer 5. After that, the surface is covered with solder resist, such as polyimide, except electrode 16a of the top wiring layer. Then, a structure at an external bonding bump side is completed. Functional elements, for example, a capacitor, a resistor, and an inductor are fabricated in wiring layer 5. It is possible to apply a conventional semiconductor diffusion process for fabricating the functional elements since they are formed on a silicon which is able to form a functional element such as a capacitor by applying a thin film process on the silicon substrate, which has a via buried with conductive material. Therefore, it is possible to achieve a manufacturing line with precise manufacturing and low cost production, for example, through suppressed investment. Next, as shown in FID. 3D, for protecting a surface at a wiring layer formation side, the surface is covered with support 17 before a thinning treatment of silicon. After turning over the silicon wafer, the silicon is thinned from about 700 μm to about 200 μm with mechanical grinding. Then, the silicon is further thinned to about 100 μm with RIE for exposing the half-through-hole. In the first embodiment, a combination of mechanical grinding and RIE has been employed for the thinning considering the manufacturing cost and the manufacturing efficiency. After the mechanical grinding, a strained layer is formed at the surface in general. A micro-crack is also formed in some case. Since there is a possibility that these decrease the reliability, a careful consideration for conditions, for example, on removal rate of the mechanical grinding and the chasing speed, is required. The thinning process can be achieved with only mechanical grinding if it does not effect on the reliability. Next as shown in FIG. 3E, after RIE treatment, a step appears due to the difference of etching rate caused by the difference of material between the through-electrode area and the other area. After that, the cupper is exposed by entirely removing insulating layer 11b with CMP as well as planarizing the RIE treated surface. Then, a SiO2 film of insulating layer 11c is formed on the surface, and patterning is conducted on the film with photolithography. Finally, as shown in FIG. 3F, after forming a second electrode 16b on the opening area of insulating layer 11c, cover film 18 of silicon nitride film (SiN film) is formed. After that, by removing support 17, the wiring substrate is completed. In the first embodiment, SiO2 and SiN have been used for the insulating layers 11a, 11b, 11c, and cover film 18. However, other than the above materials, SiC, SiOF, and SiOC formed with plasma CVD, which is capable of forming a film at substantially low temperature, can also be used for the film. Semiconductor chip 1 is mounted with face-down on wafer shaped wiring substrate 2 which was manufactured through processes shown in FIGS. 3A to 3F. After reinforcing semiconductor chip 1 with mold compound 8 appropriately, semiconductor chip 1 is separated individually, and external bonding bump 7 is formed to complete a semiconductor apparatus. In this manufacturing process, since the wafer shape is maintained until close to the final process, the manufacturing efficiency is high and manufacturing and inspection costs can be cut down. When a chip size of semiconductor chip 1 is over 10×10 mm and the number of external output pin is over 1000, wiring substrate 2 becomes large, such as 40˜50 mm. In this case, the thinned silicon substrate has not a sufficient mechanical strength. Then, there may be a possibility to break wiring substrate 2 during the separation of the chip individually. Therefore, it is favorable to cut wiring substrate 2 after backing up it by taping with stiffener 9 before cutting wiring substrate 2, after thinning the silicon and forming a bonding electrode of the semiconductor chip. In addition, if manufacturing of the wiring substrate and mounting of semiconductor chip can be implemented sequentially, it is favorable to mount semiconductor chip 1 on the wiring substrate as a wafer, and after that, to implement the separation process. In the present invention, a material, which is able to relax the difference of thermal expansion between a supporting substrate exemplified by a motherboard and the wiring substrate, may be used for the insulating layer. It is favorable that the material is selected considering expansion coefficients of the supporting substrate and the base substrate. Optimally, an expansion coefficient of the material for the insulating layer is smaller than that of the supporting substrate, and larger than that of the base substrate. In the first embodiment, silicon is used for semiconductor chip 1 and base substrate 3 of wiring substrate 2, but not limited to the silicon. For base substrate 3, a material, of which thermal expansion coefficient is equal to that of semiconductor chip 1 or smaller than that of wiring layer 5, is used. Other than the silicon, for example, ceramics or a photosensitive glass which is able to form a fine hole can be used. If the photosensitive glass is selected as base substrate 3, a through-hole is formed first instead of the half-through-hole. After that, an electrically conductive treatment for both sides of the glass plate and a wiring layer formation are conducted. Practically, by putting a mask which has a pattern for forming a hole on the photosensitive glass, an exposure process with a violet light which includes a predetermined spectrum, and a development process with a heat treatment are conducted. Then, a crystallized part is removed with acid to form base substrate 3 having a through-hole. Second Embodiment FIG. 4 is a cross sectional view showing a structure of semiconductor apparatus in the second embodiment of the present invention. In the second embodiment, in addition to the configuration of the first embodiment, a stiffener 9 of reinforcing frame is stuck at around a mounting surface area of semiconductor chip 1 on base substrate 3 for increasing rigidity of wiring substrate 2. Since the rigidity of wiring substrate 2 can be increased with stiffener 9, it is possible to thin the thickness of a package by thinning base substrate 3, and to provide countermeasures for increasing cooling performance against the increase of power consumption and heat generation of semiconductor chip 1 by attaching heat sink 10 at the bottom of semiconductor chip 1 using stiffener 9. It is also favorable that a thermal expansion coefficient of stiffener 9 is equal to that of semiconductor chip 1, or less than that of wiring layer 5, as well as the case of base substrate 3. Third Embodiment FIG. 5A to 5E are cross sectional views of a wiring substrate at each process of a method for manufacturing a wiring substrate of a semiconductor apparatus in a third embodiment of the present invention. In the first embodiment, wiring layer 5 is formed after forming a half-through-hole in base substrate 3, and burying the half-through-hole with an electrically conductive material. However, in the third embodiment, after forming wiring layer 5 first on base substrate 3, wiring substrate 2 is completed by forming a through-electrode and a backside electrode First, as shown in FIG. 5A, insulating layer 11a and wiring layer 5 are formed on base substrate 3 of silicon having a thickness of 700 μm with the same manufacturing method as the first embodiment. After protecting a surface of wiring layer 5 with support 17, the wafer is turned over and base substrate 3 is thinned to 180 μm from backside with mechanical grinding. Then, a central part of base substrate 3 is thinned to 80 μm with RIE. Although not shown since FIG. 4 is an enlarged illustration, when RIE is conducted, a width of 8.5 mm at peripheral area of the substrate is masked. Accordingly, a step is formed on the surface by further thinning of the central area with RIE. With the above, a thickness of the through-electrode area can be further thinned, while maintaining rigidity of base substrate 3. In this embodiment, an outside dimension of wiring substrate 2 is 30×30 mm, an outside dimension and a thickness of semiconductor chip 1 are 10×10 mm and 700 μm, respectively. In this embodiment, the though-hole part and its surrounding are unified with the same material. However, as with the second embodiment, the rigidity is secured by sticking stiffener 9 around a smooth surface of wiring substrate 2. Next, as shown in FIG. 5B, after forming SiO2 film of insulating layer 11c on a silicon wafer of base substrate 3, insulating layer 11c is bored after pattering a predetermined hole position with photolithography, and a through-hole is formed with RIE for exposing a wiring at the bottom of wiring layer 5. After that, a side wall and an upper surface of the through-hole are insulated with insulating layer 11c of TEOS film. Then, the through-hole is filled with a conductor 12 of Cu with a damoscene method, and chemical-mechanical polished (CMP) for planarization. After that, as shown in FIG. 5D, electrode 16b is formed, and as shown in FIG. 5E, SiN cover film 18 is formed. Accordingly, a wafer shaped wiring substrate 2 is completed. Fourth Embodiment FIG. 6 is a cross sectional view showing a structure of a semiconductor apparatus in a fourth embodiment of the present invention. FIGS. 7A to 7D are cross sectional views of a semiconductor apparatus at an assembly process after Flip-Chip bonding process of the semiconductor apparatus in the fourth embodiment of the present invention. In the fourth embodiment, according to FIG. 6, a central area is thinned by forming a step around base substrate 3. The back side of base substrate 3 is ground after mounting and molding semiconductor chip 1 with mold compound to achieve a thin semiconductor apparatus in total. First, as shown in FIG. 7A, semiconductor chip 1 is bonded with Flip-Chip bonding to a wafer shaped wiring substrate 2, to which support 17 is stuck. Then, as shown FIG. 7B, mold compound 8 is filled in a space between semiconductor 1 and base substrate 3. Mold compound 8 is supplied until the surface of the molded substance is covered with mold compound 8. This is implemented for the purpose of decreasing an effect of damage caused by grinding of the backside of semiconductor chip 1. It is possible to neglect the process, or to change a supply quantity of mold compound 8 arbitrarily if it does not effect on the bonding portion and the apparatus reliability. After that, as shown in FIG. 7C, the backside of semiconductor chip 1 is ground until the thickness becomes about 50 μm. The thickness of the semiconductor apparatus except an external bonding bump is set at about 220 μm. Meanwhile, wiring layer 5 is consist of two layers. Next, as shown in FIG. 7D, the wafer is diced into chips, and support 17 is peeled off. Finally, the external bonding bump is formed with a micro ball mounting method to complete the semiconductor apparatus. For example, a solder paste printing method, an evaporation method, an electrolytic plating and others may be used for forming the external bonding bump. The order of peeling off of the support and the dicing process is arbitrarily changed considering the bump formation method and production efficiency. Fifth Embodiment In the first embodiment, after forming a through-electrode on the base substrate of silicon, a wiring layer is formed and bonded to a support. Then, the silicon is thinned to expose a mounting surface of semiconductor chip 1 to form wiring substrate 2. In the third embodiment, wiring layer 5 is formed on the silicon substrate, and the silicon is thinned from the backside of it. After that, by forming a through-electrode, a mounting surface of semiconductor chip 1 is formed to form wiring substrate 2. In either case, the mounting surface of semiconductor chip 1 is formed at a final process. In a fifth embodiment, a via, which is a though-hole, is formed on base substrate 2 with RIE, followed by formation of an insulating film on the inner wall, filling of a conductor, and planarization with CMP to form a pad for mounting semiconductor chip 1. Then, the pad surface is bonded to a support, followed by arbitrary combination of grinding and RIE to thin the silicon to form a through-electrode. After that, a multi wiring layer and an external terminal are formed to form a wiring substrate. According to this method, a diffusion process technology of semiconductor manufacturing can be applied to, for example, an electrode formation process on a mounting surface of semiconductor chip 1 and a functional element formation process such as a capacitor, which are both required substantially high accuracy, before forming the support and multi wiring layer. In these embodiments, a diameter of the via is set at 80 μm. However, a diameter of 150 μm at boring process for forming the via is acceptable. Even though depending on an alignment pitch of electrodes, a smaller via is favorable from high density point of view. Then, a diameter less than 50 μm is employed. A diameter of 10 μm is achievable by selecting a via formation method. In the process for exposing a via, when the silicon and the conductor filled in the via are processed together with mechanical grounding, the grinding stone is likely to be clogged with the conductor, thereby resulting in rough surface. As a result, the process yield may be decreased. Therefore, it is favorable that a percentage of a via surface within the silicon surface, where is to be ground, is less than 2%. Because of this reason, when extraction of 60 substrates with 4000 pins from 8 inch wafer is layouted, a diameter less than 30 μm is the most suitable for the through-via. However, considering a filling efficiency of the conductive material in the via from filling process point of view, a diameter more than 10 μm is favorable. As explained in the above, according to the present embodiment, since semiconductor chip 1 is bonded to base substrate 3 of wiring substrate 2 which has a thermal expansion coefficient close to that of semiconductor chip 1, an internal stress caused by mismatch of the thermal expansion coefficient between them is substantially decreased. In addition, a change of internal stress caused by mounting a semiconductor apparatus on a motherboard and by temperature change under operating circumstances is also decreased, thereby resulting in increase in reliability. Accordingly, it becomes possible to overcome a decrease of allowance level of the internal stress due to, for instance, growing in size of semiconductor chip 1 according to increase of the number of external terminal, application of fragile Low-k film to an interlayer dielectric film, and decrease of stress relaxation ability by using an environmentally-friendly Lead-free solder. In addition, according to the present embodiment, since wiring layer 5 of wiring substrate 2 is formed on a rigid base substrate 3, it is suitable to form a fine wiring pattern, and most of the manufacturing processes of the semiconductor apparatus can be processed with a wafer. As a result, a high production efficiency and a low cost manufacturing are both can be achieved. Further, according to the present embodiment, a stress is caused by the difference of thermal expansion coefficient between the base substrate and a resin material used for the interlayer dielectric film substantially occupying wiring layer 5, which is formed at backside of the chip mounting surface of wiring substrate 2. However, by sticking a reinforcing frame partially or entirely to the outer part of a mounting position of semiconductor chip 1 at the chip mounting surface, the rigidity of base substrate 3 is maintained even if the thickness of base substrate 3 at the mounting position of semiconductor chip 1 is substantially thinned. Accordingly, it is possible to increase a mountability and a reliability by suppressing warpage of wiring substrate 2. Moreover, according to the present embodiment, a stress is caused by the difference of thermal expansion coefficient between base substrate 3 and a resin material used for the interlayer dielectric film substantially occupying wiring layer 5, which is formed at backside of a chip mounting surface of wiring substrate 2. However, by increasing the thickness partially or entirely of the outer part of the mounting position of semiconductor chip 1 at the chip mounting surface, the rigidity of base substrate 3 is maintained even if the thickness of base substrate 3 at the mounting position of semiconductor chip 1 is substantially thinned. As a result, it is possible to increase the mountability and the reliability by suppressing warpage of wiring substrate 2, as well as increasing simplicity of the process by simultaneously forming a surrounding step when base substrate 3 is thinned. Accordingly, the cost can be down. In addition, according to the present embodiment, by disposing, for example, a capacitor, a resistor, and a inductor on the surface of base substrate 3 for forming a wiring layer, or in wiring layer 5, an optimum arrangement of functional elements, for example, the capacitor, the resistor and the inductor is achieved at optimum position in wiring substrate 5 for each element. As a result, improvements of high frequency characteristics and high functionality can be achieved. Moreover, shrinkage of mounting area and increase of design freedom can be realized. Furthermore, according to the present embodiment, by stacking wiring layer 5 on base substrate 3 which has a small thermal expansion coefficient and high rigidity, it becomes possible to form a fine wiring pattern compared with the case where wiring layer 5 is stacked on a resin-based base material. It is obvious that the present invention is not limited to each embodiment, and the each embodiment may be changed within a technological scope and sprit of the present invention. In addition, the number of components, positions, features, and the like are not limited to the embodiment, and they may be determined based on a practical application of the present invention. The identical elements at each figure are given the same symbols. POSSIBILITY FOR INDUSTRIAL APPLICATION A semiconductor apparatus, a wiring substrate for the semiconductor apparatus, and a method for manufacturing the wiring substrate according to the present invention are applicable to all semiconductor apparatuses and not limited the possibility of application, if the semiconductor apparatus is such that a semiconductor chip is mounted on a wiring substrate with Flip-Chip method. While the present invention has been described by associating with some preferred embodiments and examples, it is to be understood that these embodiments and examples are merely for illustrative of the invention by an example, and not restrictive. While it will be obvious to those skilled in the art that various changes and substitutions by equivalent components and techniques are eased upon reading the specification, it is believed obvious that such changes and substitutions fit into the true scope and spirit
<SOH> BACKGROUND OF THE INVENTION <EOH>All of patents, patent applications, patent publications, scientific articles and the like, which will hereinafter be cited or identified in the present application, will hereby be incorporated by references in their entirety in order to describe more fully the state of the art, to which the present invention pertains. Recently, for improving mounting density of a semiconductor package, shrinkage, miniaturization, and pin-multiplication of the package has been progressed. Aligning electrode terminal in the area is an effective technology against the shrinkage and pin-multiplication, while maintaining a wide pitch between electrode terminals. In the second mounting for bonding the semiconductor package and a motherboard, this technology means a Ball Grid Array type of semiconductor packaging technology which bonds the electrode to the motherboard with solder bumps arranged on an interposer substrate. On the other hand, in the first mounting for bonding a semiconductor chip and the interposer substrate, this means a Flip-Chip bonding technology for bonding the both by area aligning, for example, the solder bumps or gold bumps on a functional surface of the semiconductor chip. FIG. 1 is a cross sectional view showing a structure of conventional semiconductor apparatus. A semiconductor apparatus, which uses the packaging technology like the above and the Flip-Chip bonding technology, is a Flip-Chip Ball Grid Array (FCBGA) shown in FIG. 1 . This has advantages for the shrinkage, miniaturization, and pin-multiplication of the package, as well as having a low wiring resistance compared with a wire bonding type of semiconductor package which bonds the semiconductor chip and the interposer substrate with a gold wire, thereby suitable for high speed operation. Therefore, an increase of the technology application is being expected. A material of the interposer substrate is divided into a resin material and a ceramic material. The resin material having advantages in manufacturing cost and in electrical characteristics has been mainly used. An example using the Flip-Chip bonding technology has been disclosed in Japanese Laid-Open Patent Publication No. 08-167630, in which a structure forming a wiring in a polymer material having a low thermal expansion coefficient close to that of silicon, and bonding a chip and the wiring with a through-hole is shown. Since a mounting area of this structure is decreased compared with the wire bonding, as well as shortening a bonding distance, and by using a material having a thermal expansion coefficient close to that of silicon, a thermal stress is also relaxed. Up to now, a development of LSI has been carried out based on a scaling rule, in which if a dimension of a transistor is shrunk by 1/k, the density of the LSI becomes k2 times and an operation speed becomes k times. With a progress of the shrinkage and a demand for high speed operation, so-called, RC delay due to increase in a wiring resistance (R) and a capacitance (C) between wirings (hereinafter, referred to as wiring capacitance) has become not negligible. Therefore, employments of Cu as a wiring material for decreasing the wiring resistance and a low dielectric film (Low-k film) for an interlayer dielectric film for decreasing the wiring capacitance are supposed to be promising. In addition, for stable operation of LSI at high frequency region, a stabilization of power voltage and an arrangement of decoupling capacitor against a high frequency noise are essential. Therefore, a capacitor apparatus, which has a large capacitance formed on a silicon having a through-hole, or on a substrate composed of insulating film containing silicon, or on a sapphire substrate, and a module mounting the capacitor apparatus have been proposed. This is disclosed in Japanese Laid-Open Patent Publication No. 2002-008942. In addition, because of high-scale integration of LSI and progress of pin-multiplication due to development of System-On-Chip technology configuring a system by forming, for example, various functional elements and memories on a single chip, a semiconductor chip still has a tendency to grow in size even after compensating contribution of the shrinkage and miniaturization by the electrode area alignment of the Flip-Chip. However, according to the conventional technology, in the structure of Flip-Chip type of semiconductor apparatus shown in FIG. 1 , when a resin substrate is used for the interposer substrate, a linear expansion coefficient of the resin substrate is around 15 ppm/C in contract with 2.6 ppm/C of that of semiconductor chip of which base material is mainly silicon. The difference is large, thereby causing a large internal stress within the semiconductor apparatus by the difference of thermal expansion coefficient between them. Currently, the reliability of the semiconductor apparatus is maintained by filling a resin in a space at bonding part between the semiconductor chip and the interposer substrate. However, by increase in internal stress due to growing in size of semiconductor chip according to increase of the number of external terminal in a future, it is predicted to become difficult to maintain the reliability. In the above-described Japanese Laid-Open Patent Publication No. 2002-008942, the semiconductor chip is bonded on an organic layer forming a capacitor. Then, the issue of thermal stress concentration due to the difference of the expansion coefficient has not been solved. In addition, including the bonding structure disclosed in Japanese Laid-Open Patent Publication No. 167630, the reliability of package mounted on the interposer substrate, of which thermal expansion coefficient is matched to that of silicon, is decreased due to an internal stress caused by the difference of thermal expansion coefficient when the package is mounted on a motherboard. Furthermore, a dielectric constant of Low-k film, which is being supposed to be applied as a countermeasure for the RC delay, is decreased by doping, for example, fluorine, hydrogen, and organics in a silicon oxide (SiO2) film, or making the material porous. Then, it is well known that the Low-k film is fragile compared with a conventional interlayer dielectric film such as silicon oxide film. This means a decrease in allowable limit of the internal stress caused by the difference of linear expansion coefficient between the semiconductor chip and the interposer substrate, and may cause a reliability issue when the shrinkage and pin-multiplication are further progressed in a future. Moreover, recently, there is a tendency to replace a Tin-Lead solder, which has conventionally been used so far for the solder material, with a Lead-free solder. Electronics industries have a plan to abolish completely a solder containing Lead. The Lead-free solder, in which Tin is a base material, has a substantially small stress relaxation effect compared with the Tin-Lead solder, which has a stress relaxation effect to decrease a stress generated at the bonding part through composition change of solder itself. Accordingly, the internal stress increases, and may cause a reliability issue when the shrinkage and pin-multiplication are further progressed in a future.
<SOH> BRIEF DESCRIPTION OF THE DRAWINGS <EOH>FIG. 1 is a cross sectional view showing a structure of conventional semiconductor apparatus. FIG. 2A is a cross sectional view showing a structure of first example of semiconductor apparatus in the first embodiment of the present invention. FIG. 2B is a cross sectional view showing a structure of second example of semiconductor apparatus in the first embodiment of the present invention. FIG. 2C is a cross sectional view showing a structure of third example of semiconductor apparatus in the first embodiment of the present invention. FIG. 3A to 3 F are cross sectional views of a wiring substrate at each process of a method for manufacturing the wiring substrate of the semiconductor apparatus in the first embodiment of the present invention. FIG. 4 is a cross sectional view showing a structure of semiconductor apparatus in the second embodiment of the present invention. FIG. 5A to 5 E are cross sectional views of a wiring substrate at each process of a method for manufacturing the wiring substrate of the semiconductor apparatus in the third embodiment of the present invention. FIG. 6 is a cross sectional view showing a structure of semiconductor apparatus in the fourth embodiment of the present invention. FIG. 7A to 7 D are cross sectional views of a semiconductor apparatus at each assembly process after Flip-Chip bonding process of the semiconductor apparatus in the fourth embodiment of the present invention. detailed-description description="Detailed Description" end="lead"?
20050523
20100601
20060713
97111.0
H01L2312
1
HARRISON, MONICA D
SEMICONDUCTOR DEVICE, WIRING SUBSTRATE, AND METHOD FOR MANUFACTURING WIRING SUBSTRATE
UNDISCOUNTED
0
ACCEPTED
H01L
2,005
10,536,054
ACCEPTED
Device for detachably linking a wiper blade with a driven wiper arm
The invention relates to a device and a method for releasably connecting a wiper blade to a drivable wiper arm, In one embodiment, the invention is characterized in that the coupling section has a tongue-like insertion section, in that the connecting element has a seat for the insertion section, and in that the coupling section and the connecting element have securing sections for providing a mutual permanent connection.
1. Device for releasably connecting a wiper blade to a drivable wiper arm, wherein the wiper blade comprises a wiper strip which faces the windscreen to be wiped, at least one strip-like elongate support element, a slide element which is connected to the support element, and a connecting element for connection to a coupling section of the wiper arm, which connecting element is mounted on the slide element in a manner such that it can pivot, characterized in that the coupling section has a tongue-like insertion section, in that the connecting element has a seat for the insertion section, and in that the coupling section and the connecting element have securing sections for providing a mutual permanent connection, wherein, in order to reach a preassembly position (FIG. 5) in which the longitudinal axis of the wiper arm and the longitudinal axis of the connecting element enclose an angle α in the range from approximately 10° to 100°, the insertion section can be inserted in a substantially rectilinear manner into the seat, and wherein, in order to reach a final assembly position (FIG. 6), the wiper arm and the connecting section can be pivoted onto one another about the insertion section/seat contact area until the securing sections allow a permanent mutual connection. 2. Device according to claim 1, characterized in that the an insertion direction for reaching a preassembly position lies in a plane of pivoting for reaching the final assembly position. 3. Device according to claim, characterized in that the coupling section is designed to be U-shaped in cross section and comprises a back and two legs, wherein the insertion section is generally hook-like and is arranged on the back of the coupling section. 4. Device according to claim 3, characterized in that the insertion section comprises an arc-shaped end, in the direction of the extension of the wiper arm and in side view in the direction of the windscreen to be wiped, in such a manner that it does not protrude beyond the back. 5. Device according to claim 1, characterized in that a region of the connecting element which cooperates with the insertion section and adjoins the insertion opening is designed to be complementary to the insertion section. 6. Device according to claim 1, characterized in that the region of the connecting element and of the insertion section which cooperates with the insertion section is designed to be arc-shaped, and in particular shaped like a segment of a circle, in longitudinal section. 7. Device according to claim 1, characterized in that the connecting element is designed to be U-shaped in cross section and comprises a back and two legs. 8. Device according to claim 1, characterized in that the seat comprises an insertion opening is designed as a cut-out on the back. 9. Device according to claim 1, characterized in that, in the final assembly position (FIG. 6), the coupling section covers the connecting element at least in part. 10. Device according to claim 1, characterized in that the securing sections are designed as locking sections. 11. Device according to claim 1, characterized in that the connecting element has, on its side facing away from the insertion opening in the longitudinal direction, legs, in each case a locking tongue which extends in the longitudinal direction and is elastically flexible in the transverse direction, which locking tongues cooperate with locking edges provided on the legs of the coupling section. 12. Device according to claim 11, characterized in that the locking edges of the locking tongues and the locking edges of the legs enclose an acute angle (β), in particular an angle in the range from approximately 30° to 80°, with the longitudinal axis. 13. Device according to claim 11, characterized in that actuating sections for releasing the locking connection are provided on the free ends of the locking tongues. 14. Device according to claim 11, characterized in that the sides of the locking tongues which face the back of the coupling section are suitably bevelled for easier locking. 15. Device according to claim 11, characterized in that the sides of the legs of the coupling section which face the windscreen are suitably bevelled for easier locking. 16. Device according to claim 11, characterized in that the connecting element and the coupling section have a coding. 17. Device according to claim 1, characterized in that the legs of the connecting element comprises legs that are double-walled legs. 18. Device according to claim 1, characterized in that the connecting element has, legs, and a hinge pin between the legs which is mounted in a hole on the slide element for the pivotable arrangement of the connecting element. 19. Device according to claim 1, characterized in that the slide element has a bearing bolt or alternatively two hinge pins which project with their ends from the slide element and on which the connecting element is pivotably mounted by bearing holes in its legs, which bearing holes are designed in a corresponding manner and are arranged so as to be aligned. 20. Device according to claim 19, characterized in that the bearing holes provided in the legs of the connecting element are opened above in each case a slot which runs radially with respect to the bearing hole. 21. Device according to claim 20, characterized in that the slots run from the bearing hole to an edge of the leg which lies opposite the back of the connecting element. 22. Device according to claim 20, characterized in that in each case the slot expands from the bearing hole towards an edge of the leg, wherein the narrowest point of the slot is smaller than the diameter of the bearing bolt or the alternative bearing pins. 23. Device according to claim 1, wherein connecting element comprises legs having stud-like raised areas on the side facing the windscreen. 24. Device according to claim 1, characterized in that, in a final assembly position, the coupling section and the connecting element have a substantially closed, substantially continuous and substantially smooth surface. 25. Device according to claim 1, characterized in that the coupling section of the wiper arm has at least one opening suitable for air to flow through. 26. Device according to claim 25, characterized in that the at least one opening is provided in the back of the coupling section. 27. Device according to claim 1, characterized in that at least one spoiler-like air guide means is provided on the coupling section of the wiper arm. 28. Device according to claim 27, characterized in that the at least one air guide means is arranged on the back of the coupling section. 29. Device according to claim 28, characterized in that the air guide means is formed by a section cut free from the back of the coupling section and bent upwards in a spoiler-like manner. 30. Device according to claim 1, characterized in that at least one spoiler-like air guide means is preferably made in one piece with the connecting element is arranged on a back of the connecting element, and in that this at least one air guide means protrudes through a, preferably corresponding, an opening in the back of the coupling section. 31. A method of assembling the device according to of claim 1 characterized in that, in order to reach a preassembly position (FIG. 5) in which the longitudinal axis of the wiper arm and the longitudinal axis of the connecting element enclose an angle α in the range from approximately 10° to 100°, the insertion section is inserted in a substantially rectilinear manner into the seat, and in that, in order to reach a final assembly position (FIG. 6), the wiper arm and the connecting section can be pivoted onto one another about the insertion section/seat contact area until the securing sections enter into a permanent mutual connection. 32. A device for releasably connecting a wiper blade to a drivable wiper arm having a coupling section, said device comprising: a connecting element coupled to said wiper blade; said connecting element being pivotally coupled to one end of the coupling section; and at least one securing section for securing said connecting element to said coupling section when said connecting element is pivoted to a closed position whereupon said wiper blade becomes detachably secured to said wiper arm. 33. The device as recited in claim 32 wherein said connecting section comprises a seat and said coupling section comprises an insertion section, said insertion section being received in said seat when said wiper blade is detachably secured to said wiper arm. 34. The device as recited in claim 33 wherein said coupling section comprises a plurality of resilient securing sections for detachably coupling said connecting element to said wiper arm when said connecting element is pivoted to said closed position. 35. The device as recited in claim 32 wherein said coupling section comprises at least one locking edge for engaging and cooperating with said at least one securing section to retain said connecting element in a closed position on said coupling section. 36. The device as recited in claim 32 wherein said at least one securing section is resilient to permit said coupling section and said connecting portion to be detachably coupled together. 37. The device as recited in claim 32 wherein said connecting element comprises a shape that is complementary to a shape of the coupling section. 38. The device as recited in claim 33 wherein a portion of said insertion section is arc-shaped in cross-section. 39. The device as recited in claim 32 wherein said connecting element is generally U-shaped in cross-section and is defined by a back and two legs. 40. The device as recited in claim 33 wherein said seat is defined as a cut-out on a back of said connecting element for receiving said insertion section. 41. The device as recited in claim 32 wherein when said coupling section and said connecting element are coupled together, said coupling section covers at least a portion of said connecting element. 42. The device as recited in claim 34 wherein said plurality of resilient securing sections define a plurality of resilient locking sections. 43. The device as recited in claim 32 wherein said at least one securing section comprises a plurality of elastically flexible locking tongues for engaging legs of said coupling section in order to lock said connecting element to coupling section. 44. The device as recited in claim 43 wherein said locking tongues enclose an acute angle with a longitudinal axis of said coupling section. 45. The device as recited in claim 32 wherein at least one of said connecting element or coupling section comprise a coding. 46. The device as recited in claim 32 wherein said connecting element comprises at least one bearing hole that is coupled to a slide element using at least one bolt or pin, respectively, said slide element receiving and holding said wiper blade. 47. The device as recited in claim 46 wherein said at least one bearing hole comprises a slot for receiving said at least one bolt or pin. 48. The device as recited in claim 32 wherein when said coupling section and said connecting element are coupled together, they cooperate to define a substantially continuous and smooth surface. 49. The device as recited in claim 32 wherein said device comprises a spoiler situated on at least one of said coupling section and said connecting element. 50. The device as recited in claim 32 wherein said coupling section comprises at least one opening for permitting air to flow from one side of said coupling section to another side of said coupling section. 51. The device as recited in claim 32 wherein said device further comprises a spoiler situated on said coupling section. 52. The device as recited in claim 49 wherein said spoiler is formed by a section integrally formed with said coupling section and extending from said coupling section. 53. The device as recited in claim 32 wherein said at least one securing section comprises at least one resilient detent.
The invention relates to a device and a method for releasably connecting a wiper blade to a drivable wiper arm, wherein the wiper blade comprises a wiper strip which faces the windscreen to be wiped, at least one strip-like elongate support element, a slide element which is connected to the support element, and a connecting element for connection to a coupling section of the wiper arm, which connecting element is mounted on the slide element in a manner such that it can pivot. Such a device is known for example from WO 02/40328 A1. The device described therein, by means of which a flat wiper blade can be connected to the coupling section, has a large number of complex components which are difficult to manufacture. Moreover, the operation of connecting the coupling section of the wiper arm to the connecting element of the wiper blade is relatively complex and requires a certain amount of skill. It is therefore an object of the present invention to propose a device for releasably connecting a wiper blade to a drivable wiper arm, in which the operation of connecting the connecting element to the coupling section can be carried out in a simple manner. Moreover, it is to be ensured that the coupling section is joined in a permanently secure manner to the connecting section, wherein the wiper blade can nevertheless be released from the wiper arm in a simple manner. According to the invention, this object is achieved by a device of the type described above in that the coupling section has a tongue-like insertion section, in that the connecting element has a seat for the insertion section, and in that the coupling section and the connecting element have securing sections for providing a mutual permanent connection, wherein, in order to reach a preassembly position in which the longitudinal axis of the wiper arm and the longitudinal axis of the connecting element enclose an angle α in the range from approximately 10° to 100°, the insertion section can be inserted in a substantially rectilinear manner into the seat, and wherein, in order to reach a final assembly position, the wiper arm and the connecting section can be pivoted onto one another about the insertion section/seat contact area until the securing sections allow a permanent mutual connection. The invention has the advantage that only two steps which are simple to carry out are required in order to connect the wiper blade to the wiper arm, namely firstly rectilinear insertion of the insertion section into the seat provided on the connecting element, and pivoting of the coupling section or of the wiper arm and of the connecting element onto one another. Moreover, such a device has the advantage that it is of a very flat and very narrow design. On the one hand, wind noise is minimized as a result. On the other hand, the view of the vehicle driver is only slightly impaired by the wiper blade and the wiper arm. Furthermore, force introduction preferably takes place over the longitudinal axis of the wiper blade, substantially perpendicular to the windscreen to be wiped, and as a result the occurrence of tilting moments is suppressed. Preferably, the insertion direction for reaching the preassembly position lies in the plane of pivoting for reaching the final assembly position. This has the advantage that the two movements lie in one plane, and as a result the assembly operation is simplified. One embodiment of the invention is characterized in that the coupling section is designed to be U-shaped in cross section and comprises a back and two legs, wherein the insertion section is designed in a hook-like manner and is arranged in a stand-alone manner on the back of the coupling section. The coupling section, which is designed to be U-shaped in cross section, advantageously engages over the connecting element at least in part in the final assembly position. As a result, transverse forces acting on the connecting element can be absorbed by the legs of the coupling section. The insertion section is preferably designed such that it is arc-shaped at the free end, in the direction of the extension of the wiper arm and in side view in the direction of the windscreen to be wiped, in such a manner that it does not protrude beyond the back. This has the advantage that the insertion section, in the final assembly position, does not protrude in a disruptive manner beyond the back of the coupling section. Given a suitably designed connecting element, the insertion section is not visible in the final assembly position. It is advantageous if the region of the connecting element which cooperates with the insertion section and adjoins the insertion opening is designed to be complementary to the insertion section. In this way it can be ensured, in the final assembly position, that the insertion section bears reliably against the complementarily designed region of the connecting element. A further embodiment of the invention is obtained when the region of the connecting element and of the insertion section which cooperates with the insertion section is designed to be arc-shaped, and in particular shaped like a segment of a circle, in longitudinal section. When the coupling section and the connecting element are pivoted onto one another in the final assembly position, this ensures that during the pivoting movement the insertion section bears with a substantial part of its surface against the region of the connecting element which cooperates with the insertion section. This ensures reliable guidance when assembling the device from the preassembly position to the final assembly position. Stress peaks are avoided on account of the large-surface bearing. One further embodiment is obtained when the connecting element is designed to be U-shaped in cross section and comprises a back and two legs. On account of the U-shaped design of the connecting element, a spoiler section of the wiper strip which faces away from the windscreen to be wiped can extend between the two legs of the connecting element in the longitudinal direction of the wiper blade. Furthermore, the connecting element can advantageously be coupled at the legs to the slide. Advantageously, the insertion opening is designed as a cut-out on the back. This has the advantage that the insertion opening can be clearly seen on the wiper blade in plan view, as a result of which insertion of the insertion section into the insertion opening is simplified. According to the invention, it is furthermore conceivable that, in the final assembly position, the coupling section covers the connecting element at least in part. In the state mounted on the wiper arm, the inner sides of the legs of the U-shaped coupling section then preferably bear against the outer sides of the legs of the U-shaped connecting element. The outer side of the back of the connecting element preferably bears against the inner side of the back of the coupling section. A further advantageous embodiment of the invention is obtained when the securing sections are designed as locking sections. When the coupling section and the connecting element are pivoted onto one another, the locking sections advantageously lock with one another in the final assembly position. It may be provided that the connecting element has, on its side facing away from the insertion opening in the longitudinal direction, on the legs, in each case a locking tongue which extends in the longitudinal direction and is elastically flexible in the transverse direction, which locking tongues cooperate with locking edges provided on the legs of the coupling section. In order to ensure secure locking, it may advantageously be provided that the locking edges of the locking tongues and the locking edges of the legs enclose an acute angle, in particular an angle in the range from approximately 30° to 80°, with the longitudinal axis of the wiper blade in the final assembly position. In order to release the locking connection, and thus to release the wiper blade from the wiper arm, in a further embodiment of the invention it may be provided that actuating sections are provided on the free ends of the locking tongues. The actuating sections are designed in such a way that the locking tongues can be pressed towards one another, as a result of which the locking edges of the locking tongues can come out of engagement with the locking edges on the legs of the coupling section. In order to allow easier locking, it is advantageously provided that the sides of the locking tongues which face the back of the coupling section and meet the legs of the coupling section when pivoted into the final assembly position are bevelled. Easier locking is also assisted if the sides of the legs of the coupling section which face the windscreen and which are met by the facing sides of the locking sections when pivoted into the final assembly position are bevelled. Shortly prior to reaching the final assembly position, the bevelled sides of the locking tongues consequently cooperate with the bevelled sides of the legs of the coupling section in such a way that the locking tongues are pivoted out in directions towards one another. In the final assembly position, the locking tongues snap behind the locking edges of the coupling section in directions facing away from one another. In order to prevent a wiper blade from being arranged the wrong way round on a wiper arm, the coupling section may have a suitable coding. Incorrect assembly of the wiper blade, for example on the incorrect wiper arm, is thus prevented. A coding may be produced for example by a suitable bezel on the coupling section and by a suitable web on the connecting element which cooperates with the bezel. A further advantageous embodiment of the invention is obtained when the legs of the connecting element are designed as double-walled legs which are slightly elastically flexible in the transverse direction. Such double-walled legs have a better friction behaviour with respect to the slide element against which they are pivotably arranged. Advantageously, the connecting element has, between the legs, a hinge pin which is mounted in a hole on the slide element for the pivotable arrangement of the connecting element. Another embodiment of the invention provides that the slide element has a bearing bolt or alternatively two hinge pins which project with their ends from the slide element and on which the connecting element is pivotably mounted by bearing holes in its legs, which bearing holes are designed in a corresponding manner and are arranged so as to be aligned. In this case, the bearing bolt is or the bearing pins are connected fixedly against rotation to the slide element, and the connecting element is mounted on the slide element in a manner such that it can rotate or pivot. When a wiper blade is replaced, therefore, the entire bearing device is exchanged. According to a further embodiment of the invention, the bearing holes provided in the legs of the connecting element are opened above in each case a slot towards the edge, which slot runs radially with respect to the bearing hole. This may advantageously be used to simplify the assembly of the individual parts. According to another embodiment, if the slot in each case runs from the bearing hole to the edge of the leg which lies opposite the back of the connecting element, the risk of the bearing bolt or bearing pin undesirably sliding out of the bearing hole is small. One further advantageous embodiment provides that in each case the slot expands from the bearing hole towards the edge of the leg, wherein the narrowest point of the slot is smaller than the diameter of the bearing bolt or the alternative bearing pins. This embodiment allows simplification of assembly and disassembly. The bearing bolt or bearing pins can be pressed in radially through the slot in the manner of a locking connection, negotiating the narrow point. Likewise, the bearing bolt or bearing pins can also be removed in the opposite direction, again negotiating the narrow point. To this end, it may be necessary for the connecting element to be made of a suitable plastics material which allows the narrow point of the slot to be negotiated by the bearing bolt or bearing pins. The slide element and/or the bearing bolt or the bearing pins may be made of metal or likewise made of a suitable plastics material. A further, advantageous embodiment of the invention provides that the legs of the connecting element have stud-like raised areas on the side facing the windscreen. These raised areas serve for support on either the wiper rubber or the support element, as a result of which easier assembly and disassembly of the wiper blade is made possible. The coupling section and the connecting element are preferably designed in such a way that, in the final assembly position, they have a substantially closed and substantially smooth surface. To this end, the sections of the connecting element which are covered by the coupling section may lie deeper than the sections of the connecting element which are visible in the final assembly position, the difference in depth being the wall thickness of the coupling section. Further advantageous refinements are provided in order to improve the aerodynamic behaviour of the wiper arm/wiper blade combination, particularly at high travelling speeds or airflow velocities, and thus to counteract in particular the known effect of lifting of the wiper blade connected to the wiper arm off the windscreen to be wiped. By virtue of the measure that the coupling section of the wiper arm has at least one opening suitable for air to flow through, a dynamic pressure which arises below the U-shape of the coupling section is substantially broken down. As a result, the lifting force on the wiper arm is reduced. It is particularly advantageous to provide the at least one opening in the back of the coupling section. However, an improvement is also possible if one or more airflow openings are placed in the legs of the coupling section, in particular in the lee-side leg. The maximum effect can probably be achieved by a combination of the individual possibilities. Another embodiment provides that at least one spoiler-like air guide means is provided on the coupling section of the wiper arm. In this way, the incoming air can be guided in such a way that the effect of the wiper blade or wiper arm being lifted off the windscreen is counteracted. It is advantageous in this connection for the at least one air guide means to be arranged on the back of the coupling section. A spoiler acts particularly effectively at this location. The advantages of an embodiment, according to which the air guide means is formed by a section cut free from the back of the coupling section and bent upwards in a spoiler-like manner, are to be seen in the combination of the effects of the spoiler and of the airflow opening formed in this way. The pressing force is thus directly increased and at the same time the dynamic pressure inside the coupling section is reduced. Moreover, an air guide means produced in this way is particularly cost-effective. A further advantageous embodiment provides that at least one spoiler-like air guide means which is preferably made in one piece with the connecting element is arranged on the back of the connecting element, and that this at least one air guide means protrudes through a, preferably corresponding, opening in the back of the coupling section. Since the connecting element is advantageously made of plastics material, a very large number of design possibilities are provided for the shape of the spoiler-like air guide means with regard to particularly favourable fluidic properties. The object mentioned in the introduction is also achieved by a method of assembling a device according to the invention, which method is characterized in that, in order to reach a preassembly position in which the longitudinal axis of the wiper arm and the longitudinal axis of the connecting element enclose an angle α in the range from approximately 10° to 100°, the insertion section is inserted in a substantially rectilinear manner into the seat, and in that, in order to reach a final assembly position, the wiper arm and the connecting section can be pivoted onto one another about the insertion section/seat contact area until the securing sections enter into a permanent mutual connection. Further details and advantages of the invention can be found in the following description in which the invention is described and explained in more detail with reference to examples of embodiments shown in the drawings. In the drawings: FIG. 1 shows a device according to the invention in a perspective view; FIG. 2 shows the device of FIG. 1 without the wiper arm; FIG. 3 shows a partial section through FIG. 2; FIG. 4 shows a view from below of the coupling section shown in FIG. 1; FIG. 5 shows a partial section through the device of FIG. 1 in a preassembly position; FIG. 6 shows a partial section through the device of FIG. 5 in the final assembly position; FIG. 7 shows another embodiment of a device according to the invention in a perspective view; FIG. 8 shows a further embodiment of a device according to the invention in a perspective view; FIG. 9 shows a final embodiment of a device according to the invention in a perspective view; FIG. 10 shows the device of FIG. 9 without the wiper arm; and FIG. 11 shows another embodiment of a device according to the invention without the wiper arm. FIG. 1 shows a device 10 according to the invention for releasably connecting a wiper blade 12, shown in part, to a drivable wiper arm 14 which is likewise shown in part. The wiper blade 12 has a wiper strip 16 which faces the windscreen to be wiped (not shown) and comprises two strip-like elongate support elements 18, 20, a slide element 22 which is connected to the support elements 18, 20, and a connecting element 24 which is arranged on the slide element 22 in a manner such that it can pivot. The connecting element 24 serves for connection to a coupling section 26 on the wiper arm 14. The coupling section 26 has, as can be seen in particular in FIG. 4, a tongue-like insertion section 28 which, in the final assembly position shown in FIGS. 1 and 6, engages in a seat 30 which can be clearly seen in FIG. 2. The connecting element 24, which like the coupling section 26 is U-shaped in cross section, has a back 32 and two legs 34. The seat 30 is provided in the back 32 of the connecting element 24. A bearing hole 36 for a bearing bolt 38, which bearing hole extends in the transverse direction, is provided on the legs 34 of the connecting element 24. On account of the bearing hole 36, and the bearing bolt 38, a pivoting arrangement of the connecting element 24 with respect to the slide element 22 is obtained. In order to achieve a certain flexibility of the legs 34 while having sufficient stiffness, the legs 34 are designed to be double-walled. As can likewise be seen from FIG. 2, the connecting element 24 has, on its side facing away from the insertion opening 30 in the longitudinal direction, on the legs 24, in each case a locking tongue 40 which extends in the longitudinal direction and is elastically flexible in the transverse direction. The locking tongues 40 each comprise a locking edge 42 and an actuating section 44. The region of the connecting element 24 which is covered by the coupling section 26 in the final assembly position is set back from the other regions of the connecting element 24 which are formed essentially by the two actuating sections 44 and a head section 46 which lies in the axial extension of the coupling section. As a result, in the final assembly position, the coupling section 26 and the connecting element 24 form a substantially closed and substantially smooth surface. As can be seen from FIG. 3, the region 48 which cooperates with the insertion section 28 and adjoins the insertion opening 30 is designed to be complementary to the insertion section 28. As can be seen from FIGS. 4 and 5, the insertion section 28 is designed in an arc-shaped manner in the direction of the extension of the wiper arm 14 and in side view in the direction of the windscreen to be wiped. Correspondingly, as can be seen from FIGS. 3 and 5, the region 48 is likewise designed to be arc-shaped, in particular in the shape of a segment of a circle. It can be seen from FIG. 4 that the coupling section is designed in a U-shaped manner in cross section and has a back 50 and legs 52, 54 which adjoin the back. The insertion section 28 is in this case arranged in a stand-alone manner in the extension of the back 50. Provided on the legs 52, 54 are locking edges 56 which enclose an angle β of approximately 70° with the longitudinal axis 58 of the wiper arm 14 (FIGS. 5 and 6). The locking edges 42 of the locking tongues 40 enclose a corresponding angle β. In the final assembly position shown in FIG. 6, the locking edges 42 of the locking tongues 40 bear against the locking edges 56 of the legs 52, 54 of the coupling section 26. It can be seen from FIGS. 2 and 5 that the sides 60 of the locking tongues 40 which face the back 50 of the coupling section 26 are slightly bevelled. In a corresponding manner, the sides 62 of the legs of the coupling section 26 which face the windscreen and cooperate with the sides 60 of the coupling section 26 when pivoted into the final assembly position are also slightly bevelled. For assembly of the coupling section 26 to the connecting element 24, in order to reach a preassembly position which is shown in FIG. 5, the insertion section 28 is inserted into the seat 30 in a substantially rectilinear manner in the direction of the arrow 64. In this preassembly position, the longitudinal axis of the wiper arm 14 and the longitudinal axis of the connecting element 24 or of the wiper blade 12 enclose an angle α which may lie in the range from approximately 10 to 100°. In the example of embodiment shown in FIG. 5, the angle α has a value of approximately 40°. In order to reach the final assembly position, which is shown in FIG. 1 and FIG. 6, the wiper arm 14 and the connecting section 24 are pivoted onto one another about the contact area 66 in which the insertion section 28 bears against the region 48 of the seat 30. On account of the complementary design of the insertion section 28 and the region 48, the pivoting operation is carried out to a limited extent. Shortly prior to reaching the final assembly position, the bevelled sides 62 of the coupling section 26 and the correspondingly bevelled sides 60 of the locking tongues 40 meet one another in such a way that the locking tongues 40 are pivoted elastically in a direction facing one another. Upon reaching the final assembly position, the locking tongues 40 snap behind the locking edges 56 of the legs 52, 54 of the coupling section 26 in a direction facing away from one another. As a result, the coupling section 26 is permanently held on the connecting element 24 in the final assembly position. In the final assembly position, the coupling section 28 bears against the region 48 of the connecting element 24 over a large part of its surface. Furthermore, the end side 68 of the coupling section 26 which faces the head area 46 of the connecting element 26 bears against a bearing edge 70 of the connecting element which corresponds thereto. On account of the locking edges 42, 56 which are not perpendicular to the longitudinal axis of the wiper blade but rather enclose an acute angle β with the longitudinal axis, in the assembled state the coupling section 26 is acted upon in the direction of the head section 46. As a result, a play-free connection is obtained in the axial direction. Moreover, by virtue of the obliquely arranged locking edges 42, 56, the coupling section 26 is acted upon in the direction of the wiper blade 12, as a result of which a play-free connection is produced in the direction perpendicular to the wiper blade. The insertion section 28 in this case bears against the contact region 48 of the connecting element 24 with slight prestress. In order to release the connection, the actuating sections 44 are pressed towards one another. As a result, the locking edges 42 of the locking tongues 40 come out of the engagement region of the locking edges 56 of the coupling section 26. Since the actuating sections are arranged opposite one another, the actuating sections 44 can be pressed together by a simple hand grip, using one hand. The coupling section 26 is then pivoted away from the connecting element 24 until the preassembly position reached in FIG. 5 is almost reached. The insertion section 28 is then moved out of the seat 30 in the direction counter to the arrow 64. As can be clearly seen in FIG. 5, it may be provided that the legs 34 of the connecting element have stub-like raised areas 72 on the side facing the windscreen. These raised areas serve for support on the slide element 22. The raised areas 22 restrict the pivoting range of the connecting element 24 with respect to the slide element 22. As a result, easier assembly and disassembly of the wiper blade 12 from the wiper arm 14 is possible. In the bent region of the insertion section 28, a material cut-out in the form of a cylindrical hole 74 is provided. In order to prevent it from being possible for the wiper blade, which has a spoiler-like projection 76 on its side facing away from the wiper strip 16, to be mounted on the incorrect wiper arm, a coding may be provided on the connecting element 24 and on the coupling section 26. Such a coding may be formed for example by a bevelled corner 78 on the leg 54 of the coupling section 26, as shown in a corresponding manner in FIG. 4. The bevelled corner 78 may in this case correspond to a material deposit at the corresponding location on the connecting element 24, which material deposit is designed in a complementary manner and is not shown in the figures. Since only one of two wiper blades, the respective right-hand or left-hand wiper blade, has a corresponding material deposit on the connecting element, a clear assignment of the right-hand or left-hand wiper blade to the right-hand or left-hand wiper arm is ensured. For the example of embodiment shown in FIG. 7, in general the same description as above in respect of the first example of embodiment shown in FIGS. 1 to 6 applies. The same references have thus been used in FIG. 7 as in FIG. 1. The essential difference of the example of embodiment shown in FIG. 7 is that an opening 80 is additionally provided in the back 50 of the coupling section 26 belonging to the wiper arm 14. This opening 80 makes it possible for air flowing below the U-shape of the coupling section to leave the space formed below the U-shape on a relatively short path by flowing through the opening 80. In this way, the dynamic pressure below the coupling section 26 is reduced compared to an embodiment without the opening 80, and this leads to a comparative reduction in the lifting force of the wiper arm 14 as air flows through. Instead of the one opening 80, it would also be possible for a number of openings 80 to be provided in the coupling section 26, wherein one or more openings 80 may also be made in one of the two legs 52, 54 or in both legs 52, 54. The size, shape and position of the one or more openings 80 should be optimized with regard to as considerable an effect as possible in a manner depending on the geometric conditions of the individual components of the device 10 and of the device 10 as a whole. Likewise, the shape and size of the one or more openings 80 may be adapted to the design of the coupling section 26. Also for the further example of embodiment shown in FIG. 8, the same description as that given above in respect of the first example of embodiment shown in FIGS. 1 to 6 applies. The essential difference of the example of embodiment shown in FIG. 8 is that a spoiler-like air guide means 82 is formed on the back 50 of the coupling section 26. In order to produce the air guide means 82, a more or less rectangular section which is oriented in the longitudinal direction of the coupling section 26 has been cut free from or punched out of the back 50 of the coupling section 26, at its two narrow sides and on one longitudinal side, and bent upwards out of the plane of the back 50. In this case, the air guide means 82 may be given a rounded, wing-like shape. The air guide means 82 is connected on its longitudinal side facing the incoming air to the back 50. By virtue of the bending-out operation, the opening 80 in the back 50 is made at the same time behind the air guide means 82, which opening can be flowed through by a stream of air. In FIG. 8, the reference line belonging to reference 80 is shown in dashed line because the view of the opening 80 is hidden by the air guide means 82 in this perspective view. The air guide means 82 and the opening 80 may be produced from steel sheet as a punched and bent part in a cost-effective manner by punching and bending during the process of manufacturing the coupling section. The aerodynamic advantages of such a design are on the one hand the pressing force produced by the air guide means, which pressing force acts on the wiper arm 14, and on the other hand the reduction in the dynamic pressure below the U-shape of the coupling section 26. The special feature of the example of embodiment shown in FIGS. 9 and 10 is that an opening is provided in the back 50 of the coupling section 26 and that a spoiler-like air guide means 84 arranged on the back 32 of the connecting element 24 passes through this opening to the top side of the coupling section 26. When air flows across the air guide means 84, the pressing force of the wiper arm 14 is increased and the lifting force is reduced. In FIG. 9, it can be seen that the shape and the size of the opening in the coupling section 26 and the base area of the air guide means 84 are adapted to one another. Moreover, the air guide means 84 is connected to the back 32 of the connecting element 24 via a pedestal 86. The height of the pedestal 86 corresponds to the wall thickness of the back 50 of the coupling section 26, so that the top side of the back 50 adjoins the air guide means 84 at least virtually free of any clearance or shoulder. As a result, the aerodynamics are improved and airflow noises are reduced. Unlike the diagram in FIGS. 9 and 10, the opening in the back 50 of the coupling section 26 may advantageously also be greater than the base area of the air guide means 84 or the pedestal 86 thereof. In this case, only part of the opening would be filled by the air guide means 84. The part of the opening which is not filled thus acts as an airflow opening, and as a result the dynamic pressure below the U-shape of the coupling section 26 is in turn reduced. This embodiment is not shown in the drawing. Another embodiment which is not shown in the drawing consists in that, in a device as shown in FIGS. 9 and 10, additionally at least one opening is provided in the back and/or in at least one of the legs 52, 54 for reducing the dynamic pressure below the U-shape of the coupling section 26. A final example of embodiment is shown in FIG. 11. This example of embodiment corresponds in a very large number of features to the embodiment shown in FIG. 2, which is why the fundamental design will not be repeated here and the same reference numerals are used for identical parts and elements. In the example of embodiment shown in FIG. 11, the slide element 22 has two bearing pins 88 which are arranged so as to be aligned with one another and which project from the slide element 22 transversely with respect to the longitudinal direction of the wiper blade 12. The bearing pins 88, only one of which can be seen in FIG. 11 on account of the perspective view, are made in one piece with the slide element 22. The slide element 22 will advantageously be manufactured as a whole as a diecast metal part or as an injection-moulded plastic part. Bearing holes 90 which are aligned with one another are formed in the two legs 34 of the connecting element 24, said connecting element having essentially the shape of a U in cross section, once again only one of the bearing holes 90 being visible in FIG. 11 on account of the perspective view. The bearing holes 90 are adapted to the bearing pins 88 in such a way that pivoting of the slide element 22 relative to the connecting element 24 can take place in as play-free a manner as possible. One essential difference compared to the embodiment shown in FIG. 2 is that the bearing holes 90 are each opened radially above a slot 92 which runs from the bearing hole 90 towards the lower edge of the leg 34, that is to say the edge opposite the back 32 of the connecting element 24. The slot 92 expands from the edge of the bearing hole 90 towards the edge of the leg 34. The narrow point of the slot 92 is in this case narrower than the diameter of the respective bearing pin 88. Upon assembly or disassembly of the slide element 22 and the connecting element 24, the bearing pins 88 are pressed radially into the bearing holes 90 or out of the latter through the slots 92 in the manner of a locking connection, negotiating the narrow point. As a result, these processes are considerably simplified, and moreover a sufficiently reliable seating or holding of the bearing pins 88 in the bearing holes 90 is ensured. Usually, the connection of a wiper blade 12 provided with such a slide element 22 and such a connecting element 24 to a wiper arm 14 or to the coupling section 26 of a wiper arm 14, and removal thereof in the opposite direction, take place in the same general manner, as has been described in connection with FIGS. 1 to 6. However, in the embodiment shown in FIG. 11, there is also the possibility firstly of attaching the connecting element 24, separated from the wiper blade 12, in this general way to the coupling section 26 of the wiper arm 14 and then mounting the slide element 22 connected to the wiper blade 12 on the connecting element 24 by pushing the bearing pins 88 radially through the slots 92 into the bearing holes 90. It is also conceivable to carry out a disassembly operation by reversing the sequence of these last-mentioned steps. Devices for releasably connecting a wiper blade to a wiper arm which correspond to the examples of embodiments shown in FIGS. 1 to 10 are suitable in particular for use in wiper systems for front windscreens of vehicles, whereas the device corresponding to the example of embodiment shown in FIG. 11 is suitable in particular for use in wiper systems for rear windows of vehicles. All of the features found in the description, the drawings and the claims may be essential to the invention both individually and in any desired combination with one another.
20060119
20110222
20060608
74097.0
B60S140
4
NGUYEN, DUNG V
DEVICE FOR DETACHABLY LINKING A WIPER BLADE WITH A DRIVEN WIPER ARM
UNDISCOUNTED
0
ACCEPTED
B60S
2,006
10,536,190
ACCEPTED
Test stand for simulation of the exhaust flow of an internal combustion engine
This invention relates to a test stand for simulation of the exhaust flow of an internal combustion engine, comprising a cylinder (36) and a base body (39) which is designed as a cylinder head and in which at least one exhaust port (41, 42) which is monitored by a charge cycle valve (43, 44) is provided for simulation, and/or, mapping, of a combustion chamber and a trough and/or cup (40) is also provided, whereby the charge cycle valve (43, 44) can be operated with the help of a valve lift switching [device], a control device for the valve lift shifting and a device for filling the cylinder (36) with compressed air.
1-11. (canceled) 12. Test stand for simulation of an internal combustion engine exhaust flow, comprising a cylinder and a base body configured as a cylinder head and in which at least one exhaust port which is operatively associated with a charge cycle valve is provided for at least one of simulation, and mapping of a combustion chamber, and at least one of a trough and cup is also provided, whereby the charge cycle valve is operateable with the aid of a valve lift switching; a device for controlling the valve lift switching, and a device for filling the cylinder with compressed gas. 13. Test stand as claimed in claim 12, wherein a housing is mounted on the base body, and switchable bucket tappets are accommodated in the housing so as to be operable by a camshaft mounted on the housing. 14. Test stand as claimed in claim 13, wherein the bucket tappets include internal and external lifting pistons cooperate with a cam arrangement to implement a valve lift and a zero lift, with the internal lifting piston cooperating with a camshaft area of the camshaft having a circular diameter. 15. Test stand as claimed in claim 12, wherein, the internal and external lifting pistons of the bucket tappet are arranged to be at least one of switched and locked in relation to one another via a hydraulically operable locking unit. 16. Test stand as claimed in claim 15, wherein the bucket tappets include internal and external lifting pistons cooperate with a cam arrangement to implement a valve lift and a zero lift, with the internal lifting piston cooperating with a camshaft area of the camshaft having a circular diameter. 17. Test stand as claimed in claim 15, wherein oil pump is driven by a motor for oil pressure supply of a hydraulic system. 18. Test stand as claimed in claim 17, wherein the hydraulic system comprises a shift valve, an oil tank and an oil filter. 19. Test stand as claimed in claim 13, wherein the camshaft is driven by an electric motor via a belt drive. 20. Test stand as claimed in claim 19, wherein a frequency converter operatively arranged for driving the electric motor. 21. Test stand as claimed in claim 12, wherein sensors for detecting physical parameters of state are operatively arranged in the cylinder and in the at least one exhaust port. 22. Test stand as claimed in claim 21, wherein at least one pressure sensor and at least one temperature sensor are provided in the cylinder and in the at least one exhaust port. 23. Test stand as claimed in claim 21, wherein microphones for measuring the sound pressure are distributed at selected locations in the at least one exhaust port. 24. Method for simulation of an internal combustion engine exhaust flow comprising: using a test stand apparatus to at least one of simulate and map a combustion chamber of varying configurations, employing valve lift switching for a change cycle valve arrangement, filling the simulated combustion chamber with pressurized gas, and sensing pressure characteristics at preselected locations on the apparatus.
The present invention relates to a test stand for simulating the exhaust flow of an internal combustion engine. BACKGROUND OF THE INVENTION The power characteristic of a four-cycle engine is determined to a significant extent by the quality of the charge cycle. In a combustion engine, the exhaust valve practically always opens the cylinder at a supercritical pressure gradient, so the flow processes in the charge cycle channels are highly non-steady. When the exhaust valve is opened before reaching bottom dead center (BDC) of the piston, a pre-exhaust wave, i.e., an exhaust process with a supercritical pressure gradient, is generated. Since the exhaust port monitored by the exhaust valve of a combustion engine can be regarded as a poorly designed Laval nozzle, a flow discontinuity occurs due to the non-steady-state flow conditions. This always results in the development of a perpendicular compression wave. Due to the perpendicular compression wave, flow is immediately decelerated to subsonic speed so the exhaust mass flow drops greatly. In addition, due to the pre-exhaust wave, aerodynamic noises are generated, resulting in corresponding pressure fluctuations. To counteract the inadequacies described above, in particular in the pre-exhaust wave, numerous studies have been conducted with regard to improving the charge cycle load processes. For example, a computational method and a program for the aerodynamic supersonic flow of the exhaust and for the shaping of the valve were developed as described in MTZ (Motor Technische Zeitschrift [Automotive Engineering Journal] 51, 1990, No. 7/8, pp. 336 to 343). The goal was to design the exhaust port and/or the valve geometry so that the calculated system will function without waves or pulsation. The possibility of completing the flow by reducing the exhaust velocities of the combustion gases was also taken into account. SUMMARY OF THE INVENTION To be able to better understand and investigate the non-steady-state flow processes described previously in the charge cycle processes, an object of this invention is to develop a test stand that will simulate the exhaust processes that actually occur on the basis of various channel models and will yield reproducible results in a process while still being equipped for easy design implementation with standard components. This object has been achieved by providing a test stand having a cylinder and a base body configured as a cylinder head and in which at least one exhaust port which is operatively associated with a charge cycle valve is provided for at least one of simulation, and mapping of a combustion chamber, and at least one of a trough and cup is also provided, whereby the charge cycle valve is operatable with the aid of a valve lift switching, a device for controlling the valve lift switching, and a device for filling the cylinder with compressed gas. With the test stand of the present invention, exhaust flow processes are easily simulated, and their results can be used in the implementation of channel geometries and/or valve and valve seat geometries. To be able to investigate various exhaust port forms and geometric shapes of exhaust valves and valve seat rings, the cylinder head has a replaceable base body in which the exhaust port and a trough and/or cup are integrated to map the combustion chamber. A housing is adjacently mounted on the base body of the cylinder head with switchable bucket tappets accommodated in the housing so that they can be cooperate with a camshaft mounted on the housing. The switchable drive guide is designed so that an internal lifting piston of the bucket tappet cooperates with a diameter of a circle of the camshaft for implementation of a zero stroke, while an external lifting piston of the bucket tappet cooperates with a cam of the camshaft for implementation of a valve lift. With this switchable valve drive, the desired exhaust processes at the preselected and/or desired operating points can be simulated. The internal and external lifting pistons of the bucket tappets can be switched and locked in relation to one another via a hydraulically operable locking unit. A motor-driven oil pump is provided for the oil pressure supply of the hydraulic system. The hydraulic system for supplying the oil pressure for the hydraulic valve clearance adjustment and for the valve lift switching has an oil tank, an oil filter and a shift valve in addition to the oil pump with the motor and a pressure-limiting valve. For the drive of the camshaft, the test stand is provided with an electric motor which drives the camshaft via a belt drive. To be able to simulate the rotational speeds required for today's high performance engines, the electric motor is driven by a frequency converter which helps to regulate the rotational speed of the three-phase motor in the range of 250 to 8000 rpm. To be able to investigate different geometries of the exhaust port, the exhaust valve and the valve seat ring acoustically and in terms of gas dynamics on the flow test stand, multiple sensors and microphones are provided. One or more pressure and temperature sensors are provided in both the cylinder and the exhaust port, whereas microphones for measuring the sound pressure are provided at several locations in the exhaust port. BRIEF DESCRIPTION OF THE DRAWINGS Other objects, advantages and novel features of the present invention will become apparent from the following detailed description of the invention when considered in conjunction with the accompanying drawings. FIG. 1 is a side view showing the essential components of a test stand according to the present invention, FIG. 2. is a plain view of the lower base plate of the test stand of FIG. 1, FIG. 3. is a plain view of an upper base plate of the test stand of FIG. 1, FIG. 4 is a partial cross-sectional view of an intermediate plate of the test stand with two pulleys, FIG. 5 is a partial longitudinal cross-section view through the cylinder head of the flow test stand, FIG. 6 is a plain view of a base body of the cylinder head from beneath, FIG. 7 is a sectional view along line VI-VI in FIG. 6, FIG. 8 is an isolated cross sectional view through a lift transmission element, FIG. 9 is a partial longitudinal sectional view through a lift transmission element, FIG. 10 is a hydraulic schematic diagram for the switchable drive, and FIG. 11 is a schematic view of the cylinder and cylinder head with the provided measurement sites. DETAILED DESCRIPTION OF THE DRAWINGS The test stand depicted in FIG. 1 includes a rectangular housing 2 which has lower and upper base plates 4, 6, the two plates being held a distance apart by four corner sections 8. An electric motor 10 mounted on the lower base plate 4 is provided for driving a camshaft 12 (to be described in greater detail below). The electric motor 10 is driven with the aid of a frequency converter which is accommodated, e.g., in a switchbox (not shown) mounted on the upper base plate 6. In addition, an intermediate plate 16 is also mounted on the lower base plate 4 by way of two mounting angles 14, 15. The intermediate plate extends to the upper base plate 6 where it is attached. As shown in FIG. 4, an opening is provided in the intermediate plate 16, with a camshaft 20 rotatably mounted in the opening by way of two deep groove ball bearings 18, 19. On each side of the intermediate plate 16, a pulley 21, 22 is placed on the intermediate shaft 20 and secured axially by a hexagon head screw 23 and a hexagon nut 24. A pulley 25 is also mounted on the drive shaft of the electric motor 10, with a primary drive toothed belt 26 being situated between the pulley 25 of the electric motor 10 and the pulley 21 of the intermediate shaft 20. In addition, an oil pump 27 (FIG. 2) which is driven by a motor is mounted on the lower base plate 4 and is provided for supplying oil pressure to the switchable valve drive to be described in greater detail below. As shown in FIG. 3, an oil tank 28 having a rectangular flange face 29 that is sealed with respect to the base plate 6 is mounted and sealed on the upper base plate 6. The upper base plate 6 also has a first circular opening 30 through which is inserted an oil filter 31 that is integrated into the oil circulation (to be described in greater detail below). The oil filter 31 is mounted on an oil filter block 32 (FIG. 1) which is combined as one modular unit with a shift valve block 34 accommodating a shift valve 33. A second circular opening 35 is provided in the upper base plate 6 through which a cylinder 36 passes. A valve 38 is provided in the bottom end face 37 of the cylinder 36 and serves to fill the cylinder 36 with compressed air. The cylinder 36 which is in the form of a pot is open at the top and is sealed with respect to a base body 39. As shown in FIGS. 6 and 7, a cup 40 for mapping, i.e., simulating a combustion chambers is provided in the base body 39 along with exhaust ports 41, 42 that communicate with the cup 40. The two exhaust ports 41, 42 are controlled and/or monitored by two exhaust valves 43, (FIGS. 8 and 9) 44. A bucket tappet housing 45 (FIG. 5) is connected to the base body 39 and has two bucket tappets 46, 47 acting as cam follower elements guided therein. As shown in FIGS. 8 and 9, the bucket tappets 46, 47 have two concentrically arranged cup elements, referred to below as the external lifting piston 48 and the internal lifting piston 49, each cooperating with different cams (partial cams) 50 to 52 and/or 50′ to 52′. The cams 50, 52 and 50′, 52′ are all identical in design, i.e., they have the same height of lift and phasing and they cooperate with the external lifting piston 48. The camshaft area 51 and/or 51′ formed between the two cams 50, 52 and 50′, 52′ is provided with a circular diameter, however, so that regardless of the rotational position of the cam shaft 12 in cooperation with the internal lifting piston 49, a zero lift is created in which the exhaust valves 43, 44 are not opened. The two lifting pistons 48, 49 have a bore 53 (FIG. 8) in their bottom area. The lifting pistons are aligned with one another in the basic circular phase of the partial cams 50 to 52 and/or 50′ to 52′ so that the external lifting piston 48 with the internal lifting piston 49 can be locked in this position by piston elements 54, 55 that are displaceable longitudinally in the bore 53. The displacement of the piston elements 54, 55 and thus the locking are accomplished hydraulically. To this end, an end face of the piston element 55 is acted upon with hydraulic oil through an opening 56. The locking mechanism is not described further here as it is described, for example, in greater detail in DE 196 01 587 A1 or DE 195 28 505 A1. If the external and internal lifting pistons 48, 49 are locked with respect to one another via the piston elements 54, 55 in a first working position, i.e., switch position, then a corresponding valve lift is transmitted to the exhaust valves 43, 44 via the external cam areas 50, 52 and/or 50′, 52′. The pressure exerted on the piston 55 is interrupted and/or reduced by the operation, i.e., switching of a control valve situated in a hydraulic supply line (to be explained in greater detail below) to the extent that the spring-loaded piston 54, 55 is returned from its locked operating position so that both lifting pistons 48, 49 are again arranged to be freely movable with respect to one another. As already explained, no lift is transmitted to the exhaust valves 43, 44 in this operating state because of the partial cam 51 and/or 51′ designed as a diameter of a circle. On the left end face of the camshaft 12 as viewed in FIG. 2, a pulley 72 is mounted and is connected to the pulley 22 of the intermediate shaft 20 via a secondary driving toothed belt 57. A tension roller 58 is provided on the intermediate plate 16 and mounted on a shaft 59, which is in turn rotatably mounted on the intermediate plate 16, to ensure a proper belt tension (FIG. 4). In addition, a flywheel element 60 is mounted on the right end face of the camshaft 12 (FIG. 5). The camshaft 12 is rotatably mounted on the bucket tappet housing 45 with the help of two deep groove ball bearings 60, 61. The hydraulic switching circuit provided for the variable valve drive is described below on the basis of FIG. 10. To facilitate a better overview, the depiction of hydraulic connections, lines, etc. between the individual components situated in the hydraulic circuit has been omitted in the other figures. The connection of the individual hydraulic components is implemented with the help of conventional steel flex lines. These steel flex lines are attached to the components with double connections and fittings in a known way. With the help of the oil pump 27, hydraulic oil is conveyed out of the oil tank 28 and to the bucket tappets 46, 47. The oil pump has a spring-loaded pressure-limiting valve 71 with which the system pressure can be adjusted directly on the oil pump 27. The valve lift switching of the switchable bucket tappets 46, 47 is controlled with the shift valve 33 configured as a 4/3-way valve in the hydraulic feeder line. In the left switch position of the shift valve 33, the lock is activated via the bore 53 provided in the bucket tappets 46, 47 so that the valve lift which is defined by the partial cams 50, 52 and/or 50′, 52′ is activated. When the electrically triggerable shift valve 33 is moved into its right switching position, the pressure line leading to the bucket tappets 46, 47 is blocked. The pressure-limiting valve 71 opens and the hydraulic oil is returned to the oil tank 28 in the short circulation loop. The hydraulic oil pressure in the bore 53 drops and the two spring-loaded piston elements 54, 55 are moved into a position in which the external and internal lifting pistons 48, 49 are again freely movable toward one another. In this position, as explained above, a zero lift is generated whereby the exhaust valves 43, 44 do not open. Two lines and/or bores (not shown) for the oil supply of the known hydraulic valve clearance adjustment lead out of the oil filter block 32 directly to the bucket tappet guides. An exhaust pipe 62 connected to the two exhaust ports 41, 42 is mounted on the base body 39 with the help of a flange 63 (FIGS. 3 and 11). A pressure sensor 64 and a temperature sensor 65 are arranged in the interior of the cylinder 36. Second and third pressure sensors 66, 67 are provided in the exhaust ports 41, 42 (two pressure sensors 66) each in immediate proximity to the valve seat rings, and one pressure sensor 67 is provided at the end of the exhaust ports 41, 42 which are combined in the base body 39. Two first microphones 68 are also situated in immediate proximity to the valve seat rings and a second microphone 69 is also situated at the end of the exhaust ports 41 42 which are combined in the base body 39. A third microphone is mounted in the exhaust pipe 62. To simulate the pre-exhaust wave, the cylinder 36 is filled with compressed air through the valve 38 via an external compressed air supply. The camshaft 12 is driven by the primary and secondary toothed belts 26, 57 via the electric motor 10 which is driven with the aid of the frequency converter. frequency converter allows the electric motor 10 to be operated in the range of 250 to 8000 rpm. With the valve lift switching described above, it is now possible to switch from the zero lift (average camshaft range 51 and/or 51′) to a valve lift (partial cams 50, 52 and/or 50′, 52′), which produces a sudden opening of the two exhaust valves 43, 44 at the desired measurement points in time and/or when selected operating points prevail. With the opening of the exhaust valves 43, 44, the pressure characteristics over the valve lift are measured by the pressure sensors 64, 66 and 67, with the static pressures being recorded. The characteristic of the cylinder pressure and the residual pressure in the cylinder 36 at the end of the measurement (piston at bottom dead center) are critical criteria for evaluating the quality of the entire pre-exhaust flow. To be able to make more accurate estimates specifically regarding the pre-exhaust wave, it is necessary to measure the pressure gradient between the beginning of the channel and cylinder 36. For this reason, the pressure sensor 66 is situated directly at the beginning of the channels 41, 42. The pressure allows an estimate of the development of compression waves with respect to the valve lift in the area of the exhaust valves 43, 44 and/or the valve seat rings. The pressure characteristics between the start of the channel and the end of the channel can be used to determine the loss of static pressure in the exhaust ports 41, 42. It is thus possible to estimate the flow losses in the exhaust ports 41, 42 because these are reflected in the static pressure. With the aid of the three microphones 68, 69, 70, the sound pressure is measured. The sound pressure level can be determined from this information. For a more detailed analysis, the total noise is divided into so-called frequency bands (octave bands and third-octave bands). The influence of the respective frequency range on the total sound level can thus be determined. The microphone 68 measures the sound pressure directly at the start of the channel, which represents the area of greatest interest for the acoustic analysis. The microphone 68 is in the mixed zone of turbulent-free streaming which develops directly behind the exhaust valves 43, 44. In the mixing processes, free eddies develop and a great deal of turbulent stresses which causes the corresponding pressure fluctuations. For the reproducibility of the measurements, the temperature sensor 65 is provided in the cylinder 36 because otherwise the temperature differences that occur in the starting state would influence the measurements. On the basis of the easy interchangeability of the base body 39 attached to the upper base plate 6, all conventional exhaust port designs (including steep experimental port designs) can be analyzed inexpensively. Thus, this makes available a test stand and method for simulation of the exhaust flow of an internal combustion engine with which turbulent flow that occurs in practice with the opening of the exhaust valves before bottom dead center can be investigated easily.
<SOH> BACKGROUND OF THE INVENTION <EOH>The power characteristic of a four-cycle engine is determined to a significant extent by the quality of the charge cycle. In a combustion engine, the exhaust valve practically always opens the cylinder at a supercritical pressure gradient, so the flow processes in the charge cycle channels are highly non-steady. When the exhaust valve is opened before reaching bottom dead center (BDC) of the piston, a pre-exhaust wave, i.e., an exhaust process with a supercritical pressure gradient, is generated. Since the exhaust port monitored by the exhaust valve of a combustion engine can be regarded as a poorly designed Laval nozzle, a flow discontinuity occurs due to the non-steady-state flow conditions. This always results in the development of a perpendicular compression wave. Due to the perpendicular compression wave, flow is immediately decelerated to subsonic speed so the exhaust mass flow drops greatly. In addition, due to the pre-exhaust wave, aerodynamic noises are generated, resulting in corresponding pressure fluctuations. To counteract the inadequacies described above, in particular in the pre-exhaust wave, numerous studies have been conducted with regard to improving the charge cycle load processes. For example, a computational method and a program for the aerodynamic supersonic flow of the exhaust and for the shaping of the valve were developed as described in MTZ ( Motor Technische Zeitschrift [Automotive Engineering Journal] 51 , 1990 , No. 7/8, pp. 336 to 343). The goal was to design the exhaust port and/or the valve geometry so that the calculated system will function without waves or pulsation. The possibility of completing the flow by reducing the exhaust velocities of the combustion gases was also taken into account.
<SOH> SUMMARY OF THE INVENTION <EOH>To be able to better understand and investigate the non-steady-state flow processes described previously in the charge cycle processes, an object of this invention is to develop a test stand that will simulate the exhaust processes that actually occur on the basis of various channel models and will yield reproducible results in a process while still being equipped for easy design implementation with standard components. This object has been achieved by providing a test stand having a cylinder and a base body configured as a cylinder head and in which at least one exhaust port which is operatively associated with a charge cycle valve is provided for at least one of simulation, and mapping of a combustion chamber, and at least one of a trough and cup is also provided, whereby the charge cycle valve is operatable with the aid of a valve lift switching, a device for controlling the valve lift switching, and a device for filling the cylinder with compressed gas. With the test stand of the present invention, exhaust flow processes are easily simulated, and their results can be used in the implementation of channel geometries and/or valve and valve seat geometries. To be able to investigate various exhaust port forms and geometric shapes of exhaust valves and valve seat rings, the cylinder head has a replaceable base body in which the exhaust port and a trough and/or cup are integrated to map the combustion chamber. A housing is adjacently mounted on the base body of the cylinder head with switchable bucket tappets accommodated in the housing so that they can be cooperate with a camshaft mounted on the housing. The switchable drive guide is designed so that an internal lifting piston of the bucket tappet cooperates with a diameter of a circle of the camshaft for implementation of a zero stroke, while an external lifting piston of the bucket tappet cooperates with a cam of the camshaft for implementation of a valve lift. With this switchable valve drive, the desired exhaust processes at the preselected and/or desired operating points can be simulated. The internal and external lifting pistons of the bucket tappets can be switched and locked in relation to one another via a hydraulically operable locking unit. A motor-driven oil pump is provided for the oil pressure supply of the hydraulic system. The hydraulic system for supplying the oil pressure for the hydraulic valve clearance adjustment and for the valve lift switching has an oil tank, an oil filter and a shift valve in addition to the oil pump with the motor and a pressure-limiting valve. For the drive of the camshaft, the test stand is provided with an electric motor which drives the camshaft via a belt drive. To be able to simulate the rotational speeds required for today's high performance engines, the electric motor is driven by a frequency converter which helps to regulate the rotational speed of the three-phase motor in the range of 250 to 8000 rpm. To be able to investigate different geometries of the exhaust port, the exhaust valve and the valve seat ring acoustically and in terms of gas dynamics on the flow test stand, multiple sensors and microphones are provided. One or more pressure and temperature sensors are provided in both the cylinder and the exhaust port, whereas microphones for measuring the sound pressure are provided at several locations in the exhaust port.
20050524
20080408
20060309
62412.0
G01M1509
0
JENKINS, JERMAINE L
TEST STAND FOR SIMULATION OF THE EXHAUST FLOW OF AN INTERNAL COMBUSTION ENGINE
UNDISCOUNTED
0
ACCEPTED
G01M
2,005
10,536,245
ACCEPTED
Heating system comprising at least two different radiations
The invention relates to a heating system used, for example, in applications such as the drying of paint. This heating system comprises a reflector (201, 505) having a concave section symmetrical with respect to an axis of symmetry (208, 508). It comprises in addition a first radiation system having at least a first radiation member (202, 501) capable of emitting a first type of radiation and a second radiation system having at least a second radiation member (203, 502) capable of emitting a second type of radiation. The second radiation system is positioned in a direction parallel to said axis of symmetry with respect to the first radiation system.
1. A heating system comprising a reflector (201, 505) having a concave cross-section that is substantially symmetrical with respect to an axis of symmetry (208, 508); a first radiation system comprising at least a first radiation member (202, 501) capable of emitting a first type of radiation; a second radiation system comprising at least a second radiation member (203, 502) capable of emitting a second type of radiation, said second radiation system being positioned in a direction substantially parallel to said axis of symmetry with respect to said first radiation system. 2. A heating system as claimed in claim 1, wherein said first radiation member comprises a first envelope and further comprises a first reflecting layer (301) deposited on a portion of said first envelope. 3. A heating system as claimed in claim 2, wherein said second radiation member comprises a second envelope and further comprises a second reflecting layer (302) deposited on a portion of said second envelope. 4. A heating system as claimed in claim 3, wherein said first reflecting layer has a first concave section that is substantially symmetrical with respect to a first axis of symmetry parallel to the axis of symmetry of the cross-section of the reflector, said second reflecting layer has a second concave section that is substantially symmetrical with respect to a second axis of symmetry parallel to the axis of symmetry of the cross-section of the reflector, and the first and the second reflecting layer have mutually opposed directions of concavity and are adjacent to one another. 5. A heating system as claimed in claim 1, wherein the first radiation type is situated in the short infrared range and the second radiation type is situated in the medium infrared range. 6. A heating system as claimed in claim 5, wherein the second radiation member is located between the reflector and the first radiation member. 7. A heating system as claimed in claim 1, wherein said first radiation member (501) comprises a first envelope, and the reflector (505) is a first reflecting layer deposited on a portion of said first envelope. 8. A heating system as claimed in claim 7, wherein said second radiation member (502) comprises a second envelope, and said second radiation member in addition comprises a second reflecting layer deposited on a portion of said second envelope. 9. A heating system as claimed in claim 8, wherein said second reflecting layer has a concave section that is substantially symmetrical with respect to an axis of symmetry parallel to the axis of symmetry of the cross-section of the first reflecting layer, the first and the second reflecting layer having mutually opposed directions of concavity and being mutually adjacent. 10. A heating system as claimed in claim 2, wherein the reflecting layers used are ceramic layers. 11. A heating system as claimed in claim 1, wherein the first and the second radiation member are kept in position by at least one cap (207, 506) in which an end of the first radiation member and an end of the second radiation member are inserted.
FIELD OF THE INVENTION The invention relates to a heating system comprising at least two radiation members capable of emitting at least two different types of radiation. The invention finds its application, for example, in a heating system designed for industrial purposes such as curing of synthetic resins by heat, drying of paper, or baking of paints. BACKGROUND OF THE INVENTION U.S. Pat. No. 6,421,503 published Jul. 16, 2002 describes a heating system comprising two radiation members capable of emitting two different types of radiation. These radiation members are tubular in shape. The first radiation member comprises an incandescent filament capable of emitting a radiation in the near infrared range, whereas the second radiation member comprises a carbon ribbon capable of emitting a radiation in the medium infrared range. It is a disadvantage of such a system that a given point of a coating under treatment is not simultaneously exposed to the two types of radiation. FIG. 1 is a cross-sectional view of such a heating system and of a coating treated by this heating system. The heating system shown in FIG. 1 corresponds to a heating system of FIG. 5 from U.S. Pat. No. 6,421,503. Such a heating system comprises a first radiation member 10 comprising a first quartz envelope 12 and a carbon ribbon 14, and a second radiation member 11 comprising a second quartz envelope 13 and an incandescent filament 15 kept in position by a support 15a. The two radiation members 10 and 11 are fixedly joined together by a central section 17. Each of the two radiation members 10 and 11 is covered with a reflecting layer 16 on an upper half of the respective quartz envelope 12 or 13. Under these operating conditions, the radiation emitted by the first and the second radiation member 10 and 11 is necessarily downwardly directed when the heating system is arranged as shown in FIG. 1. Consequently, an object 18 to be treated by this heating system is present below said heating system. This object 18 comprises a coating 19 which is to be treated by the heating system. This may relate to, for example, a metal plate on which a paint comprising a pigment and a solvent has been deposited. In such a configuration, the rays emitted by the radiation members 10 and 11 are not focused on the same location of the coating 19. As a result, the overlap of the two types of radiation, which is particularly advantageous in applications such as the drying of paints, is limited, i.e. the spectral combination of the spectra of the two types of radiation is limited. In addition, the fact that the rays emitted by the radiation members 10 and 11 are not focused on the same location of the coating 19 leads to a prolonged treatment time for the coating 19, since each point of the coating 19 must be exposed to two types of radiation. Another disadvantage of such a heating system is that the heating system is cumbersome. An oven for drying the coating will in fact generally comprise several heating systems arranged side by side, parallel to a direction in which the objects under treatment are moved. The dimensions of the heating system of FIG. 1 are important in view of this direction, because the heating system comprises two radiation members 10 and 11 arranged in this direction. DESCRIPTION OF THE INVENTION It is an object of the invention to provide a compact heating system giving an enhanced spectral combination. To achieve this object, the invention provides a heating system comprising a reflector having a concave cross-section that is substantially symmetrical with respect to an axis of symmetry, a first radiation system comprising at least a first radiation member capable of emitting a first type of radiation and a second radiation system comprising at least a second radiation member capable of emitting a second type of radiation, said second radiation system being positioned in a direction substantially parallel to said axis of symmetry with respect to said first radiation system. According to the invention, the radiation systems are arranged in a direction parallel to the axis of symmetry of a cross-section of the reflector with respect to one another, and not in a direction perpendicular to the axis of symmetry of a cross-section of the reflector, as in the prior art. In this manner the rays emitted by the two radiation systems are focused for a major portion onto a same region of the coating under treatment. The spectral combination of the different emitted radiation types is enhanced thereby. In addition, the radiation systems are superimposed in the direction of emission of the rays, which makes such a heating system compact. Advantageously, the first radiation member comprises a first envelope and further comprises a first reflecting layer deposited on a portion of said first envelope. This renders it possible to improve the focusing of the radiation emitted by the first radiation member and accordingly to enhance the spectral combination of the emitted rays. Advantageously, the second radiation member comprises a second envelope and further comprises a second reflecting layer deposited on a portion of said second envelope. This renders it possible to improve the focusing and to enhance the spectral combination of the emitted rays still further. Preferably, the first reflecting layer has a first concave section that is substantially symmetrical with respect to a first axis of symmetry parallel to the axis of symmetry of the cross-section of the reflector, the second reflecting layer has a second concave section that is substantially symmetrical with respect to a second axis of symmetry parallel to the axis of symmetry of the cross-section of the reflector, and the first and second reflecting layers have mutually opposed directions of concavity and are adjacent to one another. Such a configuration renders possible in particular a thermal protection of the radiation members. Such a disposition of the reflecting layers renders it possible to protect each radiation member from the radiation emitted by the other radiation member. Such a thermal protection renders it possible to prolong the operational life of such a heating system. Advantageously, the first radiation type is situated in the short infrared range, the second radiation type is situated in the medium infrared range, and the second radiation member is located between the reflector and the first radiation member. Such a configuration provides an even more enhanced spectral combination when these two types of radiation are used in such a heating system. In an advantageous embodiment of the invention, the reflector is a first reflecting layer deposited on a portion of the envelope of the first radiation member. This renders it possible in particular to omit the use of an external reflector, which reduces the bulk of such a heating system. Advantageously, the second radiation member comprises in addition a second reflecting layer deposited on a portion of the envelope of the second radiation member. This renders it possible to improve the focusing and to enhance the spectral combination of the emitted rays. Preferably, the second reflecting layer has a concave section that is substantially symmetrical with respect to an axis of symmetry parallel to the axis of symmetry of the cross-section of the first reflecting layer, the first and second reflecting layers having mutually opposed directions of concavity and being mutually adjacent. Such a heating system provides in particular a thermal protection of the radiation members. Such a heating system is used by preference in combination with an external reflector, for example in an oven already fitted with reflectors. The heating system does not have an external reflector, so that is not necessary to remove an external reflector if the heating system is to be used in an oven fitted with a reflector. Preferably, the reflecting layers used are ceramic layers. Such reflecting layers provide a good focusing of the radiation, are resistant to high operating temperatures of such a heating system, form good thermal protection means, and are easy to deposit on the radiation members. Advantageously, the first and the second radiation member are kept in position by at least one cap in which an end of the first radiation member and an end of the second radiation member are inserted. It is not necessary in this manner to interconnect the radiation members permanently as is the case in the prior art. This renders possible in particular an easy exchange of one of the radiation members when it is defective. BRIEF DESCRIPTION OF THE FIGURES The invention will be better understood and further details will become apparent from the following description which is given with reference to the annexed drawings, which merely represent non-limitative examples and in which: FIG. 1 is a cross-sectional view of a heating system from the prior art; FIG. 2a is a cross-sectional view of a first heating system according to the invention, and FIG. 2b is a longitudinal sectional view of such a system; FIGS. 3a and 3b show a preferred embodiment of a heating system according to the invention, in cross-section and in longitudinal section, respectively; FIG. 4a is a cross-sectional view of a second heating system according to the invention, and FIG. 4b is a longitudinal sectional view of such a system; and FIG. 5a is a cross-sectional view of a heating system in an advantageous embodiment of the invention, and FIG. 5b is a longitudinal sectional view of such a system. DETAILED DESCRIPTION OF AT LEAST ONE EMBODIMENT OF THE INVENTION FIGS. 2a and 2b show a first heating system according to the invention in cross-section and in longitudinal section, respectively. FIG. 2b corresponds to a section in a plane AA in FIG. 2a. FIG. 2a corresponds to a section in a plane BB in FIG. 2b. Such a heating system comprises an external reflector 201, a first radiation member 202 comprising an incandescent filament 204, a second radiation member 203 comprising a star-shaped filament 205, two supports 206, and two caps 207. The first radiation member 202 in this example is a halogen tube capable of emitting in the short infrared range, denoted IR-A below, covering mainly the wavelengths lying between 0.78 and 1.4 microns. A definition of the wavelength has been given in 1987 by the International Electrotechnical Commission (IEC) in section 845-01“Radiation, Quantities and Units”. Such a radiation member 202 in the form of a halogen tube with an incandescent filament 204 is known to those skilled in the art. For example, applicant has made such a halogen tube commercially available under reference 13402Z. The incandescent filament 204 is supplied with current through external contacts 210 which are connected to molybdenum foils 209, on which two ends of the incandescent filament 204 are welded. The first radiation member 202 has an exhaust tube tip 211 which results from the filling of the halogen tube with a rare gas and halogen mixture during the manufacture of this tube. The second radiation member 203 in this example is a halogen tube capable of emitting in the medium infrared range, denoted IR-B, comprising mainly wavelengths lying between 1.4 and 3 microns. Such a radiation member 203 in the form of a halogen tube with a star-shaped filament 205 is known to those skilled in the art. For example, applicant has made such a halogen tube commercially available under reference 17010Z, said tube being one from a range of lamps generally denoted “High-Speed Medium Wave”. The second radiation member 203 comprises external contacts 210, molybdenum foils 209, and an exhaust tube tip 211, as does the first radiation member 202. Alternative types of radiation members may obviously be used without departing from the scope of the invention. It is possible, for example, to use single-ended lamps, or also radiation members such as those described in U.S. Pat. No. 6,421,503. The cross-section of the external reflector 201 shown in FIG. 2a is a concave section having an axis of symmetry 208. The first and the second radiation member 202 and 203 are positioned in a direction parallel to said axis of symmetry 208 with respect to one another. In the example shown in FIG. 2a, the axis of symmetry 208 of the external reflector 201 is shown in vertical position, so that the first and second radiation members 202 and 203 are positioned one above the other. This positioning causes the rays emitted by the first and the second radiation member 202 and 203 to be mainly focused onto one and the same region centered on the axis of symmetry 208. A major spectral combination is thus obtained at the level of said region. When an object is thus treated by such a heating system, for example for drying a coat of paint, a point of the object under treatment is simultaneously exposed to the two types of radiation. As a result, the processing time of the object is short, and the treatment is efficient. Furthermore, such a heating system is more compact than a heating system from the prior art, in which the radiation members are mutually positioned in a direction perpendicular to the axis of symmetry 208. This is particularly advantageous because it is necessary in an oven comprising a plurality of heating systems to reduce the space occupation in the direction of movement of the objects under treatment, i.e. a direction perpendicular to the axis of symmetry 208. It is important to note here that according to the invention the radiation members 202 and 203 are not necessarily positioned on the axis of symmetry 208. The radiation members 202 and 203 may be positioned with respect to one another in a direction substantially parallel to the axis of symmetry 208, i.e. in a direction enclosing a small angle with the axis of symmetry, for example an angle smaller than 30°. In the example of FIG. 2a, the second radiation member 203 may thus be slightly shifted to the left or to the right with respect to the position in which it is shown, without departing from the spirit of the invention. In fact, such a slight shift will have little influence on the spectral combination obtained in a region of an object under treatment. In the example of FIGS. 2a and 2b, the external reflector 201 has an elliptical shape, the first and the second radiation member 202 and 203 being positioned around a focus of said ellipse. Such an elliptical shape is particularly advantageous because it renders possible a good focusing of the rays emitted by the two radiation members 202 and 203. Moreover, the fact that radiation members of the halogen type are used is particularly advantageous because the rays emitted by such radiation members can be easily focused. In the example of FIGS. 2a and 2b, the second radiation member 203 is positioned between the external reflector 201 and the first radiation member 202. Applicant has found that a better spectral combination is obtained thereby than if the first radiation member 202 were positioned between the external reflector 201 and the second radiation member 203, in the case in which the first radiation member 202 emits in the short infrared range and the second radiation member 203 in the medium infrared range. The first and second radiation members 202 and 203 in this example are kept in position with respect to one another by two caps 207 in which the ends of the radiation members 202 and 203 are inserted. Advantageously, these caps 207 are ceramic caps, and the ends of the radiation members 202 and 203 are joined to the respective caps by means of cement. Obviously, alternative types of caps may be used, in particular caps having reversible fixation means for the ends of the radiation members, for example by means of a rapid joint of the R7s type. This provides an easy replacement of one of the radiation members when it is out of order. It is obviously possible to dispense with such caps, for example in that the radiation members 202 and 203 are joined integrally together by their central sections as described in U.S. Pat. No. 6,421,503. Such a solution, however, necessitates a delicate fusion step and prevents the replacement of one of the radiation members when it is defective. In the example of FIGS. 2a and 2b, the first and the second radiation member 202 and 203 are kept in position with respect to the external reflector 201 by supports 206 which form part of said external reflector 201. Alternative types of fixation may obviously be envisaged for keeping the radiation members in position in the external reflector 201. It is to be noted that it is possible to dispense with the caps 207 or with a central fusion section by inserting the ends of the two radiation members 202 and 203 into the supports 206, in which case the radiation members 202 and 203 are not one integral whole. The supports 206 thus serve to ensure the positioning of the radiation members with respect to one another and their positioning with respect to the external reflector 201. FIGS. 3a and 3b show a heating system in a preferred embodiment of the invention in cross-section and in longitudinal section, respectively. This heating system comprises, in addition to the elements shown in FIG. 1, a first reflecting layer 301 and a second reflecting layer 302. The first and the second reflecting layer 301 and 302 have concave sections which are symmetrical with respect to the axis of symmetry 208. The first and the second reflecting layer 301 and 302 have mutually opposed concavities and are adjacent. The first reflecting layer 301 in this example is deposited on an upper portion of the first radiation member 202, and the second reflecting layer 302 is deposited on a lower portion of the second radiation member 203. Such a heating system provides an improved focusing of the radiation emitted by the first and second radiation members 202 and 203, as well as an enhanced energy efficacy as compared with the heating system of FIGS. 2a and 2b. The radiation emitted in downward direction by the second radiation member 203 is in fact reflected by the second reflecting layer 302 before it is reflected by the external reflector 201 so as to reach an object under treatment arranged below the heating system. The radiation emitted in upward direction by the first radiation member 202 is directly reflected by the first reflecting layer 301 so as to reach the object under treatment. In this manner the major portion of the radiation emitted by the two radiation members 202 and 203 will reach the object under treatment and will be focused onto a region of the object, which region has a reduced surface area. The spectral combination is thus enhanced in this region, as is indeed the power level. The reflecting layers used are known to those skilled in the art. They may be, for example, reflecting layers of gold. They may alternatively be reflecting layers of a ceramic material. Such a reflecting layer of ceramic material is used in particular in a halogen lamp made commercially available by applicant under reference 13185Z/98. It is to be noted that the reflecting layers 301 and 302 are very thin in relation to the thickness of the envelopes of the radiation members 202 and 203. For example, the thickness of a reflecting layer is of the order of 10 microns, whereas the thickness of the envelope of a radiation member is of the order of 1 mm. The thickness of the reflecting layers 301 and 302 in FIG. 3a is purposely exaggerated so that these two reflecting layers can be distinguished. It is also to be noted that alternative configurations may be used in accordance with the invention. For example, a heating system may have a ceramic layer on only one of the radiation members, which provides an improved focusing, an improved spectral combination, and an improved power level compared with the heating system of FIGS. 2a and 2b. In the example of FIGS. 3a and 3b, the reflecting layers 301 and 302 are ceramic layers and are deposited such that they provide a thermal protection for the radiation members 202 and 203. In fact, the radiation emitted by one of the radiation members will not reach the respective other radiation member directly, which leads to a lowering of the temperature of the radiation members 202 and 203 compared with the heating system of FIGS. 2a and 2b. This leads to a prolonged useful life of the radiation members 202 and 203. In the example of FIGS. 3a and 3b, the external reflector 201 has two elliptical parts. The first radiation member 202 is centered on the focus of one of the two ellipses, the second radiation member 203 on the focus of the other ellipse. Such an external reflector 201 is particularly advantageous because it makes it possible to improve the focusing of the rays emitted by the radiation members 202 and 203. FIGS. 4a and 4b show a second heating system according to the invention in cross-section and in longitudinal section, respectively. Such a heating system comprises, in addition to the elements shown in FIGS. 2a, 2b, 3a, and 3b above, a third radiation member 401. The first radiation member 202 forms a first radiation system. The second radiation member 203 and the third radiation member 401 form a second radiation system. In this example, the second radiation system is situated below the first radiation system. The invention is obviously not limited to these radiation systems. For example, the invention may comprise a first radiation system comprising two radiation members and a second radiation system comprising two radiation members. In the example of FIGS. 4a and 4b, the third radiation member 401 is a discharge lamp capable of emitting in the ultraviolet range. The third radiation member 401 comprises two electrodes 402 and is covered with a reflecting layer 403 on an upper portion of the envelope that constitutes the third radiation member 401. Such a third radiation member 401 is known to those skilled in the art. For example, a discharge tube capable of emitting in the ultraviolet range is described in U.S. Pat. No. 6,421,503. Such a heating system renders it possible to obtain a wide spectrum of wavelengths at the level of a region of an object under treatment. It will be noted, however, that it is possible to treat an object with only one or two types of radiation at a time with such a heating system. It is possible, for example, to treat an object with a combination of radiation in the short infrared and medium infrared ranges, while the third radiation member 401 is not supplied with current. On the other hand, it is possible to treat an object with exclusively a radiation in the ultraviolet range. An advantage of such a heating system is that the system is compact and can be used in a large number of applications that require various spectra of wavelengths. It is also to be noted that it is possible to vary the spectra of the radiation of the first and second radiation members 202 and 203 in dependence on the desired application in that the supply voltages for these radiation members are varied. This makes for an increase in the number of possible applications for such a heating system. In the example of FIGS. 4a and 4b, the concave section of the external reflector 201 is composed of segments. Such an external reflector is easy to construct and renders it possible to obtain a good focusing of the radiation emitted by the two radiation systems. If an external reflector of parabolic shape is used, such as the external reflector 201 of FIG. 2, it is advantageous to vary the respective positions of the radiation members 202, 203, and 401 as a function of the desired application. For example, if a drying process through radiation of medium infrared is carried out, it is advantageous to place the second radiation member 203 around the focus of the external reflector, i.e. in the location of the first radiation member 202. This may be effected in that the radiation members are rotated by means of, for example, a cap 207 capable of rotation with respect to the external reflector. The reflecting layers 301, 302, and 403 are advantageously positioned at 120° with respect to one another in this case. FIGS. 5a and 5b show a heating system in an advantageous embodiment of the invention in cross-section and in front elevation, respectively. This heating system comprises a first radiation member 501 comprising an incandescent filament 503 and a second radiation member 502 comprising a star-shaped filament 504. The first radiation member 501 comprises an envelope of which a portion is covered with a reflecting layer 505. This reflecting layer 505 comprises a concave section which is symmetrical with respect to an axis of symmetry 508. The radiation members 501 and 502 have exhaust tube tips 507, molybdenum foils 509, and external contacts 510. The radiation members 501 and 502 are kept in position with respect to one another by means of caps 506 in which the ends of the radiation members are accommodated. The reflecting layer 505 in such a heating system performs the function of the external reflector 201 of FIGS. 2a and 2b. Such a heating system is accordingly particularly advantageous, because it is less bulky than the heating system of FIGS. 2a and 2b. Furthermore, such a system may be used in an oven that is already provided with a reflector. The heating system in this advantageous embodiment of the invention is not limited to the individual embodiment shown in FIGS. 5a and 5b. For example, the second radiation member 502 may also comprise a reflecting layer. The first radiation member 501, for example, may comprise a reflecting layer on a lower half of its envelope, and the second radiation member 502 may have a reflecting layer on an upper half of its envelope. Such a system will be used to advantage with an external reflector such as the external reflector 201 of FIGS. 2a and 2b, but it may alternatively be autonomously used in an oven provided with, for example, reflecting walls. The verb “comprise” and its conjugations should be given a wide interpretation, i.e. as not excluding the presence of elements other than those listed after said verb, and it is also possible for a plurality of elements to be present if listed after said verb and preceded by the article “a” or “an”.
<SOH> BACKGROUND OF THE INVENTION <EOH>U.S. Pat. No. 6,421,503 published Jul. 16, 2002 describes a heating system comprising two radiation members capable of emitting two different types of radiation. These radiation members are tubular in shape. The first radiation member comprises an incandescent filament capable of emitting a radiation in the near infrared range, whereas the second radiation member comprises a carbon ribbon capable of emitting a radiation in the medium infrared range. It is a disadvantage of such a system that a given point of a coating under treatment is not simultaneously exposed to the two types of radiation. FIG. 1 is a cross-sectional view of such a heating system and of a coating treated by this heating system. The heating system shown in FIG. 1 corresponds to a heating system of FIG. 5 from U.S. Pat. No. 6,421,503. Such a heating system comprises a first radiation member 10 comprising a first quartz envelope 12 and a carbon ribbon 14 , and a second radiation member 11 comprising a second quartz envelope 13 and an incandescent filament 15 kept in position by a support 15 a . The two radiation members 10 and 11 are fixedly joined together by a central section 17 . Each of the two radiation members 10 and 11 is covered with a reflecting layer 16 on an upper half of the respective quartz envelope 12 or 13 . Under these operating conditions, the radiation emitted by the first and the second radiation member 10 and 11 is necessarily downwardly directed when the heating system is arranged as shown in FIG. 1 . Consequently, an object 18 to be treated by this heating system is present below said heating system. This object 18 comprises a coating 19 which is to be treated by the heating system. This may relate to, for example, a metal plate on which a paint comprising a pigment and a solvent has been deposited. In such a configuration, the rays emitted by the radiation members 10 and 11 are not focused on the same location of the coating 19 . As a result, the overlap of the two types of radiation, which is particularly advantageous in applications such as the drying of paints, is limited, i.e. the spectral combination of the spectra of the two types of radiation is limited. In addition, the fact that the rays emitted by the radiation members 10 and 11 are not focused on the same location of the coating 19 leads to a prolonged treatment time for the coating 19 , since each point of the coating 19 must be exposed to two types of radiation. Another disadvantage of such a heating system is that the heating system is cumbersome. An oven for drying the coating will in fact generally comprise several heating systems arranged side by side, parallel to a direction in which the objects under treatment are moved. The dimensions of the heating system of FIG. 1 are important in view of this direction, because the heating system comprises two radiation members 10 and 11 arranged in this direction.
<SOH> BRIEF DESCRIPTION OF THE FIGURES <EOH>The invention will be better understood and further details will become apparent from the following description which is given with reference to the annexed drawings, which merely represent non-limitative examples and in which: FIG. 1 is a cross-sectional view of a heating system from the prior art; FIG. 2 a is a cross-sectional view of a first heating system according to the invention, and FIG. 2 b is a longitudinal sectional view of such a system; FIGS. 3 a and 3 b show a preferred embodiment of a heating system according to the invention, in cross-section and in longitudinal section, respectively; FIG. 4 a is a cross-sectional view of a second heating system according to the invention, and FIG. 4 b is a longitudinal sectional view of such a system; and FIG. 5 a is a cross-sectional view of a heating system in an advantageous embodiment of the invention, and FIG. 5 b is a longitudinal sectional view of such a system. detailed-description description="Detailed Description" end="lead"?
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CAMPBELL, THOR S
HEATING SYSTEM COMPRISING AT LEAST TWO DIFFERENT RADIATIONS
UNDISCOUNTED
0
ACCEPTED
F21V
2,005
10,536,315
ACCEPTED
Image authenticating methods
To authenticate images taken by image capturing elements (3) of offending vehicles, for example, when exceeding the authorized speed, provided elements are provided for allowing informative data on the offence to be supplied, such as the speed of the vehicle, the date, the time and the place of the offence and various processing methods are provided which enable, during exploitation of the images, detection of whether or not manipulations have been carried out on the images.
1. A method of authenticating images and particularly images of offending vehicles comprising the following steps: allocating image capturing systems (3), arranged to allow the taking of images and the capture of identification elements (101) of offenders (100), means of taking pictures supplying the data representative of the images taken, hereafter called captured image data (30); providing means, hereafter called informative systems (2) for capturing physical information relative to the offence, hereafter called offence data (20); providing first memory and/or transmission means (430A) for memorising and/or transmitting the captured image data and the offence data providing operating systems (430A) for exploiting the memorised and/or transmitted data and being essentially characterised in that the operating systems apply to the captured image data, any known processing suitable for improving or conserving the quality of the images in question and/or reducing the amount of data necessary for reconstruction of the images, without any significant loss of quality, in order to reduce the size of the memories necessary for storing the captured image data and/or the capacity of the means for transmitting this data, the intermediate data representative of -images after these processings being called initial graphical data (10); the operating systems calculating from the offence data and from a graphical representation of the alphanumerical characters (410) associated with the offence data, new data representative of images, called graphical offence data (11); the operating systems merging the initial graphical data and the graphical offence data in such a way as to obtain a new set of data representative of images, called graphical identifier-data (12), in which the initial graphical data and the graphical offence data constitute sub-sets accessible from this new set of data; the operating systems calculating, by applying a non-bijective function, denoted f, to the graphical identifier data, a set of data, hereafter called summary data (31), such that knowledge of only the summary data, does not allow one to return to the graphical identifier data; the operating systems applying to the summary data, a coding process denoted c, having an associated decoding process denoted c−1, for obtaining a new set of data called signature data (33); the operating systems calculating, from the signature data and from a graphical representation of the alphanumerical characters constituting the signature data, new data representative of images, called graphical signature data (13); the operating systems merging the graphical identifier data and the graphical signature data so as to obtain a new set of data representative of images, in which the graphical identifier data and the graphical signature data constitute sub-sets accessible from this new set of data, called graphical authenticable data (14), providing second means of memorisation and/or of transmission (430B) of graphical authenticable data, providing control units (5) which can respectively read and/or receive the graphical authenticable data stored in the second memory and/or transmission means, the data actually read and/or received being called graphical received data (50); the control units searching among the graphical received data for the subset of graphical identifier data, hereafter called tested graphical identifier data (51), the control units searching among the received graphical data, for the subset of graphical signature data, hereafter called tested graphical signature data (52); the control units looking for a data set representative of signature data, called tested signature data (53), from the tested graphical signature data and from a alphanumerical character recognition table (510); the control units calculating a set of data, called tested summary data (55), by applying the non-bijective function f to the tested graphical identifier data; the control units applying to the tested signature data, the method of decoding c−1 to obtain a set of data, called received summary data (54); and the control units comparing the received summary data and the tested summary data, and supplying an alert signal when the data is not identical and/or a confirmation signal when they are identical. 2. The method of claim 1, wherein the informative systems include means to measure the speed of vehicles. 3. The method of claim 1, wherein the informative systems include means of detecting the presence of a non-authorised vehicle in a reserved lane. 4. The method of claim 1, wherein the informative systems include means of detecting a vehicle jumping a red light. 5. The method of claim 1, wherein the image capturing systems provide digital images. 6. The method of claim 1, wherein the methods of coding and/or decoding use cryptographic techniques. 7. The method of claim 1, wherein the methods of coding incorporate in the signature data, an accessible sub-set of data, containing a set of alphanumerical characters sufficient for representing the signature data. 8. The method of claim 1, wherein the operating systems apply to the image data taken, successively a method of compression and an associated method of decompression, and memorising and/or transferring the data obtained towards the memory and/or transmission means. 9. The method of claim 1, wherein the first memory and/or transmission means and the second memory and/or transmission means are united. 10. The method of claim 1, wherein the character recognition table is developed by applying a character recognition program code. 11. The method of claim 1, wherein the character recognition table is developed from tested graphical signature data. 12. The method of claim 5, wherein the informative systems include means to measure the speed of vehicles. 13. The method of claim 5, wherein the informative systems include means of detecting the presence of a non-authorised vehicle in a reserved lane. 14. The method of claim 5, wherein the informative systems include means of detecting a vehicle jumping a red light. 15. The method of claim 5, wherein the methods of coding and/or decoding use cryptographic techniques. 16. The method of claim 5, wherein the methods of coding incorporate in the signature data, an accessible sub-set of data, containing a set of alphanumerical characters sufficient for representing the signature data. 17. The method of claim 5, wherein the operating systems apply to the image data taken, successively a method of compression and an associated method of decompression, and memorising and/or transferring the data obtained towards the memory and/or transmission means. 18. The method of claim 5, wherein the first-memory and/or transmission means and the second memory and/or transmission means are united. 19. The method of claim 5, wherein the character recognition table is developed by applying a character recognition program code. 20. The method of claim 5, wherein the character recognition table is developed from tested graphical signature data.
BACKGROUND OF THE INVENTION 1. Field of Invention The present invention relates to a method allowing the authentication of images and in particular the authentication of images of vehicles caught committing an offence, such offences may be for example related to exceeding authorised speed limits, jumping red lights or the passage of a unauthorised vehicle in a lane reserved for public transport vehicles. 2. Description of Related Art In fact, up until now, two methods of control have been used, methods requiring human intervention during detection of the offence or semi-automatic methods with capture of the image of the offending vehicles. In the first case, the speed controls require the physical intervention of the police who in general and firstly note the offence. The police statement resulting from this detection is then used for punishment of the offence and if necessary to implement ways to make the offending driver pay the corresponding fines. However, such a series of operations requires human intervention at each stage of the process. The probability of a speed control therefore remains relatively low and the weight of the subsequent processing of statements leads to a quite low rate of collection of payment of fines. Consequently, this gives some motorists the feeling of impunity, which is detrimental in terms of security. The same problem arises for offences of different types, for example, jumping a red light or driving in a reserved lane. In the second case, the set-up of automatic procedures from the detection of the offence up to the recovery of the amount claimed as fines seems to greatly improve security and respect of the highway code. Several approaches have been proposed in the past to attempt to automate such procedures. For example, U.S. Pat. No. 5,381,155 proposes using a Doppler effect radar, firstly to measure the speed of vehicles and therefore to be able to detect is they are offending, then to trigger a camera to capture images of the offending vehicle or vehicles. These images are then transmitted to a calculating unit to enable recognition and identification of the licence plates of the vehicles in question, then the images can be stored in non volatile memories. When the said licence plates have been identified, it is then possible to transmit the registration numbers of the offending vehicles by telecommunication systems reserved for the police and thereby allowing intervention of the latter. The presence of representatives of the police is therefore necessary for the noting of the offence. Where an offence is contested by the driver or drivers concerned, the recorded images at the moment of the offence can be extracted from the memory in which they have been stored and can be used. However, such an approach comes up against a major obstacle. It is indeed easy, for example by using image touching up software, to modify the images stored and to replace, for example, the numbers of the license plates with other numbers. Once such a manipulation can be easily implemented, the legal value of the transmitted images is greatly reduced. In an attempt to avoid this disadvantage, U.S. Pat. No. 5,563,590 proposed inserting, in the image taken at the moment of the offence, information relating to the speed of the vehicle, the hour and time of the offence, etc., in the form of alphanumerical characters. From the alphanumerical information gathered in this way, new alphanumerical control characters are constructed which are also inserted in the image. The photographs corresponding to the offending vehicles contain both the above characteristic information and the control alphanumerical characters. Subsequently, when these documents are contested, it is possible to verify that the control alphanumerical characters are really those which correspond to the characteristic information taken at the time of the offence. However, the device described in this patent presents significant disadvantages of different natures. In particular, it uses silver photography techniques which require chemical process of films. This leads to a need for regular and costly human intervention, for example to load the film rolls in the cameras and to replace them when they have been used. The simple use of digital storage mediums instead of silver mediums does not resolve any of these problems. Indeed, the alphanumerical characters used to characterise the images and assure control of the images appear in this case directly identifiable on the images and it is relatively easy to modify them, for example, with the aid of the previous touching up graphics software. Furthermore, this information hides a part of the image which may lead to contentions in some cases. In another improvement, U.S. Pat. No. 6,269,446, proposes calculating a digital signature from the images, this signature being placed in a hidden and non standardised way, in the header of the image files. These solution presents however at least three serious disadvantages: firstly, certain formats of image files do not have a header, in particular, most of the image representative files recorded without image compression type processing, i.e. those with the best definition, secondly, with the signature in question being masked it can be contested by offending motorists because it is not an integral part of the elements of the judicial file for the offence, finally, because of the non standardised character of these operations, this signature may be deleted irreversibly during simple operations for saving the files. SUMMARY OF THE INVENTION The present invention has in particular the object of proposing an image authentication process and particularly of images of offending vehicles and accordingly, a method according to the invention comprises the following steps: allocating image capturing systems, arranged to allow the taking of images and the capture of identification elements of offenders, means of taking pictures supplying the data representative of the images taken, hereafter called captured image data, providing means, hereafter called informative systems, triggered by the capture of physical information relative to the offence, measure of the speed, time, date, location, etc. hereafter called offence data providing first memory and/or transmission means for memorising and/or transmitting the captured image data and the offence data providing operating systems for exploiting the memorised and/or transmitted data and is essentially characterised in that: the operating systems apply to the captured image data, any known processing suitable for improving or conserving the quality of the images in question and/or to reduce the amount of data necessary for reconstruction of the images, without any significant loss of quality, in order to reduce the size of the memories necessary for storing the captured image data and/or the capacity of the means transmitting this data, the intermediate data representative of images after the processings being called initial graphical data, the operating systems calculating from the offence data and from a graphical representation of the alphanumerical characters associated with this offence data, new data representative of images, called graphical offence data, the operating systems merging the initial graphical data and the graphical offence data in such a way as to obtain a new set of data representative of images, called graphical identifier data, in which the initial graphical data and the graphical offence data constitute sub-sets accessible from this new set of data, the operating systems calculating, by applying a non-bijective function, denoted f, to the graphical identifier data, a set of data, hereafter called summary data, such that knowledge of only the summary data, does not allow one to return to the graphical identifier data, the operating systems applying to the summary data, a coding process denoted c, having an associated decoding process denoted c−1, for obtaining a new set of data called signature data, the operating systems calculating, from the signature data and from a graphical representation of the alphanumerical characters associated with the signature data, new data representative of images, called graphical signature data, the operating systems merging the graphical identifier data and the graphical signature data so as to obtain a new set of data representative of images, in which the graphical identifier data and the graphical signature data constitute sub-sets accessible from this new set of data, called graphical authenticable data, providing second means of memorisation and/or of transmission of graphical authenticable data, providing control units which can respectively read and/or receive the graphical authenticable data stored in the second memory and/or transmission means, the data actually read and/or received being called graphical received data, the control units searching among the graphical received data for the subset of graphical identifier data, hereafter called tested graphical identifier data, the control units searching among the received graphical data, for the subset of graphical signature data, hereafter called tested graphical signature data, the control units looking for a data set representative of signature data, called tested signature data, from the tested graphical signature data and from a alphanumerical character recognition table, the control units calculating a set of data, called tested summary data by applying the non-bijective function f to the tested graphical identifier data, the control units applying to the tested signature data, the method of decoding c−1 to obtain a set of data, called received summary data, and the control units compare the received summary data and the tested summary data, and supply an alert signal when the data is not identical and/or a confirmation signal when they are identical, In preferred embodiments of the method according to the invention, one has recourse to one and/or another of the following arrangements: the informative systems include means to measure the speed of vehicles, the informative systems include means of detecting the presence of a non-authorised vehicle in a reserved lane, the informative systems include means of detecting a vehicle jumping a red light, the image capturing systems provide digital images, the methods of coding and/or decoding use cryptographic techniques, the methods of coding incorporate in the signature data, a sub-set of data, the subset being accessible and containing a set of alphanumerical characters sufficient for representing the signature data, the operating systems applying to the image data taken, successively a method of compression and an associated method of decompression, and memorising and/or transferring the data obtained towards the memory and/or transmission means, the first memory and/or transmission means of memorisation and the second memory and/or transmission means are united, the character recognition table is developed by applying a character recognition program code, the character recognition table is developed from tested graphical signature data. Other features and advantages of the invention will appear from the following detailed description of one of the embodiments, given by way of a non-limiting example with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS In the drawings: FIG. 1 is a schematic view of a method according to the prior art where a vehicle (1) moving on the road (100) in the direction indicated by the arrow (F), is intercepted by the radar beam (200) of an informative system including in particular a speedometer (2) linked to operating systems (4), and to image capturing systems (3), FIG. 2 is a schematic view of a step of the method according to the invention where a processor (400) of the operating systems merges the initial graphical data (10), of a vehicle (1), taken from the front and including identification elements (101) and graphical offence data (11), for obtaining the graphical identifier data (12), FIG. 3 is a schematic view of an intermediate step of the method according to the invention where a processor (400) of the operating systems calculates from the graphical identifier data (12) and by action of an appropriate program code (40) placed in a non-volatile memory means, the summary data (31), FIG. 4 is a schematic view of an intermediate step of the method according to the invention where a processor (400) of the operating systems (4) calculates from the summary data (31) and by action of an appropriate program code (41) placed in a non-volatile memory means, the signature data (33), FIG. 5 is a schematic view of an intermediate step of a method according to the invention where a processor (400) of the operating systems (4) merges the graphical identifier data (12) and the graphical signature data (13), to constitute graphical authenticable data (14), FIG. 6 is a schematic view representing an example of a series of steps of the process according to the invention, the operating systems and the control units, here placed outside so as not to overload the figure, being connected by any known means to the different elements. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS When the speed of a vehicle (1), including an identification element (101), such as a licence plate, exceeds the authorised speed limit, a device according to the prior art including a speedometer (2) and an image capturing system (3) is arranged to take images of the offending vehicle in such a way as to enable its identification. The speedometer may be for example made up of a Doppler effect radar, of a magnetic tape buried under the road or of a laser system. Means are provided for providing associated physical information, such as the time and the date of the offence, the position of the device, etc. First means are provided for recording and/or transmitting the data representative of the images taken by the image capturing systems, hereafter designated captured image data (30) and the data representative of the physical information, hereafter called offence data (20), preferably in the form of digital data. In the example of FIG. 6, memory and/or transmission means have been placed at three points of the diagram, but it will be apparent that such means can be disposed at any other point of the diagram, at positions naturally determined in ways known by skilled men in the art. The memory means may also be made in any known way, by using for example semiconductor memories, magnetic memories etc. The data transmission means may be of different types, transmission by cable, by communication bus or by the radio. The operating systems (4) are provided for operating on this data. In order, in particular, to reduce the transmission times of the offence data and the captured image data and/to carry out the different processes implemented in the method, it is advantageous to equip the operating systems with one or more processors (400) and first volatile and non volatile memory and/or transmission means (430A). In the particular embodiment examples, the processors can be integrated in semiconductor FPGA type components or specialised ASIC type semiconductor components. The contents of these first memory means can of course be read and written by the processors of these operating systems. It is possible to apply to the captured data, well known data compression methods enabling the size of memory used for storing the data or the capacity of the transmission means of the data to be reduced. Among the methods of data compression, it is possible to use methods known as without information loss or methods known as entropy, with information loss, applied in particular to the data representative of images and obtaining in this way compressed data. A compression factor allowing identification of offending vehicles without any ambiguity during the display of the images, is chosen. The choice of compression factor can be made, for example, during installation of the image capturing systems, the operating systems recording in the memory means, data representative of images taken for different compression factors, and transmitting the contents of these memory means to the control units (5), used only during the installation phase. The control units use display means in order to verify the quality of the images reconstructed from the compressed data. Similarly, when necessary, for example in the case of bad lighting or bad weather conditions, the operating systems can apply any known processing method to the image data taken in order to facilitate the identification of the offending vehicles. For example it is possible to intensify the contrast of the images and to recognise the alphanumerical characters registered on the licence plate. After the possible application of these processes, new data representative of the offending vehicles called initial graphical data (10) is obtained which can be memorised or transmitted. Any know method of memorisation can be used, and in particular non-volatile methods. Non-volatile memory means are used to store the graphical representation of the alphanumerical characters output from the informative systems, this memory means being called a non volatile font memory. In a first embodiment, the non-volatile font memory contains the graphical representation of the alphanumerical character in the form of point matrixes. In a second embodiment, the non-volatile font memory contains the graphical representation of the alphanumerical character in the form of bar codes. New data representative of images displaying the offence data, is determined from the offence data and from the graphical representation of the alphanumerical characters, these images being for example: 123 km/h=01/01/02 10 h:30 Paris Alma as illustrated in FIG. 2, this data being subsequently called, graphical offence data. In the particular case where data compression has not been applied to the captured image data and where one wishes to be able to simultaneously display the image of the offending vehicle and the images displaying the offence data, a new set of data, called graphical identifier data (12) is developed through the following steps: determining the relative sizes of the images of the data representative of the images incorporating the initial graphical data and the graphical offence data, this operation having being done during installation of the system, and recording in a memory the initial graphical data and the graphical offence data In FIG. 6, the dotted lines in the memory and/or transmission means (430A) are a symbolic representation of the fact that the graphical offence data comes from the offence data (20) and that the initial graphical data comes from the captured images (30). In this way, the graphical offence data and the initial graphical data constitute two sub-sets accessible from the graphical identifier data. In the particular example represented in FIG. 2, the images representing the offence data are placed under the images taken by the image capture systems. It is apparent, that the images representing the offence data could in an equivalent way be, for example, placed above images taken by the image capturing systems, or on the sides or any other place. It should be noted that when one of the data compression methods has been used, the merging of the graphical identifier data and the graphical offence data is also possible. In this case, it is for example possible to apply in an intermediary step, the method of decompression associated with the two data sets, which allows it to be reduced to the previous case, then applying once again the method of compression to obtain the graphical identifier data. A program code (40) necessary for applying to a selected set of data, a non bijective calculation method known in the prior art and hereafter called function f, is memorised in a non volatile memory. For example, it is possible to use the calculation method described in the standardisation document FIPS PUB 180-1, published by the National Technical Information Service, U.S. Department of Commerce, Springfield Calif. 22161. The implementation of this method on the graphical identifier data leads to a new set of data, hereafter called summary data (31). In the above case, the summary data is then sets of 160 bits of information. It should be noted, that with images with a definition permitting the identification of offending vehicles, i.e. including several tens of thousands of image elements, it is evidently impossible, from the summary data of 160 bits, to reconstruct the graphical identifier data by using an inverse calculation method. A method of coding known as public key/private key, such as is described for example in U.S. Pat. No. 4,405,829 is then applied to the summary data, which leads to new data, hereafter designated coded summary data. There again, the program code (41) necessary for the application of the coding method in question is memorised in a non volatile memory. The abovementioned private key is known only to skilled personnel. The private key can be permanently memorised in the operating systems or preferably in volatile memories, allowing the security of the method to be improved. In the latter case, the key can be downloaded from a highly secure database. Accordingly, in case of theft of a device implementing the process, the private key remains inaccessible, even if the elements constituting the device are analysed. In a particular embodiment, the operating systems merge the coded summary data with another set of data, called alphabet data (420), for example by placing after the coded summary data the set of alphanumerical characters sufficient for representing the coded summary data. For example, when the coded summary data is represented in a hexadecimal base, the operating systems place after the coded summary data, alphanumerical characters 0 to 9 and A to F which constitute in this case the alphabet data. It should be noted that in the particular example of implementation given above, the alphabet data is placed after the coded summary data, but that this alphabet data could be also be placed before the coded summary data or in any other way allowing the whole of the subset of alphabet data to be reconstituted. The coded summary data, which may merge with the alphabet data, is called signature data (33). It should also be noted that merging the alphabet data with the coded summary data does not change the decoding method c−1, since the coded summary data still forms an accessible sub-set of the signature data From the signature data and from the graphical representation of the alphanumerical characters new data representative of images displaying the signature data is determined, these images being for example: 13579BDF02468ACE1357 as illustrated in FIG. 5, the new data subsequently being called graphical signature data (13). The graphical representations in question can be formed of point matrixes or bar codes for example. The graphical identifier data (12) is merged with the graphical signature data (13), for example, according to the method already used for merging the graphical offence data (11) with the initial graphical data (10) and in this way the authenticable graphical data is obtained (14). In the particular example of FIG. 5, the images representing the signature data are placed under the images representing the graphical identifier data. It will be apparent, that the images representing the signature data could also be placed above the images representing the graphical identifier data, or on the sides or at any other place. Furthermore the operating systems are also equipped with second memory and/or transmission means (430B) in order to enable the diffusion of the graphical authenticable data. In a first embodiment, the operating systems include removable non volatile memory means, for example in the form of a memory card which can be removed from the system by an operator and placed in a control unit (5). Such a control unit may be made be made up of a portable computer or a much smaller box capable of reading the contents of the card when it is associated with it. In this first embodiment, the removable non volatile memory means can also be used as first memory means. In a second embodiment, the operating systems include telecommunication means, for example, linked to a telephone line, allowing the transmission of authenticable graphical data towards a control unit. Such a unit may be made up of a computer equipped with a modem connected to a telephone line. In this second embodiment, the transmission means can also be used as first transmission means for telecommunication with the image capture systems. In a third embodiment, the operating systems include wireless telecommunication means and are arranged to transmit the authenticable graphical data to a control unit. The control unit may be constituted of a computer comprising a radio modem. In the third embodiment, the first transmission means can be of the same kind as those above. The data actually read and/or received by the control units is called received graphical data. The control units include one or several processors. The control units can record in third memory means (530A), like hard disks for example, the received graphical data in the form of computer files. These memory means can be also used for storing all the algorithms and data necessary for looking for the size and position of the graphical identifier data and the graphical signature data. The set of received graphical data is therefore separated into two sub-sets of data called tested graphical identifier data (51) and tested graphical signature data (52), the two sub-sets being associated with sub-sets of graphical identifier data and graphical signature data, respectively, of the set of data memorised and/or transmitted by the operating systems. In a first embodiment, the control units include in the non-volatile memory means, a program code (510A) for recognising the characters which convert the tested graphical signature data into alphanumeric characters to form a new set of data called signature data. In a second embodiment and when the coded summary data has been merged as described above with the alphabet data (420), to form signature data, the following steps are carried out at the control units: looking for tested graphical signature data in the received graphical data, looking for graphical representations of the alphabet data in the graphical signature data, called tested graphical alphabet data (510B), calculating the tested signature data (53) by comparing the tested graphical signature data with the tested graphical alphabet data. The memory means can also contain the non-bijective calculation operating program code used above, defined by the function f, as well as the operating program code of the decoding program c−1, known through the public key associated with the private key which was used to code the summary data. The function f is applied to the tested graphical identifier data (51) leading to new data called tested summary data (55) and the decoding program c−1 is applied to the tested signature data leading to new data called received summary data (54), respectively. The tested summary data and the received summary data are compared. When the two sets of data are identical, the images are considered as being authenticated. An alphanumeric message of validation directly readable by a human operator can be displayed on the screen. On the contrary, when two sets of data are not identical, a signal visually readable on the screen or by any other method indicating that manipulation of the image has been detected, can be provided. By using the method which has just been described, it is therefore possible to verify if there has been any falsification of an image, for example by giving an offending vehicle the identification characteristics of another vehicle. The resulting image authentication thereby solves the unsolved problems mentioned above. As is evident, and is apparent from the foregoing, the invention is not limited to the example of the particular embodiment which has just been described, on the contrary it includes all variants in particular those in which the method is implemented when the offence is other than that which is associated with exceeding authorised speed by a vehicle and for example, when it relates to the detection of a person in a protected access zone for which the person has no authorisation.
<SOH> BACKGROUND OF THE INVENTION <EOH>1. Field of Invention The present invention relates to a method allowing the authentication of images and in particular the authentication of images of vehicles caught committing an offence, such offences may be for example related to exceeding authorised speed limits, jumping red lights or the passage of a unauthorised vehicle in a lane reserved for public transport vehicles. 2. Description of Related Art In fact, up until now, two methods of control have been used, methods requiring human intervention during detection of the offence or semi-automatic methods with capture of the image of the offending vehicles. In the first case, the speed controls require the physical intervention of the police who in general and firstly note the offence. The police statement resulting from this detection is then used for punishment of the offence and if necessary to implement ways to make the offending driver pay the corresponding fines. However, such a series of operations requires human intervention at each stage of the process. The probability of a speed control therefore remains relatively low and the weight of the subsequent processing of statements leads to a quite low rate of collection of payment of fines. Consequently, this gives some motorists the feeling of impunity, which is detrimental in terms of security. The same problem arises for offences of different types, for example, jumping a red light or driving in a reserved lane. In the second case, the set-up of automatic procedures from the detection of the offence up to the recovery of the amount claimed as fines seems to greatly improve security and respect of the highway code. Several approaches have been proposed in the past to attempt to automate such procedures. For example, U.S. Pat. No. 5,381,155 proposes using a Doppler effect radar, firstly to measure the speed of vehicles and therefore to be able to detect is they are offending, then to trigger a camera to capture images of the offending vehicle or vehicles. These images are then transmitted to a calculating unit to enable recognition and identification of the licence plates of the vehicles in question, then the images can be stored in non volatile memories. When the said licence plates have been identified, it is then possible to transmit the registration numbers of the offending vehicles by telecommunication systems reserved for the police and thereby allowing intervention of the latter. The presence of representatives of the police is therefore necessary for the noting of the offence. Where an offence is contested by the driver or drivers concerned, the recorded images at the moment of the offence can be extracted from the memory in which they have been stored and can be used. However, such an approach comes up against a major obstacle. It is indeed easy, for example by using image touching up software, to modify the images stored and to replace, for example, the numbers of the license plates with other numbers. Once such a manipulation can be easily implemented, the legal value of the transmitted images is greatly reduced. In an attempt to avoid this disadvantage, U.S. Pat. No. 5,563,590 proposed inserting, in the image taken at the moment of the offence, information relating to the speed of the vehicle, the hour and time of the offence, etc., in the form of alphanumerical characters. From the alphanumerical information gathered in this way, new alphanumerical control characters are constructed which are also inserted in the image. The photographs corresponding to the offending vehicles contain both the above characteristic information and the control alphanumerical characters. Subsequently, when these documents are contested, it is possible to verify that the control alphanumerical characters are really those which correspond to the characteristic information taken at the time of the offence. However, the device described in this patent presents significant disadvantages of different natures. In particular, it uses silver photography techniques which require chemical process of films. This leads to a need for regular and costly human intervention, for example to load the film rolls in the cameras and to replace them when they have been used. The simple use of digital storage mediums instead of silver mediums does not resolve any of these problems. Indeed, the alphanumerical characters used to characterise the images and assure control of the images appear in this case directly identifiable on the images and it is relatively easy to modify them, for example, with the aid of the previous touching up graphics software. Furthermore, this information hides a part of the image which may lead to contentions in some cases. In another improvement, U.S. Pat. No. 6,269,446, proposes calculating a digital signature from the images, this signature being placed in a hidden and non standardised way, in the header of the image files. These solution presents however at least three serious disadvantages: firstly, certain formats of image files do not have a header, in particular, most of the image representative files recorded without image compression type processing, i.e. those with the best definition, secondly, with the signature in question being masked it can be contested by offending motorists because it is not an integral part of the elements of the judicial file for the offence, finally, because of the non standardised character of these operations, this signature may be deleted irreversibly during simple operations for saving the files.
<SOH> SUMMARY OF THE INVENTION <EOH>The present invention has in particular the object of proposing an image authentication process and particularly of images of offending vehicles and accordingly, a method according to the invention comprises the following steps: allocating image capturing systems, arranged to allow the taking of images and the capture of identification elements of offenders, means of taking pictures supplying the data representative of the images taken, hereafter called captured image data, providing means, hereafter called informative systems, triggered by the capture of physical information relative to the offence, measure of the speed, time, date, location, etc. hereafter called offence data providing first memory and/or transmission means for memorising and/or transmitting the captured image data and the offence data providing operating systems for exploiting the memorised and/or transmitted data and is essentially characterised in that: the operating systems apply to the captured image data, any known processing suitable for improving or conserving the quality of the images in question and/or to reduce the amount of data necessary for reconstruction of the images, without any significant loss of quality, in order to reduce the size of the memories necessary for storing the captured image data and/or the capacity of the means transmitting this data, the intermediate data representative of images after the processings being called initial graphical data, the operating systems calculating from the offence data and from a graphical representation of the alphanumerical characters associated with this offence data, new data representative of images, called graphical offence data, the operating systems merging the initial graphical data and the graphical offence data in such a way as to obtain a new set of data representative of images, called graphical identifier data, in which the initial graphical data and the graphical offence data constitute sub-sets accessible from this new set of data, the operating systems calculating, by applying a non-bijective function, denoted f, to the graphical identifier data, a set of data, hereafter called summary data, such that knowledge of only the summary data, does not allow one to return to the graphical identifier data, the operating systems applying to the summary data, a coding process denoted c, having an associated decoding process denoted c −1 , for obtaining a new set of data called signature data, the operating systems calculating, from the signature data and from a graphical representation of the alphanumerical characters associated with the signature data, new data representative of images, called graphical signature data, the operating systems merging the graphical identifier data and the graphical signature data so as to obtain a new set of data representative of images, in which the graphical identifier data and the graphical signature data constitute sub-sets accessible from this new set of data, called graphical authenticable data, providing second means of memorisation and/or of transmission of graphical authenticable data, providing control units which can respectively read and/or receive the graphical authenticable data stored in the second memory and/or transmission means, the data actually read and/or received being called graphical received data, the control units searching among the graphical received data for the subset of graphical identifier data, hereafter called tested graphical identifier data, the control units searching among the received graphical data, for the subset of graphical signature data, hereafter called tested graphical signature data, the control units looking for a data set representative of signature data, called tested signature data, from the tested graphical signature data and from a alphanumerical character recognition table, the control units calculating a set of data, called tested summary data by applying the non-bijective function f to the tested graphical identifier data, the control units applying to the tested signature data, the method of decoding c −1 to obtain a set of data, called received summary data, and the control units compare the received summary data and the tested summary data, and supply an alert signal when the data is not identical and/or a confirmation signal when they are identical, In preferred embodiments of the method according to the invention, one has recourse to one and/or another of the following arrangements: the informative systems include means to measure the speed of vehicles, the informative systems include means of detecting the presence of a non-authorised vehicle in a reserved lane, the informative systems include means of detecting a vehicle jumping a red light, the image capturing systems provide digital images, the methods of coding and/or decoding use cryptographic techniques, the methods of coding incorporate in the signature data, a sub-set of data, the subset being accessible and containing a set of alphanumerical characters sufficient for representing the signature data, the operating systems applying to the image data taken, successively a method of compression and an associated method of decompression, and memorising and/or transferring the data obtained towards the memory and/or transmission means, the first memory and/or transmission means of memorisation and the second memory and/or transmission means are united, the character recognition table is developed by applying a character recognition program code, the character recognition table is developed from tested graphical signature data. Other features and advantages of the invention will appear from the following detailed description of one of the embodiments, given by way of a non-limiting example with reference to the accompanying drawings.
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0
BITAR, NANCY
IMAGE AUTHENTICATING METHODS
SMALL
0
ACCEPTED
G06K
2,005
10,536,506
ACCEPTED
Microbial feedstock for filter feeding aquatic organisms
The present invention provides a method of cultivating filter feeders such as Artemia by substituting special microorganisms for naturally occurring microscopic algae, and providing conditions optimal for the growth of these organisms. These subsituted special microorganisms provide an abundant food source for Artemia and subsequently the Artemia provide a food source for higher order members of the marine food chain.
1. A method for cultivating filter feeders comprising the steps of: providing tanks with seawater having microorganisms; adding essential elements to said seawater; adding a food source to said seawater forming a mixture and aerating said mixture continuously thereby forming a dense bloom of bacterial; and adding artemia cysts to said mixture. 2. The method according to claim 1 wherein said essential elements are selected from the group consisting of nitrogen, iron and phosphorous. 3. The method according to claim 1 wherein said microorganisms are bacteria selected from the group consisting of Bacillus megatherium and Vibrio alginolyticus. 4. The method according to claim 1 wherein said microorganisms are wild saltwater bacteria. 5. The method according to claim 3 wherein said bacteria are genetically engineered to promote additional nutritional properties. 6. The method according to claim 3 wherein said bacteria are clonal bacteria selected from the group consisting of Bacillus megatherium and Vibrio alginolyticus. 7. The method according to claim 1 wherein said food source is sucrose. 8. The method according to claim 1 wherein said food source is selected from the group consisting of molasses, peanut cake, sugar cane syrup and sugar beet syrup. 9. The method according to claim 1 wherein said filter feeders are Artemia. 10. The method according to claim 1 wherein said filter feeders are selected from the group consisting of clams and mollusk. 11. The method according to claim 9 further comprising the step of harvesting adult Artemia from said seawater. 12. The method according to claim 1 further comprising the step of disinfecting said seawater. 13. The method according to claim 10 wherein said disinfection step comprises the addition of chlorine to said seawater. 14. The method according to claim 12 wherein said disinfection step comprises autoclaving said seawater. 15. The method according to claim 12 wherein said disinfection step comprises filtering said seawater. 16. The method according to claim 1 further comprising the step of exchanging said seawater to prevent unwanted organism. 17. A method of preparing food for larvae of fish or crustacean, whereby nauplii released by the development of Artemia cysts or deposited by ovoviviparous reproduction are fed to said larvae comprising the production of Artemia cysts or Artemia nauplii according to the method of claim 9. 18. The method according to claim 17 wherein said Artemia cysts are fed to said larvae in an admixture of other feedstock. 19. The method according to claim 17 wherein said Artemia cysts are fed to clams, oysters, mullet, milk fish and mollusks. 20. The method according to claim 1 wherein said microorganisms are selected from the group consisting of algae and blue green algae. 21. The method according to claim 1 further comprising the step of providing light exposure to said tank. 22. The method according to claim 21 wherein said light is selected from the group consisting of natural sunlight and artificial light. 23. The method according to claim 1 further comprising controlling temperature of said seawater.
CROSS REFERENCES TO RELATED APPLICATIONS This application claims priority of the U.S. Provisional Patent Application Ser. No. 60/429,095 filed Nov. 26, 2002 which is incorporated by reference in its entirety. FIELD OF INVENTION This invention relates to a method of increasing the production of filter feeding organisms such as Artemia in aquaculture, these filter feeding organisms can be used as feed in the cultivation of farmed fish, crustaceans and shellfish. BACKGROUND OF INVENTION In recent years it has become increasing popular to cultivate marine species in controlled settings. This cultivation, which is commonly referred to as aquaculture, has allowed the production of a variety of marine species for human consumption. Increasingly, many edible fishes have been produced using aquaculture. While aquaculture has shown marked technological increases, to support the growth of this industry, it is necessary to produce an artificial feed or to increase the harvest of naturally occurring foodstuff such as Artemia, Brachinus salina, Daphnia, etc. All marine life in the seas ultimately depends on microscopic algae for their growth or the growth of their food within the marine food chain. This microscopic algae, which is the first link within the marine food chain, is directly consumed by filter feeders such as shell fish, and indirectly through the complex food chain within the sea by the rest of marine life. Algae grows very slowly, however, as they only divide approximately once a day and therefore they are not easily available. This lack of availability contributes to a significant increase in the cost of aquaculture products. Attempts to replicate or replace natural foodstuff within aquaculture have been met with limited success. In U.S. Pat. No. 5,158,788 to Lavens et al. (“Lavens”), a method is described to produce a feed for aquaculture from yeast. Lavens entails a multi-step process in which yeast cells are processed by hydrolyzing its cell wall producing a digestible feed for aquaculture. Unfortunately, the multi-step process as suggested by Lavens is labor intensive and therefore not feasible economically. Most importantly, the destruction of the cell wall that is needed to produce this artificial feed causes pollution of the aquaculture by the cell materials contained within the yeast cell. One significant natural food source within the marine food chain that feeds off microscopic algae is Artemia. Artemia commonly referred to as brine shrimp is an excellent foodstuff for aquaculture, because of its position within the marine food chain and its desirability as a food source for higher members of marine culture. They are an excellent food for aquaculture, because unlike prior art foods in aquaculture they do not undergo putrefaction by microorganisms and foul water used in aquaculture, but rather they clear the water of fouling micro-organisms. It is commonly known that Artemia can be used as a feed for species such as shrimp, fishes, etc. The natural harvesting of Artemia for their use in aquaculture, however, is subject to environmental factors that have recently led to shortages. Artemia grow in large saline lakes such as the Great Salt Lake in Utah. Artemia have been harvested in the Great Salt Lake for many years. Unfortunately, recent harvests have been poor and the cost of Artemia cysts has increased more than three fold. It is thought that these recent poor harvests have been caused by changing weather patterns. Severe climatic disturbances caused by the warm weather and excessive rainfall that accompanied El Nino caused production levels of the Artemia from the Great Salt Lake to decrease dramatically. The harvest of Artemia cysts in 1995-96 and 1996-97 was approximately 15 million pounds gross weight. Of this total harvest only about fifty percent is suitable for use. The 1997-98 harvest was only approximately 6 million pounds gross weight. Decreases in harvesting of Artemia cysts, such as in the case of El Nino, not only cause problems with availability, but also sharp increases in the price of Artemia cysts. This sharp increase in cost makes the use of Artemia as a feed for aquaculture economically impermissible. Although there are several other sources of Artemia throughout the world, the Great Salt Lake provides more than ninety percent of the world's Aretmia cyst consumption. While additional sources of Artemia have been found in Russia, Turkey, and China, these additional sources have not offset the declining harvest of the Great Salt Lake. Various methods of producing Artemia within aquaculture have been explored such as in Vietnam, where Artemia have been growth in ponds having abundance of natural algae. In Hawaii, yeast and greenwater have been used to grow Artemia and rotifers for seahorse and Asian sea bass aquaculture. Unfortunately, these various efforts have been met with limited success as these prior methods of producing Artemia are labor extensive and not economically feasible. SUMMARY OF INVENTION The bulk of food for all living creatures of the sea originates with microscopic algae. This microscopic algae is directly consumed by filter feeders such as shellfish and indirectly by the rest of marine life through a complex food chain. The inventive method consists of mimicking this natural phenomenon in mariculture by substituting special microorganisms for naturally occurring microscopic algae, and providing conditions optimal for the growth of these organisms. These substituted special microorganisms then provide an abundant food source for higher order members of the marine food chain. As stated above, microscopic algae grow very slowly and even when provided with all their mineral requirements, divide only about once every 24 hours. On the other hand, microorganisms such as bacteria, and probably certain species of algae, blue green bacteria, and fungi divide about once every thirty minutes if provided with an organic energy source. According to the inventive method, mineral elements are added to seawater to provide a culture for the optimal growth of selected microorganism. The added mineral elements are nitrogen, phosphorus, and iron, because these are the only mineral elements deficient within seawater that are essential to all life. In addition to the added elements, sugar (sucrose) is added to provide an energy source. In an illustrative embodiment of the inventive method, sucrose is used to provide both energy and a carbon source. Sucrose has an advantage as an energy source, in that it consists of only carbon, oxygen, and hydrogen. Sucrose, however, is only one example of carbonaceous substances that can serve this function. Other food sources can be used to support the growth of these special microorganisms that include such inexpensive products, such as peanut cake after the oil is pressed out, molasses, which is a by-product of sugar production, sugar beet syrup and cane syrup or the like. Their disadvantage is that they can support many kinds of microorganisms, some of which could be pathogenic. This disadvantage, however, can be remedied by sterilizing seawater with chlorine or filtering the seawater. Care has to be taken, however, to prevent foreign microbes' entry into the cultures. It is contemplated within the scope of the invention that the seawater within the culture medium can be refreshed frequently to prevent unwanted organisms from taking over the culture. It is also contemplated within the scope of the invention that the inventive method can be used as an efficient method to fix atmospheric carbon dioxide. The fixing of atmospheric carbon dioxide into plant material requires a significant amount of energy. The use of the inventive method to grow shellfish on a large scale wherein the shellfish produce calcium carbonate from atmospheric carbon dioxide results in a more energy efficient method of alleviating the excess of carbon dioxide within the atmosphere. DETAILED DESCRIPTION The instant invention provides inventive methods for the growth of filter feeders such as Artemia using special microorganisms such as bacteria as a food source. It is contemplated within the scope of the invention that other filter feeders such as claims, oysters and scallops or the like. This growth of Artemia is accomplished with greater production and reliability of existing methods. According to the inventive method, seawater is placed in culture tanks and fortified with nitrogen, phosphorus and iron, and sterilized with chlorine forming a culture medium. After the chlorine is dissipated, a sugar such as sucrose or the like and a dense culture of Bacillus megatherium or any other suitable organism is added to the culture medium. After the addition of the minerals and sugar and aeration of the culture, in approximately one-day, a dense bacterial culture is formed. Artemia cysts are added and they subsequently consume bacteria and grow. The overnight culture of Bacillus megatherium should have a volume of approximately 1/10,000 within the culture tank. Because the Artemia, which are filter feeders, thrive on the Bacillus megatherium, it is contemplated within the scope of this invention that other filter feeders such as clams, oysters or the like could also grow on this diet. The culture medium is purposely simple and highly selective. Very few organisms can grow in the high salinity of seawater, and produce all their complex molecules when provided with only minerals and sugar. This simplicity of the culture medium makes it highly unlikely that the organisms would be pathogenic. This is borne out in experiments that are set forth below, where the only (predominant) bacterial organisms are Bacillus megatherium and Vibrio alginolyticus. Neither of these bacteria is considered pathogens although the Vibrio may be classified as an opportunistic pathogen. It is contemplated within the scope of this invention that any deleterious effects of unwanted organisms can be alleviated by using clonal strains of for example Bacillus megatherium. The Bacillus is a spore former so it would be relatively easy to maintain axenic or near axenic cultures. In several experiments it was found that culture tanks turned dark green when sugar was added. This change in color indicates that algae or blue green algae exist within the culture medium and their growth is enhanced by sugar. Fungus has also been found within the culture that contains large quantities of the unsaturated fatty acids that are in short supply in mariculture. It is not known if the fungus can grow in this simple media. One may find that selected special microorganisms are suitable in every respect except that they are difficult to digest. The selection of filter feeders such as Artemia or clams needs to take into account their ability to digest a selected special microorganism. It is contemplated within the scope of the invention that a naturally occurring special microorganism can be genetically altered to provide a more suitable food. This genetic alteration can be but not limited to increasing the content of unsaturated fatty acids. The present invention will be described in more detail by way of examples; these examples should be construed as merely illustrative of the inventive method and should not be construed to be limited thereto. EXAMPLE 1 To test the nutritional value of bacteria, and the procedure of culturing, the following experiment was done. Two 200-liter glass aquaria were set up out doors. The aquaria were partially shaded. The aquaria were filled with seawater from the Red Sea. On the first day, each aquarium received 10 mg of Artemia cysts from the Great Salt Lake, and iron EDTA, urea, and sodium dibasic phosphate. The final concentrations within the aquaria were as follows: ferric chloride 0.002 gms per liter, sodium EDTA 0.0035 gms per liter, sodium dibasic phosphate 0.0025 gms per liter, and urea 0.05 gms per liter. On day three, ten grams of sucrose were added to aquarium 1, and none to aquarium 2. On day 23, the Artemia were harvested with a fine aquarium net, daubed dry, and weighted. From tank 1 (with sugar) 27.0 grams of Artemia were harvested, and from tank 2 (without sugar) 3.0 grams of Artemia were harvested. The temperature during the time of the experiment ranged from approximately 25 to 36 degrees centigrade. Approximately ten times as many Artemia were produced when sugar was provided as when no sugar was given. Some Artemia were produced in the absence of sugar because, without being bound to any particular theory, it is believed that in partial sun light algae were produced as food for the Artemia. The bulk of the food was sugar-generated bacteria. In this experiment one gram of sugar produced almost three grams of Artemia (wet weight). As a result of this experiment, the production rate in ponds was calculated as follows; 27 grams per 200 liters per 23 days is equal to 27 grams per 200 liters per 23 days times 1000 liter per cubic meter or 5 times 27 grams per year, or 5 times 27 grams per cubic meter times 365/23 per year, or 5 times 27 grams per cubic meter times 10,000 cubic meter per hectare (one meter deep pond) times 365/23 per year divided by 1,000,000 grams per ton. This equals about 21 tons per hectare per year. The experiment was started with Artemia cysts so the initial period is one of slow growth until the Artemia grow to adult size and start reproducing. In a commercial production, the growing population would be kept high with continuous partial harvesting at a controlled rate. EXAMPLE 2 The next illustrative example was done indoors to control the temperature. With air conditioning the room temperature was maintained at approximately a constant 27 degrees centigrade. On day 1, each of three plastic buckets were set up with fifty liters each of sea water from the Red Sea. Each bucket received 60 mgms of Artemia cysts from the Great Salt Lake, and nitrogen, phosphorus, and iron as in the previous experiment. The buckets were aerated as in the previous experiment. On the second day, buckets 2, and 3 received 2.5 Gms of sucrose, and 50 ml of an overnight culture of bacteria. The bacterial culture was prepared by taking 500 ml of fresh sea water, and adding iron, nitrogen, and phosphorus as before and 0.2 gms of sugar per liter, and aerating overnight. Overnight the cultures became quite cloudy. On the 5th day, bucket 3 received 2.5 Gms of sugar, and nitrogen, phosphorus and iron equivalent to what had been added initially. Bucket 3 also received 50 ml of bacterial culture. On the 9th day and the 13th day bucket 3 received nitrogen, phosphorus, and iron as previously, and 50 ml of bacterial culture. On day 9, and 13, only bucket 3 received sugar, which was 5 gems each day. On the 16th day, Artemia were harvested and weighed. Bucket 1 that received no sugar except for the small amount in the bacterial inoculum yielded no detectable Artemia. Bucket 2 that had received a total of 5.0 gms of sugar yielded 2.3 gms of Artemia and bucket 3 that had received a total of 15 gms of sugar yielded 16.8 gms of Artemia. Again, when sugar is added to the culture medium, bacteria and Artemia grow. When less sugar is added less Artemia are produced. In an enclosed room without sunlight, no algae grow in the culture, and no Artemia are produced without sugar. Without being bound to any particular theory, it appears that Artemia grown with sugar but without sunlight do not reproduce. No offspring Artemia are observed, and the Artemia do not couple. This lessens the final yield because with sexual reproduction, the final yield would consist of the adults derived from the initial cyst input, but also their offspring. The yield of Artemia per gram of sugar was a little more than one gram of Artemia (wet weight) per gram of sugar. The yield per hectare of pond one meter deep per year would be about fifty tons per hectare per year. This experiment was flawed in that bucket 3 differed from bucket 1 not only in that 3 received sugar and 1 did not, but that 3 also received extra minerals and bacteria inoculum and 1 did not. This was corrected in a further experiment that showed that the crucial factor is sugar. EXAMPLE 3 A further illustrative example was undertaken with four plastic buckets with 50 liters each. Along with the sea water as noted above, nitrogen, phosphorus, iron and about 60 mgs of Artemia cysts were set up as in the previous illustrative examples. On the second day, buckets 2, 3 and 4 were given 2.5 Gms of sugar (10 ml of 0.25 Gms per cc in water). Also added to the buckets was 50 ml of overnight bacterial culture. On the 3rd day, bucket 2 was illuminated with a 100 watt light bulb suspended about six inches above water surface. The light was kept on for the duration of the experiment. On the 5th day, 2.5 gms of sucrose was added to buckets 2, 3 and 4. On the 5th day, fifty ml of bacteria culture was added to all buckets. On the 9th day, 2.5 Gms of sucrose were added to buckets 2, 3 and 4 and fifty ml of bacteria culture was also added to all buckets. On the 12th day, 2.5 gms of sugar was added to buckets 2, 3 and 4 and all buckets received 50 ml of bacterial culture and nitrogen, phosphorus, and iron equivalent to what had been added initially. On the 16th day, Artemia were harvested and weighted. Bucket 1, which received no sugar, produced no detectable Artemia. Bucket 2, which had received 10 Gms of sugar, and light, produced 7.97 Gms of Artemia. Bucket 3, which had received 10 gms of sugar and no light produced 6.08 gms of Artemia. Bucket 4 was not harvested because the air pump failed and all the Artemia were dead. When sugar is added to the culture medium, bacteria and Artemia grow. Without sugar and no sunlight, no Artemia are produced. With some light from a hundred-watt bulb, more Artemia are produced than without light. The light bulb provides much less light than the full spectrum of natural sunlight. It is contemplated within the scope of the invention that production runs will be done outdoors so that sunlight will have a strong positive effect. It is not known whether the effect of light is due to light itself or to the small production of algae. In this illustrative example approximately 0.8 Gms of Artemia were obtained per gm of sugar. EXAMPLE 4 An additional illustrative example was done with plastic tubs outdoors in the shade. On day 1, 3 plastic tubs were each filled with 20 liters of seawater, and the minerals nitrogen, phosphorus and iron as before. Each tub received about 24 mgs of Artemia cysts. The tubs were aerated. On days 2, 5, 9, 12 and 14, one gm of sucrose was added to tubs 1 and 2. On the same days that sucrose was added 20 ml of bacteria culture was added to all three tubs. On day 18, the Artemia were harvested and weighed. Tub 1 produced 2.12 gms of artemia, tub 2 produced 2.20 gms, and tub 3 which received no sugar produced 0.15 gms. Without being bound to any particular theory, it is believed that the yield was low because of the elevated temperatures, but clearly sugar is important. More than ten times as much Artemia were produced with sugar than without. EXAMPLE 5 In a further illustrative example, seawater was obtained from Honolulu Harbor in an area adjacent to the experimental site and placed within a container. Sucrose was added to the seawater in the concentration of approximately 100 mg per liter. Also added to the seawater were inorganics such as urea, sodium phosphate, EDTA and FeCl3 in concentrations of approximately 50 mg per liter. The container was sealed and air was blown into it though a glass plug. In approximately two days a dense bloom of bacteria occurred. The bacteria within the culture were primarily pleiotrophic rods, however, there was also some fast swimming bacteria. This bacterial culture comprised of “wild saltwater bacteria” (WSB) was the starter bacterial culture for this example. A large tank trial was conducted at the research center in a large polyethylene tank within approximately 5000 liters of seawater. The tank was located outdoors and partially shaded. The tank was aerated and had a water temperature of ranging approximately between 28 to 29 degrees Centigrade. The tank was sterilized by the addition of 6% hypochlorite (i.e. clorox). For every 1000 liters of seawater about 750 ml of 6% hypochlorite was added. The hypochlorite was allowed to naturally dissipate with aeration over approximately one day. After the hypochlorite dissipated from the tank approximately 60 Gms of artemia cysts were added. On the following day (day 2) and on days 5, 7, 9 and 11 a 1:000 dilution of bacteria, inorganics and sucrose were added. On day 12 the tank was harvested. Although survival from cyst to adult was only about 7 percent, the total yield of approximately 3031 Gms of artemia from approximately 60 Gms of cysts was significant. The final Artemia density was approximately 0.6 Gms per liter or approximately one artemia for every 4 ml of seawater. As the growth of Artemia within the tank was good and bacteria were being rapidly cleared from the water more concentrated dilution of bacteria were used on days 5 and 7 (1:250 dilution of bacteria) and on days 9 and 11 (1:125 dilution of bacteria). EXAMPLE 6 In yet, a further illustrative example, seawater was again obtained from Honolulu Harbor in an area adjacent to the experimental site and placed within a container. Sucrose was added to the seawater in the concentration of approximately 100 mg per liter. Also added to the seawater were inorganics such as urea, sodium phosphate, EDTA and FeCl3 in concentrations of approximately 50 mg per liter. The container was sealed and air was blown into it though a glass plug. In approximately two days a dense bloom of bacteria occurred. The bacteria within the culture were primarily pleiotrophic rods, however, there were also some fast swimming bacteria. This bacterial culture comprised of WSB was the starter bacterial culture for this work. This illustrative example was conducted in one liter of autoclaved seawater in a two liter flask containing inorganics and sucrose at the above concentrations. The two liter flask was kept in indoors and covered at all times. The flask was constantly aerated and isolated from the outside with an air blanket and the temperature was maintained at approximately 23 degrees Centigrade. On the first day 6 mgs of Artemia cysts were added to the flask. On the second day and on the 5th, 7th, 9th, and 11th day 1:1000 dilution of wild saltwater bacteria and sucrose were added. As the Artemia were growing rapidly and eating the bacteria the added bacteria was in the lesser dilution of 1:100 and additional feedings of bacteria were done on the 10th and 12th day in addition to the above feedings. On the 13th day the flask was harvested. The total yield of the flask was approximately 2.3 Gms of artemia from approximately 6 mgms of cysts. The final artemia density was approximately 2.3 gms per liter or approximately. The 2.3 Gms of artemia that were produced consume approximately 1.2 Gms of sucrose in the 13 days of growth. The hatching and survival rate of artemia was approximately 54 percent and average sizes of artemia were unusually large. Although the illustrative embodiments of the invention suggest the use of the Artemia as a feedstuff, it will be appreciated by those skilled in the art that these Artemia may be used alone or in combination with other filter feeders grown according to the inventive method or in an admixture with conventional feedstuffs. Although the illustrative embodiments of the invention suggest the use of the Artemia as a filter feeder, it will be appreciated by those skilled in the art that other filter feeders such as clams and mollusk may be used. Although the illustrative embodiments of the invention suggest the use of bacteria as special microorganisms, it will be appreciated by those skilled in the art that other microorganism that will multiple in the culture medium may be used. Although the invention has been shown and described with respect to exemplary embodiments thereof, various other changes, omissions and additions in the form and detail thereof may be made therein without departing form the spirit and scope of the invention.
<SOH> BACKGROUND OF INVENTION <EOH>In recent years it has become increasing popular to cultivate marine species in controlled settings. This cultivation, which is commonly referred to as aquaculture, has allowed the production of a variety of marine species for human consumption. Increasingly, many edible fishes have been produced using aquaculture. While aquaculture has shown marked technological increases, to support the growth of this industry, it is necessary to produce an artificial feed or to increase the harvest of naturally occurring foodstuff such as Artemia, Brachinus salina, Daphnia, etc. All marine life in the seas ultimately depends on microscopic algae for their growth or the growth of their food within the marine food chain. This microscopic algae, which is the first link within the marine food chain, is directly consumed by filter feeders such as shell fish, and indirectly through the complex food chain within the sea by the rest of marine life. Algae grows very slowly, however, as they only divide approximately once a day and therefore they are not easily available. This lack of availability contributes to a significant increase in the cost of aquaculture products. Attempts to replicate or replace natural foodstuff within aquaculture have been met with limited success. In U.S. Pat. No. 5,158,788 to Lavens et al. (“Lavens”), a method is described to produce a feed for aquaculture from yeast. Lavens entails a multi-step process in which yeast cells are processed by hydrolyzing its cell wall producing a digestible feed for aquaculture. Unfortunately, the multi-step process as suggested by Lavens is labor intensive and therefore not feasible economically. Most importantly, the destruction of the cell wall that is needed to produce this artificial feed causes pollution of the aquaculture by the cell materials contained within the yeast cell. One significant natural food source within the marine food chain that feeds off microscopic algae is Artemia. Artemia commonly referred to as brine shrimp is an excellent foodstuff for aquaculture, because of its position within the marine food chain and its desirability as a food source for higher members of marine culture. They are an excellent food for aquaculture, because unlike prior art foods in aquaculture they do not undergo putrefaction by microorganisms and foul water used in aquaculture, but rather they clear the water of fouling micro-organisms. It is commonly known that Artemia can be used as a feed for species such as shrimp, fishes, etc. The natural harvesting of Artemia for their use in aquaculture, however, is subject to environmental factors that have recently led to shortages. Artemia grow in large saline lakes such as the Great Salt Lake in Utah. Artemia have been harvested in the Great Salt Lake for many years. Unfortunately, recent harvests have been poor and the cost of Artemia cysts has increased more than three fold. It is thought that these recent poor harvests have been caused by changing weather patterns. Severe climatic disturbances caused by the warm weather and excessive rainfall that accompanied El Nino caused production levels of the Artemia from the Great Salt Lake to decrease dramatically. The harvest of Artemia cysts in 1995-96 and 1996-97 was approximately 15 million pounds gross weight. Of this total harvest only about fifty percent is suitable for use. The 1997-98 harvest was only approximately 6 million pounds gross weight. Decreases in harvesting of Artemia cysts, such as in the case of El Nino, not only cause problems with availability, but also sharp increases in the price of Artemia cysts. This sharp increase in cost makes the use of Artemia as a feed for aquaculture economically impermissible. Although there are several other sources of Artemia throughout the world, the Great Salt Lake provides more than ninety percent of the world's Aretmia cyst consumption. While additional sources of Artemia have been found in Russia, Turkey, and China, these additional sources have not offset the declining harvest of the Great Salt Lake. Various methods of producing Artemia within aquaculture have been explored such as in Vietnam, where Artemia have been growth in ponds having abundance of natural algae. In Hawaii, yeast and greenwater have been used to grow Artemia and rotifers for seahorse and Asian sea bass aquaculture. Unfortunately, these various efforts have been met with limited success as these prior methods of producing Artemia are labor extensive and not economically feasible.
<SOH> SUMMARY OF INVENTION <EOH>The bulk of food for all living creatures of the sea originates with microscopic algae. This microscopic algae is directly consumed by filter feeders such as shellfish and indirectly by the rest of marine life through a complex food chain. The inventive method consists of mimicking this natural phenomenon in mariculture by substituting special microorganisms for naturally occurring microscopic algae, and providing conditions optimal for the growth of these organisms. These substituted special microorganisms then provide an abundant food source for higher order members of the marine food chain. As stated above, microscopic algae grow very slowly and even when provided with all their mineral requirements, divide only about once every 24 hours. On the other hand, microorganisms such as bacteria, and probably certain species of algae, blue green bacteria, and fungi divide about once every thirty minutes if provided with an organic energy source. According to the inventive method, mineral elements are added to seawater to provide a culture for the optimal growth of selected microorganism. The added mineral elements are nitrogen, phosphorus, and iron, because these are the only mineral elements deficient within seawater that are essential to all life. In addition to the added elements, sugar (sucrose) is added to provide an energy source. In an illustrative embodiment of the inventive method, sucrose is used to provide both energy and a carbon source. Sucrose has an advantage as an energy source, in that it consists of only carbon, oxygen, and hydrogen. Sucrose, however, is only one example of carbonaceous substances that can serve this function. Other food sources can be used to support the growth of these special microorganisms that include such inexpensive products, such as peanut cake after the oil is pressed out, molasses, which is a by-product of sugar production, sugar beet syrup and cane syrup or the like. Their disadvantage is that they can support many kinds of microorganisms, some of which could be pathogenic. This disadvantage, however, can be remedied by sterilizing seawater with chlorine or filtering the seawater. Care has to be taken, however, to prevent foreign microbes' entry into the cultures. It is contemplated within the scope of the invention that the seawater within the culture medium can be refreshed frequently to prevent unwanted organisms from taking over the culture. It is also contemplated within the scope of the invention that the inventive method can be used as an efficient method to fix atmospheric carbon dioxide. The fixing of atmospheric carbon dioxide into plant material requires a significant amount of energy. The use of the inventive method to grow shellfish on a large scale wherein the shellfish produce calcium carbonate from atmospheric carbon dioxide results in a more energy efficient method of alleviating the excess of carbon dioxide within the atmosphere. detailed-description description="Detailed Description" end="lead"?
20060403
20080325
20060824
96797.0
A01K6100
0
ABBOTT-LEWIS, YVONNE RENEE
MICROBIAL FEEDSTOCK FOR FILTER FEEDING AQUATIC ORGANISMS
SMALL
0
ACCEPTED
A01K
2,006
10,536,671
ACCEPTED
Interlock mechanism for lateral file cabinets
The invention relates to interlocks for file cabinets and the like which generally prevent more than one drawer from being opened at a given time. The interlocks include a cable which is changeable from a slack condition to a taut condition. In the taut condition, the interlocks prevent the associated drawer from being opened. In the slack condition, the interlock allows the associated drawer to be opened. The interlocks may be used in conjunction with a lock that selectively changes the tension in the cable from a slack condition to a taut condition and vise versa. The interlocks may be constructed to exert a tension on a cable that is independent of the pulling force exerted on a locked drawer. Alternatively, the interlocks may be constructed to exert a force on the cable that is a small fraction of the pulling force exerted on a locked drawer.
1. An interlock for a drawer positionable within a cabinet, the drawer being movable in the cabinet in a first direction toward an open position and in a second, opposite direction toward a closed position, said interlock comprising: an elongated, flexible member; a rotatable level adapted to switch the amount of slack in said elongated, flexible member between a low slack condition and a high slack condition by rotating between a first and second position, respectively; an engagement member attached to said drawer and positioned to cause said rotatable lever to rotate toward said first position when said drawer is initially moved from the closed position in the first direction; and a biasing member positioned adjacent said lever, said biasing member adapted to exert a biasing force that tends to prevent said lever from rotating from said second position to said first position until said drawer is moved in said first direction to the open position. 2. The interlock of claim 1 wherein said biasing member is a spring. 3. The interlock of claim 2 wherein said spring is coupled to said lever. 4. The interlock of claim 1 wherein said elongated, flexible member is a cable. 5. The interlock of claim 1 wherein said elongated, flexible member is in communication with at least one other drawer interlock associated with another drawer, said at least one other drawer interlock adapted change said elongated, flexible member from the high slack to the low slack condition when the another drawer is moved to an open position. 6. The interlock of claim 1 wherein said elongated, flexible member is in communication with a lock, said lock adapted to selectively change said elongated, flexible member between said low and high slack conditions. 7. The interlock of claim 6 further including a second, elongated flexible member in communication with a second lock and said lever, said second lock adapted to selectively change said second elongated, flexible member between said low and high slack conditions. 8. The interlock of claim 1 wherein said lever and said biasing member are mounted on a drawer slide member, said drawer slide member mounted to said cabinet and adapted to allow said drawer to slide between said open and said closed position. 9. The interlock of claim 8 wherein said interlock is solely mounted to said drawer slide member such that removal of the drawer slide member from the cabinet also removes said interlock. 10. The interlock of claim 1 wherein said rotatable lever is configured to translate a first force exerted on the drawer in the first direction into a second force exerted against said elongated, flexible member that is less than said first force. 11. The interlock of claim 10 wherein said second force is less than one-half of said first force. 12. The interlock of claim 10 wherein said second force is less than one-fifth of said first force. 13. The interlock of claim 10 wherein said second force is less than one-twentieth of said first force. 14. The interlock of claim 12 wherein said interlock is secured to an end of a drawer slide in which said drawer slides between said open and said closed position. 15. The interlock of claim 4 further including a cable guide adapted to snap-fittingly receive the cable from at least one direction. 16. An interlock for a drawer positionable within a cabinet, the drawer being movable in the cabinet in a first direction toward an open position and in a second, opposite direction toward a closed position, said interlock comprising: an elongated, flexible member adapted to be changeable between a high slack condition and a low slack condition; and an actuating member positioned to be operatively engageable with said elongated, flexible member, said actuating member adapted to change said elongated, flexible member to said low slack position when the drawer is opened and to allow said elongated flexible member to exist in said high slack condition when the drawer is closed, said actuating member adapted to translate a first force exerted on said drawer in said first direction to a second force on said elongated, flexible member which is less than said first force. 17. The interlock of claim 16 wherein said actuating member comprises: a rotatable lever adapted to alter the amount of slack in said elongated, flexible member, said lever being rotatable between a low slack position and a high slack position, said low slack position creating the low slack condition in said elongated, flexible member and said high slack position allowing said elongated, flexible member to exist in the high slack condition; and an engagement member attached to said drawer and positioned to cause said rotatable lever to rotate to said low slack position when said drawer is initially moved in the first direction from the closed position. 18. The interlock of claim 17 further including a retainer adapted to retain said rotatable lever in said low slack position while said drawer is moved to said open position. 19. The interlock of claim 18 wherein said retainer includes a cam said cam member being coupled to said lever. 20. The interlock of claim 17 further including a spring that exerts a force on said lever that resists movement of said lever from said high slack position to said low slack position. 21-64. (canceled)
BACKGROUND OF THE INVENTION The present invention relates to filing cabinets, and more particularly to mechanisms adapted to prevent one or more of the drawers in the filing cabinet from being opened. It has been known in the past to include interlock mechanisms on filing cabinets that prevent more than one drawer in the cabinet from being opened at a single time. These interlock mechanisms are generally provided as safety features that are intended to prevent the filing cabinet from accidentally falling over, a condition that may be more likely to occur when more than one drawer in the cabinet is open. By being able to open only a single drawer at a given time, the ability to change the weight distribution of the cabinet and its contents is reduced, thereby diminishing the likelihood that the cabinet will fall over. In addition to such interlocks, past filing cabinets have also included locks that prevent any drawers from being opened when the lock is moved to a locking position. These locks are provided to address security issues, rather than safety issues. These locks override the interlocking system so that if the lock is activated, no drawers may be opened at all. If the lock is not activated, the interlock system functions to prevent more than one drawer from being opened at the same time. Oftentimes the system that locks all of the drawers and the interlock system that locks all but one of the drawers are at least partially combined. The combination of the locking system with the interlocking system can provide cost reductions by utilizing common parts. Past locking and interlocking mechanisms, however, have suffered from a number of disadvantages. One disadvantage is the difficulty of changing the drawer configurations within a cabinet. Many filing cabinets are designed to allow different numbers of drawers to be housed within the cabinet. For example, in the cabinet depicted in FIG. 1, there are three drawers in the cabinet. For some cabinets, it would be possible to replace these three drawers with another number of drawers having the same total height as the three original drawers. This reconfiguration of the drawers is accomplished by removing the drawer slides on each side of the drawer and either repositioning the drawer slides at the newly desired heights, or installing new drawer slides at the new heights. Many drawer slides include bayonet features that allow the drawer slides to be easily removed and repositioned within the cabinet. In the past, such reconfiguring of the drawers in a cabinet has been a difficult task because the interlocking and/or locking system for the drawers could not easily be adjusted to match the newly configured filing cabinet. For example, U.S. Pat. No. 6,238,024 issued to Sawatzky discloses an interlock system that utilizes a series of rigid rods that are vertically positioned between each drawer in the cabinet. The height of these rods must be chosen to match the vertical spacing between each of the drawers in the system. If the cabinet is to be reconfigured, then new rods will have to be installed that match the height of the new drawers being installed in the cabinet. Not only does this add additional cost to the process of reconfiguring the cabinet, it complicates the reconfiguring process by requiring new parts of precise dimensions to be ordered. Finding these precisely dimensioned parts may involve extensive searching and/or measuring, especially where the manufacturer of the rods is not the same entity that produced the new drawers being installed, or the manufacturer of the rods has ceased producing the parts, or has gone out of business. Another difficulty with systems like that disclosed in the Sawatzky patent is the precise manufacturing that may be required to create these rigid rods. These interlock systems only work if the rods have heights that fall within a certain tolerance range. This tolerance range, however, decreases as more interlocks are installed in a given cabinet. In other words, the tolerance of the heights of these rods is additive. In order to function properly, a cabinet with ten drawers will therefore require smaller tolerances in the rods than a two drawer cabinet. In order to create rods that can be universally used on different cabinets, it is therefore necessary to manufacture the rods within the tight tolerances required by the cabinet having the greatest expected number of drawers. These tight tolerances tend to increase the cost of the manufacturing process. Another difficulty with past interlock and lock systems for file cabinets has been the expense involved in creating a locking system that will withstand high forces exerted on the drawers. The Business and Institutional Furniture Manufacturer's Association (BIFMA) recommends that lock systems for file cabinets be able to withstand 50 pounds of pressure on a drawer. Thus, if a file cabinet does not exceed this standard, thieves can gain access to the contents of a lock drawer by pulling the drawer outwardly with more than fifty pounds of force. Many users of file cabinets, however, desire their locking system to be able to withstand much greater forces than this before failure. Increasing the durability of the locking system often adds undesired expense to the cost of building the system. A number of prior art interlock systems have used cables or straps as part of the interlocking system. Such systems, however, have suffered from other disadvantages. For example, U.S. Pat. No. 5,199,774 issued to Hedinger et al. discloses an interlock and lock system that uses a cable. The slack in the cable is decreased when a drawer is opened. The amount of slack of the cable is carefully chosen during the installation of the drawer lock so that there is just enough slack in the system to allow only one drawer to be opened at a time. The interlock on whatever drawer is opened takes up this available slack in the cable, which prevents other drawers from being opened at the same time. A similar system is disclosed in U.S. Pat. No. 5,062,678 issued to Westwinkel. This system uses a strap instead of a cable. Both systems suffer from the fact that excessive amounts of force may be easily transferred to either the cable or the strap. In other words, the cable or the strap itself are what resist the pulling force that a person might exert on a closed drawer when either the lock is activated, or another drawer is opened. The tensile strength of the cable or strap therefore determines how much force must be exerted to overcome the interlock or lock. In fact, in the interlock of Westwinkel, the system appears to be constructed so that the pulling force exerted by a person on a locked drawer will be amplified before being applied to the strap. The strap must therefore have a greater tensile strength than the highest rated pulling force that the lock or interlock system can resist. Increasing the strength of the cables or straps typically tends to increase their cost, which is desirably avoided. In light of the foregoing, the desirability of an interlock and lock system that overcomes these and other disadvantages can be seen. SUMMARY OF THE INVENTION Accordingly, the present invention provides an interlock and lock that reduces the aforementioned difficulties, as well as other difficulties. The interlock and lock of the present invention allow relatively low-tensile strength cables or flexible members to be used in systems which provide high resistance to theft and breakdown. The system of the present invention further allows changes to cabinet configurations to be easily implemented with little or no additional work required to integrate the new cabinet configuration into the interlock or lock system. The present invention provides a simple construction for locks and interlocks that can be easily manufactured without excessively restrictive tolerances, and which can be easily installed in cabinets. According to one aspect of the present invention, an interlock for a cabinet drawer is provided. The drawer is movable in the cabinet is a first direction toward an open position and in a second, opposite direction toward a closed position. The interlock includes an elongated, flexible member, a rotatable lever, an engagement member, and a biasing member. The lever is adapted to alter the amount of slack in the elongated, flexible member. The lever is rotatable between a first position and a second position. The first position creates a low amount of slack in the elongated, flexible member, and the second position allows a high amount of slack to be present in the elongated, flexible member. The engagement member is attached to the drawer and positioned to cause the rotatable lever to rotate toward the first position when the drawer is initially moved from the closed position in the first direction. The biasing member is positioned adjacent the lever and adapted exert a force that tends to prevent the lever from rotating from the first position to the second position until the drawer is moved in the second direction to the closed position. According to another aspect of the present invention, an interlock is provided that includes a cable, a slack take-up mechanism, a cam, and a biasing member. The slack take-up mechanism is engageable with the cable and movable between a high-tension position and a low-tension position. The high-tension position creates a greater amount of tension than the low-tension position in the cable. The cam is operatively coupled to the slack take-up mechanism and to the drawer. The cam is adapted to switch the slack take-up mechanism from the low-tension position to the high-tension position when the drawer is moved in the first direction toward the open position. The biasing member is adapted to exert a force against the take-up mechanism that urges the slack take-up mechanism toward the high-tension position. The force of the biasing member has a magnitude that is independent of the magnitude of the force exerted on the drawer in the first direction. According to still another aspect of the present invention, an interlock is provided. The interlock includes a cable, a rotatable lever, an engagement member, and a retainer. The lever is adapted to change the cable between high and low slack conditions. The engagement member is attached to the drawer and positioned to cause the lever to rotate to a first position that changes the cable to a low slack condition when the drawer is initially moved in the first direction from the closed position. The engagement member is also positioned such that a first force exerted on the drawer in the first direction is translated by the lever to a second force on the cable, which is less than the first force. The retainer is adapted to retain the rotatable lever in the first position while the drawer is moved to the open position. According to still another aspect of the present invention, a locking and interlocking system for a cabinet is provided. The system includes a lock, a first cable, a second cable, a first interlock, and a second interlock. The first cable extends between at least a first and second drawer. The first cable is changeable from a high slack to a low slack condition. The second cable extends between the lock and the first drawer. The lock is adapted to change the second cable from a high slack to a low slack condition. The first interlock is in communication with the first and second cables and adapted to change both said first and said second cables from the high slack to the low slack condition whenever the first drawer is opened. The first interlock is further adapted to prevent the first drawer from opening whenever the first or second cables are in the low slack condition. The second interlock is in communication with the first cable and adapted to change the first cable from the high slack to the low slack condition whenever the second drawer is opened. The second interlock is further adapted to prevent the second drawer from opening whenever the first cable is in the low slack condition. According to yet another aspect of the present invention, a cabinet is provided that includes at least one drawer movable within the cabinet in a first direction toward an open position and in a second, opposite direction toward a closed position. The cabinet further includes a frame adapted to support the drawer, an elongated, flexible member, an interlock, and a slack take up mechanism. The elongated, flexible member is positioned within the cabinet and changeable between a lower slack condition and a higher slack condition. The interlock is positioned within the frame and in operative engagement with the elongated, flexible member. The interlock is adapted to prevent the drawer from moving to the open position when the elongated, flexible member is in the lower slack condition and to allow the drawer to move to the open position when the elongated, flexible member is in the hither slack condition. The slack take up mechanism is adapted to change the elongated, flexible member from the high slack condition to the lower slack condition when the drawer is moved from the closed position to the open position. The slack take up mechanism is further adapted to translate a first force exerted on the drawer in the first direction to a second force exerted on the elongated, flexible member which is less than the first force. According to still other aspects of the present invention, the interlock may be in communication with a lock that is adapted to selectively alter the condition of the cable. The interlocks may be secured to drawer slides that are removable from the cabinet. A cable guide may be included as part of the interlock to snap fittingly receive the cable and retain it in engagement with the interlock. The various aspects of the present invention provides an interlock and lock system that is versatile, resistant to high forces, and easily installed. These and other benefits of the present invention will be apparent to one skilled in the art in light of the following written description when read in conjunction with the accompanying drawings. The interlock may be in communication with a lock that is adapted to selectively alter the tension in the cable. The interlocks may be secured to drawer slides that are removable from the cabinet. A cable guide may be included as part of the interlock to snap-fittingly receive the cable and retain it in engagement with the interlock The various aspect of the present invention provides an interlock and lock system that is versatile, resistant to high forces, and easily installed. These and other benefits of the present invention will be apparent to one skilled in the art in light of the following written description when read in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of a cabinet with three drawers in a closed position; FIG. 2 is a perspective view of the cabinet of FIG. 1 illustrated with one drawer moved to an open position; FIG. 3 is a side, elevational view of an interlock and drawer slide according to a first embodiment of the present invention; FIG. 4 is a perspective view of a pair of interlocks according to the first embodiment of the present invention; FIG. 5 is a side, elevational view of the pair of interlocks of FIG. 4; FIG. 6 is a perspective, exploded view of the interlock of FIG. 3; FIG. 7 is a perspective view of the interlock of FIG. 3 illustrated without a drawer slide attached; FIG. 8 is a perspective view of an attachment plate of the interlock of FIG. 3; FIG. 9 is a plan view the attachment plate of FIG. 8; FIG. 10 is a side, elevational view of the attachment plate of FIG. 8; FIG. 11 is a perspective view of a sliding plate of the interlock of FIG. 3; FIG. 12 is a plan view of the sliding plate of FIG. 11; FIG. 13 is a side, elevational view of the sliding plate of FIG. 11; FIG. 14 is a perspective view of a cam of the interlock of FIG. 3; FIG. 15 is a plan view of the cam of FIG. 14; FIG. 16 is a side, elevational view of the cam of FIG. 14; FIG. 17 is a perspective view of an engagement member of the interlock of FIG. 3; FIG. 18 is a front, elevational view of the engagement member of FIG. 17; FIG. 19 is a perspective view of a rivet of the interlock of FIG. 3; FIG. 20 is a side, elevational view of a spring of the interlock of FIG. 3; FIG. 21 is a perspective view of a cable guide of the interlock of FIG. 3; FIG. 22 is a bottom view of the cable guide of FIG. 21; FIG. 23 is a plan view of the cable guide of FIG. 21; FIG. 24 is a side, elevational view of the interlock and drawer slide of FIG. 3 illustrated with the interlock in a locked position; FIG. 25 is a side, elevational view of the drawer slide and interlock of FIG. 3 illustrating the interlock in a position in which two drawers are being simultaneously pulled toward an open position; FIG. 26 is a side, elevational view of the drawer slide and interlock of FIG. 3 illustrating the interlock in an open position with the drawer slide contacting the CAM; FIG. 27 is a side, elevational view of the drawer slide and interlock of FIG. 3 illustrating the interlock in an unlocked position, and the drawer slide disengaged from the cam; FIG. 28 is a side, elevational view of a drawer slide and interlock according to a second embodiment of the present invention; FIG. 29 is a bottom view of the drawer slide and interlock of FIG. 28; FIG. 30 is a side, elevational view of the drawer slide and interlock of FIG. 28 taken from a side opposite to that of FIG. 28; FIG. 31 is a front, elevational view of the interlock of FIG. 28; FIG. 32 is a perspective, exploded view of the components of the interlock of FIG. 28; FIG. 33 is a perspective view of a lever of the interlock of FIG. 28; FIG. 34 is a plan view of the lever of FIG. 33; FIG. 35 is a side, elevational view of the lever of FIG. 33; FIG. 36 is a perspective view of a cam of the interlock of FIG. 28; FIG. 37 is a side, elevational view of the cam of FIG. 36; FIG. 38 is a plan view of the cam of FIG. 36; FIG. 39 is a side, elevational view of the cam of FIG. 36 taken from a side different from that of FIG. 37; FIG. 40 is a perspective view of a cable guide of the interlock of FIG. 28; FIG. 41 is a front, elevational view of the cable guide of FIG. 40; FIG. 42 is a bottom view of the cable guide of FIG. 40; FIG. 43 is a partial, perspective view of a drawer slide member with an engagement member for engaging the interlock of FIG. 28; FIG. 44 is a side, elevational view of the spring of the interlock of FIG. 28; FIG. 45 is a perspective view of a rivet of the interlock of FIG. 28; FIG. 46 is a perspective view of another rivet of the interlock of FIG. 28; FIG. 47 is a side, elevational view of the interlock of FIG. 28 illustrated in a lock position. FIG. 48 is a side, elevational view of the interlock of FIG. 28 illustrated in a position in which two drawers are being simultaneously pulled toward the open position; FIG. 49 is a side, elevational view of the interlock of FIG. 28 illustrating the interlock in an unlocked position with the engagement member in contact with the cam; FIG. 50 is a side, elevational view of the interlock of FIG. 28 illustrated in an unlocked position in which the engagement member of the slide has moved out of engagement of the cam; FIG. 51 is a perspective view of a lock illustrated in a locked position; FIG. 52 is a side, elevational view of the lock of FIG. 51; FIG. 53 is a perspective view of the lock of FIG. 51 illustrated in an unlocked position; FIG. 54 is a side, elevational view of the lock of FIG. 53; FIG. 55 is a perspective, exploded view of the lock of FIG. 51; and FIG. 56 is a side, sectional view of a cabinet and interlock system according to one aspect of the present invention; FIG. 57 is a side, elevational view of a drawer slide and interlock according to another embodiment of the present invention; FIG. 58 is an enlarged end view of the drawer slide and interlock of FIG. 57; FIG. 59 is an enlarged view of the drawer slide and interlock of FIG. 57 illustrating the interlock in a locked position; FIG. 60 is an enlarged view of the drawer slide and interlock of FIG. 57 illustrating the interlock in an unlocked position with the engagement member in contact with the cam; and FIG. 61 is an enlarged view of the drawer slide and interlock of FIG. 57 illustrating the interlock in an unlocked position in which the engagement member of the slide has moved out of engagement of the cam. DETAILED DESCRIPTION OF THE INVENTION The present invention will now be described with reference to the accompanying drawings wherein the reference numerals in the following written description correspond to like numbered elements in the several drawings. The present invention relates to locks and interlocks that may be used with file cabinets, such as the file cabinet 60 depicted in FIGS. 1 and 2. File cabinet 60 includes three drawers 62a-c that are essentially stacked on top of each other in file cabinet 60. Each drawer can be pulled in a first direction 64 toward an open position. The lower most drawer 62c in FIG. 2 is illustrated in the open position. When it is time to close this drawer, it can be pushed in a second direction 66 back to its closed position. The interlocking system of the present invention prevents more than one drawer from being opened at a single time. While only three drawers are illustrated in file cabinet 60, the present invention is applicable to cabinets having any number of drawers. The present invention also includes a locking system that overrides the interlocking system. That is, when the locking system is activated, no drawers can be opened at any time. When the locking system is deactivated, the interlocking system is activated and prevents more than one drawer from being opened at a single time. The locking system may be activated by inserting a key into a keyhole 68 positioned at any suitable location on the file cabinet. The locking and interlocking system are highly integrated so that many of the components of the interlocking system are also used in the locking system. The interlocks of the present invention may be advantageously combined or attached to the drawer slides in which drawers 62 slidingly move between their open and closed position. An example of one of these drawer slides 70 is depicted in FIG. 2 for the lower most drawer 62c. Each drawer 62 includes two drawer slides 70, one positioned on one side of the drawer and another positioned on the opposite side of the drawer. While the interlocks of the present invention can be placed at other locations besides on drawer slide 70, the attachment of the interlocks to the drawer slide 70 allows the interlocks to be simultaneously removed and repositioned when the drawer slides 70 are removed and repositioned. This greatly facilitates the reconfiguration of a file cabinet 60 with differently sized drawers 62. An interlock 72 according to a first embodiment of the present invention is depicted in FIG. 3. Interlock 72 is attached to a drawer slide 70. Interlock 72 is operatively coupled to a cable 74 that runs vertically inside of cabinet 60. In general, interlock 72 operates according to the tension in cable 74. Specifically, cable 74 has two different basic levels of tension. When no drawers are opened and the lock is not activated, cable 74 has a first amount of tension in it. When a single drawer is opened, interlock 72 takes up the slack in cable 74 and creates a second level of tension in cable 74. With the second level of tension, the slack in cable 74 is reduced to such a small level that no other drawers in the cabinet 60 can be opened. When the open drawer is closed, the slack in the cable 74 returns and any other single drawer may thereafter be opened. If a lock is included with the cabinet 60, the lock is adapted to alter the tension in cable 74. When in the locked position, the lock removes the slack in cable 74. When in the unlocked condition, the lock provides cable 74 with sufficient slack so that a single drawer may be opened. Interlocks 72 are thus designed to only allow their associated drawer to be opened when cable 74 has sufficient slack. Further, they are designed to remove the slack in cable 74, if their associated drawer is opened. The detailed construction of interlock 72, as well as how they accomplish the aforementioned functions, will now be described. As illustrated in FIG. 6, interlock 72 generally includes an attachment plate 76, a sliding plate 78, a rotatable cam or lever 80, a spring 82, a cable guide 84, an engagement member 86, and a rivet 88. Attachment plate 76 is a stationary part that secures interlock 72 to drawer slide 70. Specifically, attachment plate 76 is secured to a stationary portion 90 of drawer slide 70. Stationary portion 90 is illustrated in FIGS. 4 and 5. Stationary portion 90 is, in turn, secured to appropriate attachment structures within file cabinet 60. Those attachment structures may allow drawer slide 70 to be easily removed and repositioned inside of cabinet 60. Attachment plate 76 may be secured to stationary portion 90 of drawer slide 70 in any suitable fashion, such as by welding, or the use of fasteners. Attachment plate 76 includes a plurality of fastener holes 92 which may be used to receive rivets, screws, or other fasteners to secure attachment plate 76 to stationary portion 90 of drawer slide 70. Attachment plate 76 is depicted in detail in FIGS. 6 and 8-10. Attachment plate 76 further includes a rivet hole 94 which receives rivet 88. Rivet 88 secures cam 80 to attachment plate 76 in a rotatable fashion. Stated alternatively, cam 80 is attached to attachment plate 76 in such a manner that it can rotate about the axis generally defined by rivet 88. Attachment plate 76 further includes a spring attachment nub 96 to which one end of spring 82 is attached. Attachment plate 76 also includes a pair of bent flanges 98. Bent flanges 98 are received inside of cable guide 84 and used to secure cable guide 84 to attachment plate 76. Each flange 98 includes a shoulder 100 that retains cable guide 84 on attachment plate 76 after they have been attached, as will be explained in more detail below. Sliding plate 78, which is depicted in detail in FIGS. 6 and 11-13, is positioned between attachment plate 76 and cam 80. Sliding plate 78 slides linearly in a direction parallel to first and second directions 64 and 66. When a drawer 62 is initially opened, sliding plate 78 slides linearly in first direction 64. As the drawer fully closes, sliding plate 78 slides back to its original position in second direction 66. Sliding plate 78 includes an elongated aperture 102 that receives rivet 88. Because elongated aperture 102 has a length much greater than the diameter of rivet 88, sliding plate 78 can slide along rivet 88 while still being supported by rivet 88. Sliding plate 78 includes an engagement lug 104 positioned at an end generally opposite to elongated aperture 102. Engagement lug 104 engages cable 74 generally along its side that faces toward elongated aperture 102. The side of sliding plate 78 adjacent engagement lug 104 is supported in a channel 106 defined by cable guide 84. When sliding plate 78 slides in first direction 64, engagement lug 104, which is in engagement with cable 74, decreases the slack in cable 74. Thus, when a drawer is open, sliding plate 78 and engagement lug 104 remove the slack from cable 74. This will be described in more detail below. Sliding plate 78 further includes a spring attachment nub 108. Spring attachment nub 108 is used to attach the other end of spring 82 to sliding plate 78. When spring 82 is connected between attachment nubs 108 and 96, spring 82 exerts a force that tends to urge attachment nubs 96 and 108 toward each other in a direction generally parallel to first direction 64. The movement of sliding plate 78 toward spring attachment nub 96 of attachment plate 76 is limited by an interior surface 110 of elongated aperture 102. When interior surface 110 contacts rivet 88, sliding plate 78 can no longer be moved any further in first direction 64. As will be described in more detail herein, spring 82 exerts the tensioning force on cable 74, by way of engagement lug 104 when a drawer is opened. Depending on the physical construction of interlock 72, as well as the type of cable 74 chosen, spring 82 may be desirably chosen to exert a force against sliding plate 78 of one to two pounds in a first direction 64 when a drawer is open. Other amounts of force can also be used within the scope of the present invention. The amount of this force should be sufficient to retain cable 74 in a taut condition whenever any other drawers are attempted to be opened. Sliding plate 78 further includes an embossment 112 on a side 114 that faces cam 80. Embossment 112 is positioned between elongated aperture 102 and engagement lug 104. Embossment 112 interacts with cam 80 in a manner that will be described in more detail herein. In general, cam 80 acts as a switch for moving sliding plate 78 between a tensioning position, in which tension is exerted on cable 74, and a non-tensioning position, in which no tension, or very little tension, is exerted on cable 74. This switching occurs when the drawer associated with interlock 72 is opened or closed. This switching utilized embossment 112, as explained more below. Cam 80, which is depicted in more detail in FIGS. 6 and 14-16, includes a central aperture 116 which receives rivet 88. As mentioned previously, cam 88 is rotatable about rivet 88. Cam 80 includes a pair of spaced flanges 118 that define a channel 120 therebetween. Channel 120 selectively receives engagement member 86. Engagement member 86 is attached to the drawer 62 such that it will move linearly in first direction 64 when the drawer is open, and in second direction 66 when the drawer is closed. Cam 80 translates this linear motion into a rotational motion. Cam 80 includes a first surface 122 that engages embossment 112 whenever the associated drawer is fully closed. Raised shoulders 124a and b are defined adjacent each end of first surface 122. Raised shoulders 124a and b tend to maintain embossment 112 on first surface 112 and thereby resist inadvertent rotation of cam 80. From the position illustrated in FIG. 6, cam 80 is generally rotatable in a direction 126. This rotation in direction 126 is activated by the associated drawer being pulled toward the open position. When the drawer is so pulled, engagement member 86 begins to move in first direction 64. Because engagement member 86 is housed within channel 120, this movement in first direction 64 causes cam 80 to begin to rotate in direction 126. As this rotation continues, raised shoulder 124a of cam 80 comes into contact with embossment 112. In order for the rotation of cam 80 to continue, sliding plate 78 must be pushed in second direction 66 a small amount in order to provide clearance for embossment 112 to overcome shoulder 124a. Shoulder 124a is an optional feature that, if provided, helps to ensure that the drawer stays shut after it is closed. If the drawer is shut hard enough to create a rebounding force that would otherwise cause the drawer to open backup again, at least partially, shoulder 124a provides sufficient resistance to prevent this rebounding force to open the drawer. Shoulder 124a thus serves to maintain a drawer in the closed position until a user exerts sufficient force on a drawer to move embossment 112 past shoulder 124a. After embossment 112 has overcome raised shoulder 124a, the force of spring 82 tends to pull sliding plate 78 in first direction 64. If cable 74 is in a taut condition, however, sliding plate 78 will not be able to move in first direction 64 because engagement lug 104 will be prevented from moving in first direction 64 by the taut cable. If the cable is taut, further rotation of cam 80 in direction 126 will only be able to continue until a stop surface 128 on cam 80 abuts against embossment 112. This condition is illustrated in FIG. 7. Once stop surface 128 comes into contact with embossment 112, further rotation of cam 80 in direction 126 is impossible. The degree of rotation of cam 80 when embossment 112 is in engagement with stop surface 128 is insufficient to allow engagement member 86 to exit from channel 120. If a person attempts to open the associated drawer, the force they exert in the first direction will be transferred from engagement member 86 to cam 80. Cam 80 will transfer this force to embossment 112 via its contact with stop surface 128. Due to the construction of cam 80, the force exerted by stop surface 128 against embossment 112 will generally be a vertical force that is perpendicular to first direction 64. The force exerted on sliding plate 78 through embossment 112 will therefore not tend to move sliding plate 78 in either first direction 64 or second direction 66. The pressure of stop surface 128 against embossment 112 will therefore not create any forces on engagement lug 104. Cable 74 is therefore shielded from the forces exerted on the drawer when the cable is in a taut condition. If cable 74 is not in a taut condition when cam 80 rotates in direction 126, then sliding plate 78 will be free to move in first direction 64 after embossment 112 has cleared raised shoulder 124a. This movement of sliding plate 78 in first direction 64 will cause embossment 112 to also move in first direction 64. This movement of embossment 112 will allow it to fit into a channel 130 defined on cam 80. Channel 130 is suitably dimensioned to allow cam 80 to continue to rotate until channel 120 is angled enough to allow engagement member 86 to exit channel 120. Thus, the drawer can be opened. The movement of embossment 112 into channel 130, which is caused by the biasing force of spring 82, will also cause engagement lug 104 to move in first direction 64. The movement of engagement lug 104 in first direction 64 will increase the tension in cable 74 to a taut condition. No other drawers will therefore be able to be opened simultaneously. When the associated drawer is closed, engagement member will cause cam 80 to rotate in a direction opposite to the direction of its rotation when the drawer is opened. This closing rotation will cause a surface 131 on cam 80 to engage embossment 112. This engagement pushes embossment 112, and consequently sliding plate 74 in second direction 66. In order to avoid requiring excessive force to close the drawer, surface 131 may be angled at about 45 degrees when it contacts embossment 112. This allows sliding plate 78 to be pushed in second direction 66 without excessive forces. Engagement member 86, which is depicted in more detail in FIG. 17, is attached to an elongated member 132. Elongated member 132 is fixedly secured to the drawer. Elongated member 132 is positioned on top of the drawer slide 70. Elongated member 132 includes various apertures that may be used to secure it to the drawer 62. Elongated member 132 includes a lower flange 134 that may be used to mount member 132 to drawer slide 70 (FIG. 18). Rivet 88 and spring 82 are depicted in FIGS. 19 and 20, respectively. Cable guide 84, which is depicted in more detail in FIGS. 21-23 serves to ensure that cable 74 is properly maintained in contact with engagement lug 104 of sliding plate 78. Cable guide 74 may be manufactured of molded plastic. Cable guide 84 preferably snap-fittingly receives cable 84 so that cable 74 may be easily threaded into guide 84 with little danger of cable 74 becoming unthreaded. Cable guide 84 includes an upper and lower portion 136a and b. Channel 106 is defined between upper and lower portions 136a and b. As has been described, channel 106 provides clearance for sliding plate 78 and engagement lug 104. Cable guide 84 includes two glide surfaces 138 that provide support to sliding plate 78. Each portion 136a and b further includes an aperture 140. Apertures 140 receive bent flanges 98 of attachment plate 76 when cable guide 84 is attached thereto. Apertures 140 are spaced apart in a vertical direction a distance that is slightly smaller than the vertical distance between shoulders 100 on flanges 98 of attachment plate 76. Thus, when flanges 98 are inserted into apertures 140, shoulders 100 contact and press against inner surfaces 142 of apertures 140. The dimensions of shoulders 100 force inner surfaces 142 to flex inwardly towards each other. When flanges 98 have been completely inserted into apertures 140, shoulders 100 have moved past inner surfaces 142, allowing them to flexibly snap back to their unstressed position. Shoulders 100 contact surfaces 144 of cable guide 84. Shoulders 100 thus prevent flanges 98 from being retracted out of apertures 140 without flexing inner surfaces 142 towards each other. Because shoulders 100 do not have a cam surface that facilitates removal of flanges 98 from apertures 140, cable guide 84 is securely retained on flanges 98 of attachment plate 76. Cable 74 is easily threaded into cable guide 84 by moving cable 74 in direction 146 into channel 106 (FIG. 21). Movement of cable 74 in this direction causes the cable 74 to come in contact with two flexible arms 148. As cable 74 is further pushed against flexible arms 148, flexible arms 148 begin to flex out of the way until sufficient clearance is provided for cable 74 to pass by flexible arms 148. As soon as cable 74 passes by arms 148, they snap back to their unflexed condition. In this unflexed condition, cable 74 is prevented from being retracted out of channel 106 in a direction opposite the direction 146 by flexible arms 148. If an interlock 72 is to be removed from the inside of a cabinet, cable 74 can be easily removed from cable guide 84 by manually pressing flexible arms 148 in direction 146. Flexible arms 148 are pressed until sufficient clearance is provided for cable 74 to be retracted out of guide 84 in a direction generally opposite to direction 146. FIGS. 4 and 5 illustrate a pair of interlocks 72a and 72b in different conditions. The cable 74 in FIGS. 4 and 5 is in a taut condition. The drawer that is attached to the drawer slide of interlock 72b is in a closed position. As has been described previously, first surface 122 of cam 80 is in contact with embossment 112 in this position. The drawer corresponding to interlock 72a illustrates the condition of interlock 72a when this drawer is trying to be opened and cable 74 is already in a taut condition due to either a lock or another interlock with its drawer open (not shown). Because cable 74 is in a taut condition, engagement lug 104 of sliding plate 78 (of interlock 72a) is prevented from moving further in first direction 64 than that illustrated in FIGS. 4 and 5. Because sliding plate 78 cannot move further in first direction 64, embossment 112 of sliding plate 78 cannot move out of the way of stop surface 128 on cam 80. Embossment 112 thus prevents cam 80 from further rotation while cable 74 is in the taut condition. Because cam 80 cannot rotate any further, engagement member 86 cannot disengage from channel 120 of cam 80. The drawer therefore cannot be opened. As noted, cable 74 of FIGS. 4 and 5 is in the taut condition due to another interlock with an opened drawer (not shown) that is in communication with cable 74. Alternatively, cable 74 could be in the taut condition because it is in communication with a lock that is moved to the locking position. FIG. 7 also illustrates an interlock 72 for a drawer that is trying to be opened when cable 74 is in the taut condition. Again, the taut condition of cable 74 is due to either a lock or another interlock that is not shown in FIG. 7. FIGS. 3 and 24-27 illustrate interlock 72 in its various positions according to different drawer conditions. FIG. 3 illustrates interlock 72 when the associated drawer is closed. FIG. 24 illustrates interlock 72 when the cable 74 has been changed to the taut condition by an un-illustrated interlock or lock and the drawer associated with interlock 72 is trying to be pulled open. The drawer is prevented from being opened by the engagement of stop surface 128 with embossment 112. Because stop surface 128 presses vertically down on embossment 112, sliding plate 78 does not experience a linear force in either first or second direction 64 or 66. Whatever force is exerted against the drawer in first direction 64 is therefore not translated to cable 74. Rather, cable 74 only experiences a tensioning force from interlock 72 that is due to spring 82 acting to pull engagement lug 104 in first direction 64. The tensile strength of cable 74 therefore does not appreciably limit the amount of force that can be applied to trying to open the locked door before the interlock system fails. Interlock 72 of the present invention may resist up to 150 pounds of force on a drawer, or more, before it fails. Further, this failure point will be due to cam 80 and its interaction with either embossment 112 or engagement member 86, not the tensile strength of cable 74. Interlock 72 thus shields cable 74 from the forces that are applied in first direction 64 to open locked drawers. FIG. 25 depicts interlock 72 in the position it would move to when a person was trying to simultaneously open two drawers in the cabinet. Because no single drawer is fully open, cable 74 includes sufficient slack to allow embossment 112 to almost move past stop surface 128. However, embossment 112 cannot totally clear stop surface 128, and neither drawer will be able to be opened in this situation due to the partial engagement of stop surface 128 with embossment 112. FIG. 26 illustrates an interlock 72 in which the drawer associated with interlock 72 is partially open. As can be seen, embossment 112 has moved into channel 130 of cam 80. This has allowed cam 80 to rotate sufficiently to allow engagement member 86 to disengage from cam 80. The complete disengagement of engagement member 86 from cam 80 is illustrated in FIG. 27. FIG. 27 illustrates the condition of interlock 72 when the drawer is open to a greater extent than that depicted in FIG. 26. When the drawer of interlock 72 is moved back to its closest position, cam 80 must be oriented so that engagement member 86 can slide back into channel 120. In order to prevent cam 80 from inadvertently rotating out of this orientation while the drawer is fully opened, cam 80 can be appropriately weighted so that it is unlikely to rotate when engagement member 86 is disengaged. This weighting can be adjusted by cutting holes in cam 80 at appropriate locations to remove weight, such as hole 127 (FIGS. 14-16). Another flange, such as flange 129 (FIGS. 14-16) may also be added to increase the weight of cam 80 on a selected side of its pivot axis. Flange 129 may also be used to provide additional structural strength to cam 80 to help resist excessive pulling forces from engagement number 86 when the drawer is locked, but being attempted to be opened. An interlock 72′ according to a second embodiment of the present invention is depicted, either partially or wholly, in FIGS. 28-50. Interlock 72′, like interlock 72, is adapted to be attached directly to a drawer slide 70′. While both interlocks 72 and 72′ are depicted attached to the back ends of drawer slides 70 and 70′, it will be appreciated that they can be attached to the drawer slides at any desirable location along the drawer slides' length. Interlock 72′ operates in conjunction with a cable 74 in a similar manner that interlock 72 operates. Specifically, interlock 72′ allows only a single drawer to be open at a given time. If a lock is included in the cabinet, the lock is in communication with cable 74 and can change the amount of slack in cable 74. If the lock is activated, cable 74 has little or no slack, and none of the drawers may be opened. Interlock 72′ differs from interlock 72 in that a small portion of the pulling force exerted on a drawer in first direction 64 is transmitted to cable 74. Nevertheless, the amount of force transmitted is so small that a cable 74 having a relatively low tensile strength can still be used in a cabinet which provides strong resistance to its locking system being overcome. Interlock 72′ operates according to the same general principal as interlock 72 and is operatively coupled to a cable 74 that runs vertically inside of cabinet 60. Specifically, cable 74 is installed within the cabinet with a certain amount of slack. In general, interlock 72′ operates according to the amount of slack in cable 74. When the first drawer of the cabinet is opened, the associated interlock 72′ removes the slack from cable 74. As long as this drawer remains open, cable 74 remains in a low slack condition. The low slack condition of cable 74 prevents any other drawers from simultaneously being opened. When the one drawer is closed, cable 74 returns to its slack condition. In other words, cable 74 has two different basic levels of slack. When a single drawer is opened, interlock 72′ takes up most of or all the slack in the cable 74 and creates a second, lower level of slack in cable 74. The lower level of slack in cable 74 is such that no other drawers in the cabinet can be opened. This lower level of slack may be zero, or may be a small amount of slack. When the drawer is closed, more slack in the cable returns. At that point, any other single drawer may be opened, or the same drawer may be opened again. If a lock is included, the lock is adapted to alter the slack in cable 74 when the lock is activated. In this activated state, no drawers may be opened in the cabinet When in the unlocked condition, the lock allows cable 74 to have sufficient slack so that a single drawer may be opened. Interlocks 72′ are thus designed to only allow their associated or attached drawer to be opened when cable 74 has sufficient slack. Further, they are designed to remove substantially all of the slack in cable 74, if their associated drawer is opened. The detailed construction and operation of interlock 72′ will now be described. For purposes of description, components of interlock 72′ that are similar to components in interlock 72 will be described with the same reference numeral followed by the prime (′) symbol. Components of interlock 72′ that are substantially different from components of interlock 72 will be described with a completely new reference numeral. As can be easily seen in FIG. 32, interlock 72′ is attached to stationary portion 90′ of drawer slide 70′. Stationary portion 90′ is fixedly secured to the interior of cabinet 60. Stationary portion 90′ includes an upper aperture 150 and a lower aperture 152. Upper aperture 150 receives a first rivet 154 that pivotally secures a lever 156 to stationary portion 90′. Lower aperture 152 receives a second rivet 158 that pivotally secures a cam 160 to stationary portion 90′. Interlock 72′ further includes a cable guide 84′ that is mounted to a pair of flanges 98′ on stationary portion 90′ in generally the same manner that cable guide 84 is mounted to attachment plate 76 of interlock 72. Interlock 72′ further includes a spring 82′ and an engagement member 86′. Engagement member 86′ comprises a flange 162 that extends off of a slidable portion 164 of drawer slide 70′. Slidable portion 164 is slidable with respect to stationary portion 90′ by way of a plurality of ball bearing cages 166 that house a plurality of ball bearings in contact with both slidable portion 164 and stationary portion 90′ of drawer slide 70′ (FIGS. 28-29). Slidable portion 164 is adapted to be secured to a drawer. Slidable portion 164 may include a plurality of attachment flanges 168 used to releasably secure slidable portion 164 to the drawer. Similarly, stationary portion 90′ may also include a plurality of attachment flanges 170 used to releasably secure stationary portion 90′ to the interior of the cabinet. Lever 156, which is illustrated in more detail in FIGS. 32-35, is pivotable about a pivot axis generally defined by first rivet 154. Lever 156 includes an aperture 172 for receiving first rivet 154. Lever 156 includes a spring attachment nub 174 over which one end of spring 82′ is secured. Lever 156 further includes an engagement lug 104′ that engages cable 74. When lever 156 rotates about its pivot axis 176 in a direction 178 (FIG. 32), engagement lug 104′ pulls against cable 74 decreasing the slack in cable 74. Spring 82′ exerts a force on lever 156 that tends to resist rotation in direction 178. Lever 156 includes an inner surface portion 180 and a crest 182. When a drawer is initially opened, cam 160 abuts against crest 182 and exerts a rotational force on lever 156. If cable 74 is not in a low slack condition, cam 160 pushes against crest 182 until lever 156 is rotated sufficiently to put cam 160 in contact with inner surface portion 180. This will be described in more detail below. Cam 160, which is depicted in detail in FIGS. 32 and 36-39, is rotationally secured to stationary portion 90′ of drawer slide 70′ by way of second rivet 158. Cam 160 includes a recess 184 into which engagement member 86′ fits when the associated drawer is in the closed position. Recess 184 includes a contact surface 186 that contacts engagement member 86′ when the associated drawer is pulled in the first direction 64. When a drawer is pulled in first direction 64, engagement member 86′ engages contact surface 186 and imparts a rotational force on cam 160. This rotational force is generally in the direction 188 (FIG. 32). Rotational direction 188 is the opposite of rotational direction 178. The rotation of cam 160 in direction 188 causes an edge 190 of cam 160 to press against crest 182 of lever 156. If sufficient rotational force is exerted on cam 160, edge 190 will push against lever 156 sufficiently to allow edge 190 to pass by the crest 182 on lever 156. Crest 182 may have an arced or radial surface that allows edge 190 to overcome it without a excessive force spike. The rotation of cam 160 in direction 188 causes lever 156 to rotate in direction 178 (FIG. 32). The rotation of lever 156 takes up any slack in cable 74 by way of engagement member 86′. If cable 74 is already in a low slack condition, lever 156 will be prevented from rotating sufficiently far enough to allow edge 190 of cam 160 to reach inner surface portion 180 of lever 156. The full rotation of cam 160 will therefore be prevented. Engagement member 86′ of slidable portion 164 of drawer slide 70′ will therefore not be able to disengage from recess 184 in cam 160. Drawer slide 70′ will therefore not be able to slide, and the attached drawer will not be able to open. When cable 74 is changed to a low slack condition by another interlock or lock, cam 160 cannot rotate further than the position depicted in FIG. 31. If cable 74 is not already in a low slack condition, then cam 160 will be able to rotate sufficiently far so that edge 190 contacts inner surface portion 180. When edge 190 is in contact with inner surface 180, cam 160 has rotated sufficiently far to allow engagement member 86′ to disengage out of recess 184. Slide 70′ is therefore free to slide and the attached drawer can be fully opened. When the drawer is fully open, spring 82′ exerts a force on lever 156 in a direction opposite to rotational direction 178. This rotational force tends to maintain edge 190 in frictional contact with inner surface portion 180. This rotational force tends to maintain edge 190 in frictional contact with inner surface portion 180. This prevents edge 190 from sliding back to contact with crest 182 before the drawer is fully closed, and this maintains cam 160 in the proper rotational altitude for recess 184 to accept engagement member 86′. When the drawer is being closed, engagement member 86′ eventually comes into contact with a contact surface 194 defined on cam 160. As the drawer is fully closed, engagement member 86′ pushes against contact surface 194 to thereby cause cam 160 to rotate in a rotational direction that is opposite to direction 188. This rotation causes edge 190 to move out of contact with surface portion 180 and into contact with crest 182. This, in turn, allows lever 156 to rotate in a direction opposite to direction 178. This rotation causes engagement lug 104′ to decrease the force on cable 74. The closing of the drawer therefore decreases any tension in cable 74 and increases its slack. In addition, to maintain cam 160 in its proper rotational orientation when a drawer is opened, spring 82′ helps prevent the drawers from rebounding open, or partially open, after they are slammed shut. Without spring 82′, it might be possible for a drawer to be slammed shut with sufficient force such that the rebound of the drawer in first direction 64 might rotate cam 160 and allow the drawer to open up again. Spring 82′ helps prevent such rebounding of the drawers into the open position by biasing lever 156 in a direction that resists the rotation of cam 160. The amount of biasing is sufficient to generally overcome the amount of force typically present in a drawer rebound. The drawers therefore do not rebound open, but rather only open when a user applies sufficient force to overcome the biasing resistance that spring 82′ exerts. Cam 160 includes a sloped surface 196 that helps ensure that engagement member 86′ is successfully guided back into recess 184 when a drawer is closed. If engagement member 86′ contacts sloped surface 196, it will exert a rotational force on cam 160 that tends to rotate cam 160 so that recess 184 is properly aligned for receiving engagement member 86′. Cam 160 further includes chamfered surfaces 198a and b. Chamfered surfaces 198a and 198b are designed to urge slidable portion 164 of drawer slide 70′ into proper axial alignment with cam 160. Stated alternatively, if slidably portion 164 of drawer slide 70′ is compressed toward stationary portion 90′, chamfered surface 198 will contact an end flange 200 on slidable portion 164 and urge it away from stationary portion 90′ (FIG. 32). Second chamfered surface 198b will continue to urge slidable portion 164 away from stationary portion 90′ as the drawer is completely closed. Chamfered surfaces 198a and b therefore serve to help maintain the proper spacing of stationary portion 90′ with respect to slidable portion 164. Cam 160 further includes a slide surface 202 that contacts a respective slide surface 204 on lever 156 (FIGS. 33-39). Slide surfaces 202 and 204 help ensure that cam 160 and lever 156 maintain the proper axial position with respect to each other as they are rotated. Edge 190 of cam 160 may preferably be arced with a radius of 0.04 inches. Crest 182 may also be arced with a radius of 0.06 inches. Other values may, of course, be used. Rounding edge 190 and crest 182 reduces the amount of force necessary to open the drawer. However, rounding these surfaces excessively will cause more of the force exerted on a locked drawer to be transferred to the cable 74. Cable guide 84′, which is depicted in detail in FIGS. 40-42, serves to ensure that cable 74 is properly maintained in contact with engagement lug 104′ of lever 156. Cable guide 74 may be manufactured of molded plastic. Cable guide 84′ preferably snap-fittingly receives cable 84′ so that cable 74 may be easily threaded into guide 84′ with little danger of cable 74 becoming unthreaded. Cable guide 84′ includes an upper and lower portion 136a and 136b. A channel 106 is defined between upper and lower portions 136a and 136b. Cable 74 is easily threaded into cable guide 84′ by moving cable 74 in direction 146 into channel 106 (FIG. 40). Movement of cable 74 in this direction causes the cable 74 to come in contact with two flexible arms 148. As cable 74 is further pushed against flexible arms 148, flexible arms 148 begin to flex out of the way until sufficient clearance is provided for cable 74 to pass by flexible arms 148. As soon as cable 74 passes by arms 148, they snap back to their unflexed condition. In this unflexed condition, cable 74 is prevented from being retracted out of cable guide 74 in a direction opposite the direction 146 by flexible arms 148. If an interlock 72 is to be removed from the inside of a cabinet, cable 74 can be easily removed from cable guide 84′ by manually pressing flexible arms 148 in direction 146. Flexible arms 148 are pressed until sufficient clearance is provided for cable 74 to be retracted out of guide 84′ in a direction generally opposite to direction 146. Cable guide 84′ includes a spring attachment nub 206 that holds an end of spring 82′ opposite spring attachment nub 174 on lever 156. Cable guide 84′ includes recesses (not shown) that receive flanges 98′ and that interact with the shoulders 100′ to secure guide 84′ to stationary portion 90′. These recesses are defined on the bottom of cable guide 84′ and do not extend all the way through cable guide 84. Shoulders 100 abut against surfaces 144 when cable guide 84′ is attached to stationary member 90′ (FIG. 42). FIG. 43 depicts slidable portion 164 of drawer slide 70′ in more detail. FIG. 44 depicts spring 82′ in more detail. FIGS. 45 and 46 depict first and second rivets 154 and 158 respectively. Second rivet 158 includes a sloped undersurface 159 (FIG. 45) that helps to maintain slideable portion 164 of the drawer slide, as well as the attached drawer, in proper alignment with the stationary portion 90′. If the drawer is subjected to pulling forces, or other types of forces, that tend to cause the drawer to rack or twist (especially if made out of thin sheet metal), these forces may move the back end of slideable portion 164 away from stationary portion 90′. In such instances, end flange 200 will come into contact with sloped undersurface 159 of rivet 158 as the drawer is closed. The sloped nature of surface 159 will create a force on end flange 200 of slideable portion 164 that pushes the back end of slideable portion 164 toward stationary portion 90′ in a direction generally parallel to pivot axis 176. This helps maintain the proper alignment of the drawer when it is closed. End flange 200 may be chamfered to correspond to the angle of undersurface 159 in order to more easily force the drawer into the proper alignment. Undersurface 159 also helps to ensure that engagement member 86′ stays aligned with cam 160 so that engagement member 86′ properly engages cam 160. Without rivet 158 and undersurface 159, it might be possible for a drawer to become excessively racked such that engagement member 86′ no longer contacted cam 160 when the drawer was opened and closed. Undersurface 159 prevents this possibility. The head of rivet 158 preferably does not extend farther away from the stationary portion 90 than does slidable portion 164. Rivet 158, therefore, does not obstruct the drawer attached to slidable portion 164 and the back end of the drawer may extend all the way back to the back end of the drawer slide. Interlock 72, therefore, does not put any space limitations on the dimensions of the drawer other than those required by the drawer slide. As mentioned previously, interlock 72′ is designed to transfer only a small fraction of a pulling force exerted on a drawer onto cable 74. This reduction in forces can best be understood with reference to FIG. 31. FIG. 31 illustrates interlock 70′ in the position it would be in when the attached drawer is being pulled in the open direction while cable 74 is in a taut or low slack condition. The tautness of cable 74 prevents interlock 70 from allowing the drawer to be opened. FIG. 31 depicts interlock 72′ with slidable portion 164 and second rivet 158 removed in order to illustrate the underlying structure. Line 208 represents the moment arm of cam 160 as it pivots about its pivot point 210 (corresponding to the center of rivet 158). Line 212 represents the moment arm of lever 156 as it pivots about its pivot point 214 (corresponding to the center of rivet 154). For purposes of discussing the forces applied to interlock 72′, it will be assumed that the cable 74 depicted in FIG. 31 is already in a low slack condition due to either an associated lock being activated, or another interlock having allowed another drawer to be opened. Interlock 72′ depicted in FIG. 31 therefore must prevent its attached drawer from opening in order to function properly. If a person exerts a strong pulling force on the drawer attached to interlock 72′ of FIG. 31, this force will be greatly reduced when it is eventually applied to cable 74. The pulling force exerted on the drawer in first direction 64 is transmitted to cam 160 by engagement member 86′. Engagement member 86′ engages cam 160 generally in recess 184. The pulling force exerted on the drawer, which is illustrated by the arrow FD, acts on moment arm 208 at a point D. This point corresponds to the location where engagement member 86′ contacts first surface 186 of recess 184. Force FD will cause cam 160 to rotate generally in a counter clock-wise direction, as depicted in FIG. 31. This rotation will cause edge 190 of cam 160 to push against crest 182 of lever 156 with a force of FC. FC refers to the amount of force exerted by cam 160 on lever 156. Because force FC will be applied by cam 160 at a location that is farther away from pivot point 210 on moment arm 208, force FC will be less than force FD. The force FC will be applied to moment arm 212 of lever 156 at a position C. Position C is located on moment arm 212 at a position that is relatively close to pivot point 214. Force FC will be transferred via lever 156 to cable 74 at a point T. Point T refers to the position where engagement lug 104′ engages cable 74. Because point T is substantially farther away from pivot point 214 along moment arm 212, the magnitude of force FT will be significantly less than the magnitude of force FC. Further, the spring 81′ will exert a force FS along lever 156 at a point S. This force FS acts in opposition to the force FT. Because point S is farther away from pivot point 214 along moment arm 212, a smaller amount of force FS is necessary to cancel out the force FT. The force FT that is exerted against cable 74 will therefore be greatly reduced as compared to the force FD that is exerted on the drawer. The tensioning force FT may be as little as 1/20th, or less, of the magnitude of the force FD. Cable 74 can therefore resist drawer-pulling forces that greatly exceed its maximum tensile strength. In addition to transferring only a fraction of the force of FD to cable 74, the arrangement of cam 160 and lever 156 also magnifies the movement of engagement lug 104′ with respect to the rotation of cam 160. Stated alternatively, if the attached drawer is moved in first direction 64 a small distance A that causes cam 160 to partially rotate, the distance that engagement lug 104′ moves in first direction 64 will be greater than the distance A. For example, if the drawer is moved in first direction 64 for 0.05 inches, this may cause engagement lug 104′ to move 0.65 inches. This feature decreases the amount of movement in the locked drawers that might otherwise be present. A drawer that is locked will therefore only be able to be pulled a small distance before taut cable 74 prevents it from being opened. Interlock 72′ can thus prevent drawers from being opened even for the small distance that might otherwise easily allow an intruder to insert a screw driver, or other lever mechanism, between the drawer and the cabinet. FIGS. 47-50 depict interlock 72′ in several different states. In FIG. 47, interlock 72′ is in the position it would be if someone were pulling on the attached drawer while the cable 74 (not shown) was in a low slack condition. The cable 74 would therefore prevent cam 160 in lever 156 of interlock 72′ from rotating further than that depicted in FIG. 47. FIG. 48 depicts the position of interlock 72′ when the drawer is trying to be pulled open simultaneously with another drawer. When two drawers are trying to be opened simultaneously, lever 156 can rotate more than it can in FIG. 47. However, the rotation of lever 156 is insufficient to allow edge 190 of cam 160 to travel past crest 182. Cam 160 therefore does not rotate sufficiently to allow engagement lever 86′ to disengage from recess 184. Therefore, neither drawer being simultaneously pulled will allow it to be opened. FIG. 49 depicts interlock 72′ in its condition when engagement member 86′ has just begun to disengage from recess 184. Engagement member 86′ has moved to a greater extent than in FIGS. 47 and 48. This greater movement creates sufficient force against cable 74 (not shown) to put the cable in a low slack condition, thereby preventing other drawers from being opened simultaneously. With surface 190 in contact with surface 180, lever 156 is prevented from rotating back, thereby maintaining cable 74 in the lower slack state when another drawer is attempted to be opened. FIG. 50 depicts an interlock 72′ in which the drawer has opened sufficiently far to disengage engagement member 86′ from recess 184. An example of a lock 216 that may be used in conjunction with the present invention is depicted in FIGS. 51-55. Lock 216 selectively changes the condition of cable 74 from a low slack condition to a low slack condition. Lock 216 includes a hole 260, which may be a keyhole, into which a key may be inserted or which may receive a bar that is coupled to a conventional lock cylinder. If hole 260 is a keyhole, insertion of the proper key therein allows a key cylinder 218 to be rotated by the key. If hole 260 received a bar, which may be desirable where lock 216 is positioned at the back end of the cabinet, the bar is coupled to any conventional lock in a manner that causes the bar to be able to rotate about its longitudinal axis when the proper key is inserted into the conventional lock. In either situation, key cylinder 218 therefore will rotate when a proper key is used. Key cylinder 218 includes a pin 220 that moves in a cam track 222 defined in a reciprocating member 224. Reciprocating member 224 is snap-fittingly attached to a cover 226 by way of a flexible arm 228. Flexible arm 228 fits into an aperture 230 defined in cover 226. Flexible arm 228 includes a shoulder 232 that retains reciprocating member 224 to cover 226 when the two are snap fit together. The snap fitting occurs when flexible arm 228 initially contacts cover 226. A cam surface 234 causes flexible arm 228 to flex as reciprocating member 224 is initially pushed toward cover 226. After the two are completely secured together, flexible arm 228 snaps back to its unflexed condition in which shoulder 232 prevents the two members from being separated. Reciprocating member 224 includes a pair of apertures 236. Cable 74 may be secured to one of the apertures 236. When key cylinder 218 is rotated toward a locking condition, reciprocating member 224 moves vertically upward with respect to cover 226 (FIGS. 51-52). This vertical movement decreases the slack in cable 74 such that no drawers in the cabinet may be opened. When lock 216 is unlocked, the unlocking rotation of key cylinder 218 moves reciprocating member 224 vertically downward with respect to cover 226 (FIGS. 53-54). This creates sufficient slack in cable 74 for a single drawer to be opened. Cover 226 may be securely fastened inside of cabinet 60 in any suitable manner. Cable 74 may be secured to one of apertures 236 by threading the cable therethrough and tying it, such as is illustrated in FIGS. 51-54. Alternatively, a more preferred method of securing cable 74 to apertures 236 is accomplished by way of a J-hook 300 (FIG. 55). J-hook 300 is crimped onto an end of cable 74 in a conventional manner. J-hook 300 includes a lower vertical section 302, a middle horizontal section 304, and an upper vertical section 306. Upper vertical section 306, along with a portion of horizontal section 304, is inserted through one of apertures 236 and manipulated until upper vertical section 306 contacts one side of the wall in which apertures 236 are defined and is oriented vertically. In this position, horizontal section 304 passes horizontally through the aperture 236 and lower vertical section 302 abuts against a side of the wall in which aperture 236 is defined that is opposite the side contacting upper section 306. In this position, J-hook 300 is maintained in aperture 236 and can only be released by manually twisting J-hook 300 appropriately to allow upper section 306 to be backed out of aperture 236. J-hook 300 thus provides a convenient way for installing and removing cable 74 from lock 216. The opposite end of cable 74 may also be fastened within a cabinet by using a J-hook that fits through an aperture attached to the cabinet, although any other method of securing cable 74 can be used with the present invention. If it is desired to avoid having an end of cable 74 be attached to the frame of the cabinet, it could alternatively be held in place by interacting with cable guide 84′. Specifically, an enlarged ring or other structure could be affixed to the end of the cable. This enlarged structure would be dimensioned so that it was too large to pass through the cable passageway defined in cable guide 84. For securing the bottom of the cable, the enlarged structure would thus abut against a bottom surface 310 of the lower-most cable guide 84′ (FIGS. 40-42). If it were desired to secure the top end of the cable in a like manner to a cable guide 84′, rather than to a lock 216, an enlarged structure could also be attached to the top end of cable 74. In this situation, the enlarged structure would abut against a top surface 312 of the uppermost cable guide 84′. The enlarged structure may preferably be shaped to snap onto, or otherwise be secured to, cable guide 84′. If an enlarged structure were used on both ends of the cable to secure it in the cabinet, the proper cable slack could be set by manufacturing the cable to the specific length that created the desired amount of slack. Lock 216 could be modified so that reciprocating member 224 utilized a spring or other structure that selectively increased or decreased the tension on cable 74. In other words, rather than having reciprocating member 224 absolutely move to is raised position when the key is rotated to the locked position, lock 216 could be modified to include a spring, or other biasing force, that urged member 224 towards its upper, locked position. If no drawers were open, this biasing force would be sufficient to raise member 224 to its locked position. If one drawer were open, this biasing force would be insufficient to move the member 224 to its upper position because the cable would be in its low slack condition, thereby preventing member 224 from moving upward while the drawer was opened. As soon as a drawer was closed, however, the biasing force would move member 224 to is locked position and remove the slack in the cable that was created by the drawer closing. This arrangement allows the lock to be switched to the locked position while a drawer is still open. Once the drawer closed, it would immediately be locked and not able to be opened until the lock 216 was deactivated. The modified lock 216 thus would allow the cabinet to be locked while a drawer was still open, and as soon as the open drawer was closed, it would immediately lock. Thereafter, no drawers could be opened until the lock was deactivated. The biasing force exerted on reciprocating member 224 in modified lock 216 should be sufficient to remove the slack in cable 74 when all the drawers are closed and to maintain the cable in the locked, low slack condition when pulling forces are exerted against one or more locked drawers. Lock 216 may be further modified to include a solenoid, or other electrically controlled switch, that controls the movement of reciprocating member 224 between its locked and unlocked position. The solenoid could be controlled remotely by a user using a hand-held device that transmitted wireless signals to a receiver in the cabinet that controlled the solenoid. The control could be carried out in a conventional manner, such as in the manner in which remote, keyless entry systems work on many current automobiles. Alternately, the cabinet could include a keypad, or other input device, in which the locking or unlocking of the cabinet was controlled by information, such as a code or password, input by a user. A single interlock 72′ is all that is needed for each drawer in the cabinet. The opposite drawer slide can thus be a regular drawer slide with no interlock attached. Interlock 72, of course, can be attached directly to the cabinet, rather than integrated with the drawer slide. During the installation of the interlock system into a cabinet, the slack in the cable may be easily set by securing one end of the cable, opening a single drawer, and then pulling the cable until substantially all of its slack is removed. The cable is then secured in that condition. When the drawer is thereafter closed, the cable will have sufficient slack to allow only a single drawer to be opened at a time. Alternatively, cables 74 could be manufactured at a preset length to fit different cabinet heights. The installer of the interlocks therefore could simply fasten the cable in the desired location and the length of the cable will create the appropriate slack to allow a single drawer to be opened. Once the appropriate length of a cable is determined for a given cabinet height, cables could be easily mass-produced by a manufacturer by simply cutting them to the appropriate lengths. An interlock system 240 is depicted in FIG. 56. Interlock system 240 is depicted on cabinet 60, which includes three drawers 62a-62c. Interlock system 240 includes three interlocks 72. It should be understood that interlocks 72 may be replaced with interlocks 72′ (or interlocks 472 described below). An upper lock 216a and a lower lock 216b are included. Upper lock 216a is adapted to selectively lock the uppermost two drawers 62a and 62b. Lower lock 216b is adapted to selectively lock the lower drawer 62c. An interlock cable 74a extends vertically within cabinet 60 and runs through each of the interlocks 72 for each of the drawers 62a-c. Cable 74a is attached within the cabinet at attachment points 242, which may utilize J-hooks 300, or any other suitable means, for attaching cable 74a within cabinet 60. These alternative means may include a screw, a bolt, or other means. An upper cable 74b runs vertically from upper lock 216a through the two interlocks 72 of the uppermost two drawers 62a and b. The lower end of upper cable 74b is secured at an attachment point 244, which may be positioned above lowermost drawer 262c. Alternatively, attachment point 244 may be positioned below drawer 62c, but cable 74b should not run through interlock 72 of lowermost drawer 62c. Lower cable 74c extends vertically from lower lock 216b to the bottom of cabinet 60. Lower cable 74c is secured to the bottom of cabinet 60 at an attachment point 74c. The interlock 72 of upper drawer 62a and b thus have two cables 74a and b passing through them. Cable 74a and b may be threaded through interlock 72 in the same manner as has been described previously. Specifically, both cables 74a and b may be threaded through cable guides 84 and around engagement lug 104. When either cable 74a or 74b is in the low slack condition, interlock 72 will prevent the associated drawers 62a or b from being opened. If both cables 74a and b are in the low slack condition, interlock 72 will also, of course, prevent the associated drawers 62a or b from being opened. Because cable 72a also runs through the interlock associated with the lowermost drawer 62c, only one drawer in the entire cabinet may be opened at a given time. Cable 74c, which runs through the interlock 72 of the lowermost drawer 62c, allows the lowermost drawer 62c to be selectively locked independently of the locking of the uppermost two drawers 62a and b. Cables 74a and c, which run through interlock 72 of the lowermost drawer 62c, may be run side by side through interlock 72 in the same manner that has been described above. Alternatively, an additional engagement lug 104 may be provided on all of the interlocks that extends outwardly in an opposite direction to engagement lug 104. Cable guide 84 may be modified to include a second channel to accommodate the second cable and align it with the added engagement lug. Other modifications may be made to accommodate the second cable. System 240 allows the two upper drawers to be locked independently of the lower-most drawer while only a single drawer may be opened at any time if either or both of the locks are not activated. An interlock 472 according to yet another embodiment of the present invention is depicted in FIGS. 57-61. Though many parts of interlock 472 are similar to the previous embodiments, the numbers have been changed for clarity, except for cable 74. Interlock 472 is attached to a drawer slide 470 and operatively coupled to a cable 74 (FIGS. 59-61) that runs vertically inside of the cabinet. In general, similar to previous embodiments, interlock 472 operates according to the amount of slack in cable 74. When no drawers are opened and the lock is not activated, cable 74 has a high amount of slack in it. When a single drawer is opened, interlock 472 takes up most or all of the slack in cable 74 and creates a second, lower level of slack in cable 74. The lower level of slack in cable 74 is such that no other drawers in the cabinet can be opened. This lower level of slack may be zero, or may include a small amount of slack. When the open drawer is closed, more slack in the cable 74 returns and any other single drawer may thereafter be opened. If a lock is included with the cabinet, the lock is adapted to alter the slack in cable 74. When in the locked position, the lock removes most or all of the slack in cable 74. When in the unlocked condition, the lock allows cable 74 to have sufficient slack so that a single drawer may be opened. Interlocks 472 are thus designed to only allow their associated or attached drawer to be opened when cable 74 has sufficient slack. Further, they are designed to remove substantially all of the slack in cable 74, if their associated drawer is opened. The detailed construction of interlock 472 will now be described below. For details of suitable locks, reference is made to the description provided above. Interlock 472 is adapted to be attached directly to a drawer slide 470. While interlock 472 is depicted attached to the back end of the drawer slide, it will be appreciated that it can be attached to a drawer slide at any desirable location along the drawer slide's length. Alternately, the interlock can be attached directly to the cabinet. Interlock 472 operates in conjunction with cable 74 so that only a single drawer can be open at a given time. As understood from FIGS. 59-61, interlock 472 is attached to stationary portion 490 of drawer slide 470. Stationary portion 490 is fixedly secured to the interior of the cabinet. Stationary portion 490 includes a first aperture 450 and a second aperture 452 (FIG. 61). Aperture 450 receives a first rivet 454 that pivotally secures a lever 456 to stationary portion 490. Aperture 452 receives a second rivet 458 that pivotally secures a cam 460 to stationary portion 490. Interlock 472 further includes a cable guide 484, which is similar to cable guide 84′ described in reference to the previous embodiment. Therefore for further details for cable guide reference is made to previous embodiments. Guide 484 is mounted to a pair of flanges (not shown) on stationary portion 490 in generally the same manner that cable guide 84 is mounted to attachment plate 76 of interlock 72. Interlock 472 further includes a spring 462 (shown in phantom in FIG. 61) and an engagement member 486. Spring mounts 462 on one end to the lever at a stop 462a and on its other end to fixed rail 490 in a manner to urge lever 456 to in a counter-clockwise direction about rivet 454 (as viewed in FIGS. 59-61). However, when, as will be more fully described below, the drawer is extended from the cabinet, lever 454 will compress spring 462 under the influence of cam 460 and will pull on cable 74 so that cable 74 is in a low slack condition (FIG. 61). In the illustrated embodiment, engagement member 486 comprises an elongate recess formed in the web 464a of slidable portion 464 of drawer slide 470. Slidable portion 464 is slidable with respect to stationary portion 490 by way of a plurality of bearings 466, such as ball bearing cages that house a plurality of ball bearings, which are in contact with both slidable portion 464 and stationary portion 490 of drawer slide 470 (FIG. 58). Slidable portion 464 is adapted to be secured to a drawer. Slidable portion 464 may include one or more attachment flanges 468 for releasably securing slidable portion 464 to the drawer. Similarly, stationary portion 490 may also include one or more attachment flanges 470 used to releasably secure stationary portion 490 to the interior of the cabinet. Lever 456 is pivotable about a pivot axis generally defined by first rivet 454. Lever 456 includes an aperture for receiving first rivet 454, similar to the previous embodiments. As noted above, lever 456 includes a spring attachment tab or nub 462a to which one end of the spring is secured and an engagement lug 404 that engages cable 74. When lever 456 rotates about its pivot axis in a counterclockwise direction (as viewed in FIGS. 59-61), engagement lug 404 pulls against cable 74 decreasing the slack in cable 74. Spring 462 exerts a force on lever 456 that tends to resist this rotation and is compressed when lever 456 rotates to pull on cable 74. Similar to the previous embodiments, lever 456 includes an inner surface portion 480 and pair of crests 482, which optionally define therebetween the range of motion of cam 460. When a drawer is initially opened, cam 460 abuts against crest 482 and exerts a rotational force on lever 456. If cable 74 is not in a low slack condition, cam 460 pushes against crest 482 until lever 456 is rotated sufficiently to put cam 460 in contact with inner surface portion 480, similar to the cam of interlock 72′. Cam 460 is rotationally secured to stationary portion 490 of drawer slide 470 by way of second rivet 458. Cam 460 includes an engagement surface 584, such as a pin 584a, with which engagement member 486 is engagement when the associated drawer is in the closed position. Pin 584a contacts engagement member 486 when the associated drawer is pulled in an extended or first direction. When a drawer is pulled in the extended direction, engagement member 486 engages pin 584a and imparts a rotational force on cam 460. The shape of recess 486a is such that as the drawer is extended, pin 584a is urged downward (as viewed in FIG. 60) to pivot cam 460 in a clockwise direction (as viewed in FIG. 60). The rotation of cam 460 in this direction causes an edge 490 of cam 460 (FIG. 61) to rotate lever 456 in a counterclockwise direction and, thereby, compress spring 462. This rotation of lever 456 takes up any slack in cable 74 by way of member 404. However, if cable 74 is already in a low slack condition, lever 456 will be prevented from rotating sufficiently so that full rotation of cam 460 will therefore be prevented. Engagement member 486 of slidable portion 464 of drawer slide 470 will therefore not be able to disengage from pin 484a of cam 460. Drawer slide 470 will therefore not be able to slide, and the attached drawer will not be able to open. When cable 74 is changed to the low slack condition by another interlock or lock, cam 460 cannot rotate further. If cable 74 is not already in a low slack condition, then cam 460 will be able to rotate sufficiently to allow engagement member 486 to disengage from pin 484a. Slide 470 is therefore free to slide and the attached drawer can be fully opened. When the drawer is fully open, the spring exerts a force on lever 456 in a direction opposite its counterclockwise rotational direction, which tends to maintain the edge 490 of cam 460 in frictional contact with inner surface portion 480 of lever 456. This prevents the edge 490 of cam 460 from sliding back to contact with crest 482 before the drawer is fully closed, and this maintains cam 460 in the proper rotational attitude for pin 584a be engaged by engagement member 486. When the drawer is being closed, engagement member 486 comes into contact with pin 584a on cam 460. As the drawer is fully closed, engagement member 486 pushes against pin 584a to thereby cause cam 460 to rotate in a counterclockwise direction (as viewed in FIG. 59). This rotation causes edge 490 of cam 460 to move into contact with crest 482. However, to stop cam 460 from passing beyond crest 482, lever 456 optionally includes a stop 483 (FIG. 61). This, in turn, allows lever 456 to rotate in a clockwise direction (as viewed in FIGS. 60 and 61). This rotation causes engagement lug 404 to decrease the force on cable 74. The closing of the drawer therefore decreases any tension in cable 74 and increases its slack. In addition to maintaining cam 460 in its proper rotational orientation when a drawer is opened, spring 462 helps prevent the drawers from rebounding open, or partially open, after they are slammed shut. Without the spring, it might be possible for a drawer to be slammed shut with sufficient force such that the rebound of the drawer might rotate the cam and allow the drawer to open up again. The spring helps prevent such rebounding of the drawers into the open position by biasing the lever in a direction that resists the rotation of the cam, as noted in reference to the previous embodiment. Referring to FIGS. 59-61, engagement member 486 includes a sloped surface 496 that helps ensure that pin 584a is successfully guided back into recess 586a when a drawer is closed. If engagement member 486 contacts sloped surface 496, it will exert a rotational force on cam 460 that tends to rotate cam 460 so that pin 584a is properly aligned to extend into recess 486a. For further details of lever 456 and the interaction with cam 460, reference is made to the lever and cam of interlock 72′. FIGS. 59-61 depict interlock 472 in several different states. In FIG. 59, interlock 472 is in the position it would be if the drawer is closed. FIG. 60 illustrates the interlock if someone were pulling on the attached drawer while the cable 74 (not shown) was in a high slack condition when engagement member 486 has just begun to disengage from pin 584a. FIG. 61 depicts an interlock 472 in which the drawer has opened sufficiently far to disengage engagement member 486 from pin 584a. An interlock 472 according to yet another embodiment of the present invention is depicted in FIGS. 57-61. Interlock 472 is attached to a drawer slide 470 and operatively coupled to a cable 74 (FIGS. 59-61) that runs vertically inside of the cabinet. In general, similar to previous embodiments, interlock 472 operates according to the amount of slack in cable 74. When no drawers are opened and the lock is not activated, cable 74 has a high amount of slack in it. When a single drawer is opened, interlock 472 takes up most or all of the slack in cable 74 and creates a second, lower level of slack in cable 74. The lower level of slack in cable 74 is such that no other drawers in the cabinet can be opened. This lower level of slack may be zero, or may include a small amount of slack. When the open drawer is closed, more slack in the cable 74 returns and any other single drawer may thereafter be opened. If a lock is included with the cabinet, the lock is adapted to alter the slack in cable 74. When in the locked position, the lock removes most or all of the slack in cable 74. When in the unlocked condition, the lock allows cable 74 to have sufficient slack so that a single drawer may be opened. Interlocks 472 are thus designed to only allow their associated or attached drawer to be opened when cable 74 has sufficient slack. Further, they are designed to remove substantially all of the slack in cable 74, if their associated drawer is opened. The detailed construction of interlock 472 will now be described below. For details of suitable locks, reference is made to the description provided above. Interlock 472 is adapted to be attached directly to a drawer slide 470. While interlock 472 is depicted attached to the back end of the drawer slide, it will be appreciated that it can be attached to a drawer slide at any desirable location along the drawer slide's length. Alternately, the interlock can be attached directly to the cabinet. Interlock 472 operates in conjunction with cable 74 so that only a single drawer can be open at a given time. As understood from FIGS. 59-61, interlock 472 is attached to stationary portion 490 of drawer slide 470. Stationary portion 490 is fixedly secured to the interior of the cabinet. Stationary portion 490 includes a first aperture 450 and a second aperture 452 (FIG. 61). Aperture 450 receives a first rivet 454 that pivotally secures a lever 456 to stationary portion 490. Aperture 452 receives a second rivet 458 that pivotally secures a cam 460 to stationary portion 490. Interlock 472 further includes a cable guide 484, which is similar to cable guide 84 described in reference to previous embodiments. Therefore, for further details for cable guide reference is made to previous embodiments. Guide 484 is mounted to a pair of flanges (not shown) on stationary portion 490 in generally the same manner that cable guide 84 is mounted to attachment plate 76 of interlock 72. Interlock 472 further includes a spring 462 (shown in phantom in FIG. 61) and an engagement member 486. Spring mounts 462 on one end to the lever at a stop 462a and on its other end to fixed rail 490 in a manner to urge lever 456 to in a counter-clockwise direction about rivet 454 (as viewed in FIGS. 59-61). However, when, as will be more fully described below, the drawer is extended from the cabinet, lever 454 will compress spring 462 under the influence of cam 460 and will pull on cable 484 so that cable 484 is in a low slack condition (FIG. 61). In the illustrated embodiment, engagement member 486 comprises an elongate recess 486a formed in the web 464a of slidable portion 464 of drawer slide 470. Slidable portion 464 is slidable with respect to stationary portion 490 by way of a plurality of bearings 466, for example, bearing cages that house a plurality of ball bearings, in contact with both slidable portion 464 and stationary portion 490 of drawer slide 470 (FIG. 58). Slidable portion 464 is adapted to be secured to a drawer. Slidable portion 464 may include one or more attachment flanges 468 for releasably securing slidable portion 464 to the drawer. Similarly, stationary portion 490 may also include one or more attachment flanges 470 used to releasably secure stationary portion 490 to the interior of the cabinet. Lever 456 is pivotable about a pivot axis generally defined by first rivet 454. Lever 456 includes an aperture for receiving first rivet 454, similar to the previous embodiments. As noted above, lever 456 includes a spring attachment tab or nub 462a to which one end of the spring is secured and an engagement lug 404 that engages cable 74. When lever 456 rotates about its pivot axis in a counterclockwise direction (as viewed in FIGS. 59-61), engagement lug 404 pulls against cable 74 decreasing the slack in cable 74. Spring 462 exerts a force on lever 456 that tends to resist this rotation and is compressed when lever 456 rotates to pull on cable 74. Similar to the previous embodiments, lever 456 includes an inner surface portion 480 and pair of crests 482, which optionally define therebetween the range of motion of cam 460. When a drawer is initially opened, cam 460 abuts against crest 482 and exerts a rotational force on lever 456. If cable 74 is not in a low slack condition, cam 460 pushes against crest 482 until lever 456 is rotated sufficiently to put cam 460 in contact with inner surface portion 480, similar to the cam of interlock 72′. Cam 460 is rotationally secured to stationary portion 490 of drawer slide 470 by way of second rivet 458. Cam 460 includes an engagement surface 584, such as a pin 584a, with which engagement member 486 is engagement when the associated drawer is in the closed position. Pin 584a contacts engagement member 486 when the associated drawer is pulled in an extended or first direction. When a drawer is pulled in the extended direction, engagement member 486 engages pin 584a and imparts a rotational force on cam 460. The shape of recess 486a is such that as the drawer is extended, pin 584a is urged downward (as viewed in FIG. 60) to pivot cam 460 in a clockwise direction (as viewed in FIG. 60). The rotation of cam 460 in this direction causes an edge 490 of cam 460 (FIG. 61) to rotate lever 456 in a counterclockwise direction and, thereby, compress spring 462. This rotation of lever 456 takes up any slack in cable 74 by way of member 404. However, if cable 74 is already in a low slack condition, lever 456 will be prevented from rotating sufficiently so that full rotation of cam 460 will therefore be prevented. Engagement member 486 of slidable portion 464 of drawer slide 470 will therefore not be able to disengage from pin 484a of cam 460. Drawer slide 470 will therefore not be able to slide, and the attached drawer will not be able to open. When cable 74 is changed to the low slack condition by another interlock or lock, cam 460 cannot rotate further. If cable 74 is not already in a low slack condition, then cam 460 will be able to rotate sufficiently to allow engagement member 486 to disengage from pin 484a. Slide 470 is therefore free to slide and the attached drawer can be fully opened. When the drawer is fully open, the spring exerts a force on lever 456 in a direction opposite its counterclockwise rotational direction, which tends to maintain the edge 490 of cam 460 in frictional contact with inner surface portion 480 of lever 456. This prevents the edge 490 of cam 460 from sliding back to contact with crest 482 before the drawer is fully closed, and this maintains cam 460 in the proper rotational attitude for pin 584a be engaged by engagement member 486. When the drawer is being closed, engagement member 486 comes into contact with pin 584a on cam 460. As the drawer is fully closed, engagement member 486 pushes against pin 584a to thereby cause cam 460 to rotate in a counterclockwise direction (as viewed in FIG. 59). This rotation causes edge 490 of cam 460 to move into contact with crest 482. This, in turn, allows lever 456 to rotate in a clockwise direction (as viewed in FIGS. 60 and 61). This rotation causes engagement lug 404 to decrease the force on cable 74. The closing of the drawer therefore decreases any tension in cable 74 and increases its slack. In addition to maintaining cam 460 in its proper rotational orientation when a drawer is opened, spring 462 helps prevent the drawers from rebounding open, or partially open, after they are slammed shut. Without the spring, it might be possible for a drawer to be slammed shut with sufficient force such that the rebound of the drawer might rotate the cam and allow the drawer to open up again. The spring helps prevent such rebounding of the drawers into the open position by biasing the lever in a direction that resists the rotation of the cam, as noted in reference to the previous embodiment. Referring to FIGS. 59-61, engagement member 486 includes a sloped surface 496 that helps ensure that pin 584a is successfully guided back into recess 486a when a drawer is closed. If engagement member 486 contacts sloped surface 496, it will exert a rotational force on cam 460 that tends to rotate cam 460 so that pin 584a is properly aligned to extend into recess 486a. FIGS. 59-61 depict interlock 472 in several different states. In FIG. 59, interlock 472 is in the position it would be if the drawer is closed. FIG. 60 illustrates the interlock if someone were pulling on the attached drawer while the cable 74 (not shown) was in a high slack condition when engagement member 486 has just begun to disengage from pin 584a. FIG. 61 depicts an interlock 472 in which the drawer has opened sufficiently far to disengage engagement member 486 from pin 584a. While other materials may be used, the interlocks described herein may be made primarily of metal. Specifically, the attachment plates, sliding plates, cams, and rivets may all be made of metal, such as steel, or any other suitable metal. The engagement members may be made of metal or any other suitable material. The cable guides may be all made from plastic. The drawer slides are preferably made of metal, such as steel, with the exception of the ball bearing cages for the ball bearings, which may be made of plastic. The levers, cams, and cable guides of interlock 72′ or interlock 472 may all be made of plastic. The first and second rivets, stationary portion, and slidable portion may also all be made of metal, such as steel. Spring 82 of interlock 72 may exert a force of 1.5 pounds. The springs of interlock 72′ pr 472 may exert a force of approximately 0.5 pounds. Other spring strength may, of course, be used. The cables may comprise steel cables each composed of seven strands, with each strand made of seven individual filaments and may have a tensile strength of 40 pounds. The cables may preferably be made of stainless steel and include a vinyl coating. For example, the diameter of the cable after coating may be 0.024 inches, although other dimensions can be used. To avoid kinking of the cables, surfaces that come in contact with the cable, such as the engagement lug, may be curved with a radius of at least 0.125 inches to help reduce the possibility of kinking. As several possible alternatives to steel, the cable could be a string, a plastic based line, such as those used as fishing lines, or any other elongated, flexible member with suitable tensile strength. While the present invention has been described in terms of the preferred embodiments depicted in the drawings and discussed in the above specification, it will be understood by one skilled in the art that the present invention is not limited to these particular preferred embodiments, but includes any and all such modifications that are within the spirit and scope of the present invention as defined in the following claims.
<SOH> BACKGROUND OF THE INVENTION <EOH>The present invention relates to filing cabinets, and more particularly to mechanisms adapted to prevent one or more of the drawers in the filing cabinet from being opened. It has been known in the past to include interlock mechanisms on filing cabinets that prevent more than one drawer in the cabinet from being opened at a single time. These interlock mechanisms are generally provided as safety features that are intended to prevent the filing cabinet from accidentally falling over, a condition that may be more likely to occur when more than one drawer in the cabinet is open. By being able to open only a single drawer at a given time, the ability to change the weight distribution of the cabinet and its contents is reduced, thereby diminishing the likelihood that the cabinet will fall over. In addition to such interlocks, past filing cabinets have also included locks that prevent any drawers from being opened when the lock is moved to a locking position. These locks are provided to address security issues, rather than safety issues. These locks override the interlocking system so that if the lock is activated, no drawers may be opened at all. If the lock is not activated, the interlock system functions to prevent more than one drawer from being opened at the same time. Oftentimes the system that locks all of the drawers and the interlock system that locks all but one of the drawers are at least partially combined. The combination of the locking system with the interlocking system can provide cost reductions by utilizing common parts. Past locking and interlocking mechanisms, however, have suffered from a number of disadvantages. One disadvantage is the difficulty of changing the drawer configurations within a cabinet. Many filing cabinets are designed to allow different numbers of drawers to be housed within the cabinet. For example, in the cabinet depicted in FIG. 1 , there are three drawers in the cabinet. For some cabinets, it would be possible to replace these three drawers with another number of drawers having the same total height as the three original drawers. This reconfiguration of the drawers is accomplished by removing the drawer slides on each side of the drawer and either repositioning the drawer slides at the newly desired heights, or installing new drawer slides at the new heights. Many drawer slides include bayonet features that allow the drawer slides to be easily removed and repositioned within the cabinet. In the past, such reconfiguring of the drawers in a cabinet has been a difficult task because the interlocking and/or locking system for the drawers could not easily be adjusted to match the newly configured filing cabinet. For example, U.S. Pat. No. 6,238,024 issued to Sawatzky discloses an interlock system that utilizes a series of rigid rods that are vertically positioned between each drawer in the cabinet. The height of these rods must be chosen to match the vertical spacing between each of the drawers in the system. If the cabinet is to be reconfigured, then new rods will have to be installed that match the height of the new drawers being installed in the cabinet. Not only does this add additional cost to the process of reconfiguring the cabinet, it complicates the reconfiguring process by requiring new parts of precise dimensions to be ordered. Finding these precisely dimensioned parts may involve extensive searching and/or measuring, especially where the manufacturer of the rods is not the same entity that produced the new drawers being installed, or the manufacturer of the rods has ceased producing the parts, or has gone out of business. Another difficulty with systems like that disclosed in the Sawatzky patent is the precise manufacturing that may be required to create these rigid rods. These interlock systems only work if the rods have heights that fall within a certain tolerance range. This tolerance range, however, decreases as more interlocks are installed in a given cabinet. In other words, the tolerance of the heights of these rods is additive. In order to function properly, a cabinet with ten drawers will therefore require smaller tolerances in the rods than a two drawer cabinet. In order to create rods that can be universally used on different cabinets, it is therefore necessary to manufacture the rods within the tight tolerances required by the cabinet having the greatest expected number of drawers. These tight tolerances tend to increase the cost of the manufacturing process. Another difficulty with past interlock and lock systems for file cabinets has been the expense involved in creating a locking system that will withstand high forces exerted on the drawers. The Business and Institutional Furniture Manufacturer's Association (BIFMA) recommends that lock systems for file cabinets be able to withstand 50 pounds of pressure on a drawer. Thus, if a file cabinet does not exceed this standard, thieves can gain access to the contents of a lock drawer by pulling the drawer outwardly with more than fifty pounds of force. Many users of file cabinets, however, desire their locking system to be able to withstand much greater forces than this before failure. Increasing the durability of the locking system often adds undesired expense to the cost of building the system. A number of prior art interlock systems have used cables or straps as part of the interlocking system. Such systems, however, have suffered from other disadvantages. For example, U.S. Pat. No. 5,199,774 issued to Hedinger et al. discloses an interlock and lock system that uses a cable. The slack in the cable is decreased when a drawer is opened. The amount of slack of the cable is carefully chosen during the installation of the drawer lock so that there is just enough slack in the system to allow only one drawer to be opened at a time. The interlock on whatever drawer is opened takes up this available slack in the cable, which prevents other drawers from being opened at the same time. A similar system is disclosed in U.S. Pat. No. 5,062,678 issued to Westwinkel. This system uses a strap instead of a cable. Both systems suffer from the fact that excessive amounts of force may be easily transferred to either the cable or the strap. In other words, the cable or the strap itself are what resist the pulling force that a person might exert on a closed drawer when either the lock is activated, or another drawer is opened. The tensile strength of the cable or strap therefore determines how much force must be exerted to overcome the interlock or lock. In fact, in the interlock of Westwinkel, the system appears to be constructed so that the pulling force exerted by a person on a locked drawer will be amplified before being applied to the strap. The strap must therefore have a greater tensile strength than the highest rated pulling force that the lock or interlock system can resist. Increasing the strength of the cables or straps typically tends to increase their cost, which is desirably avoided. In light of the foregoing, the desirability of an interlock and lock system that overcomes these and other disadvantages can be seen.
<SOH> SUMMARY OF THE INVENTION <EOH>Accordingly, the present invention provides an interlock and lock that reduces the aforementioned difficulties, as well as other difficulties. The interlock and lock of the present invention allow relatively low-tensile strength cables or flexible members to be used in systems which provide high resistance to theft and breakdown. The system of the present invention further allows changes to cabinet configurations to be easily implemented with little or no additional work required to integrate the new cabinet configuration into the interlock or lock system. The present invention provides a simple construction for locks and interlocks that can be easily manufactured without excessively restrictive tolerances, and which can be easily installed in cabinets. According to one aspect of the present invention, an interlock for a cabinet drawer is provided. The drawer is movable in the cabinet is a first direction toward an open position and in a second, opposite direction toward a closed position. The interlock includes an elongated, flexible member, a rotatable lever, an engagement member, and a biasing member. The lever is adapted to alter the amount of slack in the elongated, flexible member. The lever is rotatable between a first position and a second position. The first position creates a low amount of slack in the elongated, flexible member, and the second position allows a high amount of slack to be present in the elongated, flexible member. The engagement member is attached to the drawer and positioned to cause the rotatable lever to rotate toward the first position when the drawer is initially moved from the closed position in the first direction. The biasing member is positioned adjacent the lever and adapted exert a force that tends to prevent the lever from rotating from the first position to the second position until the drawer is moved in the second direction to the closed position. According to another aspect of the present invention, an interlock is provided that includes a cable, a slack take-up mechanism, a cam, and a biasing member. The slack take-up mechanism is engageable with the cable and movable between a high-tension position and a low-tension position. The high-tension position creates a greater amount of tension than the low-tension position in the cable. The cam is operatively coupled to the slack take-up mechanism and to the drawer. The cam is adapted to switch the slack take-up mechanism from the low-tension position to the high-tension position when the drawer is moved in the first direction toward the open position. The biasing member is adapted to exert a force against the take-up mechanism that urges the slack take-up mechanism toward the high-tension position. The force of the biasing member has a magnitude that is independent of the magnitude of the force exerted on the drawer in the first direction. According to still another aspect of the present invention, an interlock is provided. The interlock includes a cable, a rotatable lever, an engagement member, and a retainer. The lever is adapted to change the cable between high and low slack conditions. The engagement member is attached to the drawer and positioned to cause the lever to rotate to a first position that changes the cable to a low slack condition when the drawer is initially moved in the first direction from the closed position. The engagement member is also positioned such that a first force exerted on the drawer in the first direction is translated by the lever to a second force on the cable, which is less than the first force. The retainer is adapted to retain the rotatable lever in the first position while the drawer is moved to the open position. According to still another aspect of the present invention, a locking and interlocking system for a cabinet is provided. The system includes a lock, a first cable, a second cable, a first interlock, and a second interlock. The first cable extends between at least a first and second drawer. The first cable is changeable from a high slack to a low slack condition. The second cable extends between the lock and the first drawer. The lock is adapted to change the second cable from a high slack to a low slack condition. The first interlock is in communication with the first and second cables and adapted to change both said first and said second cables from the high slack to the low slack condition whenever the first drawer is opened. The first interlock is further adapted to prevent the first drawer from opening whenever the first or second cables are in the low slack condition. The second interlock is in communication with the first cable and adapted to change the first cable from the high slack to the low slack condition whenever the second drawer is opened. The second interlock is further adapted to prevent the second drawer from opening whenever the first cable is in the low slack condition. According to yet another aspect of the present invention, a cabinet is provided that includes at least one drawer movable within the cabinet in a first direction toward an open position and in a second, opposite direction toward a closed position. The cabinet further includes a frame adapted to support the drawer, an elongated, flexible member, an interlock, and a slack take up mechanism. The elongated, flexible member is positioned within the cabinet and changeable between a lower slack condition and a higher slack condition. The interlock is positioned within the frame and in operative engagement with the elongated, flexible member. The interlock is adapted to prevent the drawer from moving to the open position when the elongated, flexible member is in the lower slack condition and to allow the drawer to move to the open position when the elongated, flexible member is in the hither slack condition. The slack take up mechanism is adapted to change the elongated, flexible member from the high slack condition to the lower slack condition when the drawer is moved from the closed position to the open position. The slack take up mechanism is further adapted to translate a first force exerted on the drawer in the first direction to a second force exerted on the elongated, flexible member which is less than the first force. According to still other aspects of the present invention, the interlock may be in communication with a lock that is adapted to selectively alter the condition of the cable. The interlocks may be secured to drawer slides that are removable from the cabinet. A cable guide may be included as part of the interlock to snap fittingly receive the cable and retain it in engagement with the interlock. The various aspects of the present invention provides an interlock and lock system that is versatile, resistant to high forces, and easily installed. These and other benefits of the present invention will be apparent to one skilled in the art in light of the following written description when read in conjunction with the accompanying drawings. The interlock may be in communication with a lock that is adapted to selectively alter the tension in the cable. The interlocks may be secured to drawer slides that are removable from the cabinet. A cable guide may be included as part of the interlock to snap-fittingly receive the cable and retain it in engagement with the interlock The various aspect of the present invention provides an interlock and lock system that is versatile, resistant to high forces, and easily installed. These and other benefits of the present invention will be apparent to one skilled in the art in light of the following written description when read in conjunction with the accompanying drawings.
20051213
20090203
20061130
64229.0
E05B6546
0
WILKENS, JANET MARIE
INTERLOCK MECHANISM FOR LATERAL FILE CABINETS
UNDISCOUNTED
0
ACCEPTED
E05B
2,005
10,537,175
ACCEPTED
Games console adaptor unit
An adaptor is provided for a games console which allows users to gain access to interactive television services through the games console. The adaptor includes a television tuner for receiving broadcast television channels, a communications controller which controls communications between the adaptor and the games console and an interface for interfacing the adaptor to the games console. In a preferred embodiment, the adaptor also includes a hard disc for storing video data and for storing game history data. The adaptor may also include a modem via which the user can gain access to remote servers connected to a data network.
1. A games system comprising a games console and an adaptor unit, wherein the games console comprises: (i) a console housing; (ii) a game interface within said console housing for receiving a game product; (iii) a display interface within said console housing for interfacing said games console to a display; (iv) a user interface within said console housing for receiving user input; (v) a game controller within said console housing for receiving game data from said game interface and said user input from said user interface and for generating therefrom game video data for output to said display interface; (vi) an adaptor interface within said console housing for coupling the games console with said adaptor unit; and (vii) a video player within said housing for receiving encoded video data from said adaptor unit via said adaptor interface and for outputting decoded video data to said display interface; wherein said adaptor unit comprises: (i) an adaptor housing; (ii) a video data receiver within said adaptor housing for receiving encoded video data from a remote video provider; (iii) a games console interface within said adaptor housing for interfacing said adaptor unit to said adaptor interface of said games console; and (iv) a communications controller within said adaptor housing for outputting encoded video data to said video player of said games console via said console interface and said adaptor interface. 2. A system according to claim 1, wherein the adaptor unit further comprises encryption means for encrypting the video data to be output to said video player via said console interface and wherein said video player includes decryption means for decrypting the video data. 3. A system according to claim 2, wherein said video player includes embedded data for decrypting the encrypted video data. 4. A system according to claim 3, wherein said adaptor unit further comprises a secure processor for storing an encryption key for use by said encryption means for encrypting said video data. 5. A system according to claim 4, wherein an intermediate decryption key is provided in said secure processor, wherein said communications controller is operable to pass said intermediate decryption key to said video player via said console interface and said adaptor interface and wherein said decryption means of said video player is operable to decrypt said video data using said embedded data and said intermediate decryption key. 6. A system according to claim 4, wherein said secure processor is formed on a smart-card which is retractable from a smart-card reader mounted within said adaptor housing. 7. A system according to claim 1, wherein said adaptor unit further comprises a large capacity storage means for storing video data or game data and wherein said games console further comprises a controller responsive to a user input from said user interface and operable to transmit game history data to said communications controller of said adaptor unit via said console interface and said adaptor interface and wherein said communications controller is operable to store said game history data in said large capacity storage means. 8. A system according to claim 1, wherein said adaptor unit further comprises a modem within said adaptor housing for connecting the adaptor unit to a data network. 9. A system according to claim 8, wherein said games console further comprises a web browser within said console housing for receiving menu pages from a remote server via said modem in said adaptor unit, said console interface and said adaptor interface and for generating menu screens for output to said display interface. 10. A system according to claim 8, wherein said games console is operable to transmit and to receive game data to and from said data network via said modem and said adaptor unit to provide network gaming to a user thereof. 11. An adaptor unit for use with a games console, the adaptor unit comprising: an adaptor housing; a video data receiver within the adaptor housing for receiving encoded video data from a remote video provider; a games console interface within said adaptor housing for interfacing said adaptor unit to said games console; and a communications controller within said adaptor housing for outputting encoded video data to said games console via said console interface. 12. An adaptor unit according to claim 11, further comprising encryption means for encrypting the video data to be output to said games console via said console interface and a secure processor within said adaptor housing for storing an encryption key for use by said encryption means for encrypting said video data. 13. An adaptor unit according to claim 12, wherein said secure processor is retractable from said adaptor housing and is formed on a smart-card and wherein said adaptor housing includes a smart-card reader for reading the encryption key from said smart-card processor. 14. An adaptor unit according to claim 11, further comprising a large capacity storage means for storing video data or game data and wherein said communications controller is operable to receive game history data from said games console via said console interface and is operable to store the received game history data in said large capacity storage means. 15. An adaptor unit according to claim 11, further comprising a modem within said adaptor housing for connecting the adaptor unit to a data network. 16. An adaptor unit according to claim 15, wherein said adaptor unit is operable to receive game data from said games console and to transmit the received game data to said data network and is operable to receive game data from said data network and to transmit the game data received from the data network to said games console, to provide network gaming to a user of the games console. 17. A games console for use in the system according to claim 1, the games console comprising: a console housing; a game interface within said console housing for receiving a game product; a display interface within said console housing for interfacing said games console to a display; a user interface within said console housing for receiving user input; a game controller within said console housing for receiving game data from said game interface and said user input from said user interface and for generating therefrom game video data for output to said display interface; an adaptor interface within said console housing for coupling the games console with said adaptor unit; and a video player within said housing for receiving encoded video data from said adaptor unit via said adaptor interface and for outputting decoded video data to said display interface. 18. A games console according to claim 17, wherein said games console further comprises a controller responsive to a user input from said user interface and operable to transmit game history data to said adaptor unit. 19. A games console according to claim 17, further comprising a web browser within said console housing for receiving menu pages from a remote server via a modem in said adaptor unit, and for generating menu screens for output to said display interface. 20. A games console according to claim 19, operable to transmit and to receive game data to and from said data network via said modem and said adaptor unit to provide network gaming to a user thereof. 21. A method of providing video data for display, the method comprising the steps of: interfacing an adaptor unit with a games console; receiving at said adaptor unit encoded video data from a remote video provider; outputting encoded video data from said adaptor unit to said games console through said interface; decoding in said games console said encoded video data to generate decoded video data; and outputting the decoded video data for display.
The present invention relates to an adaptor unit for use with a games console. The invention has particular, although not exclusive relevance to an adaptor unit which connects to the games console and which increases the functionality of the games console. Various games consoles have been proposed which connect to a television set and which allow users to play game products which can be bought for the console. Examples of this type of games console include the Sony Playstation, the Nintendo Game Cube or Microsoft's Xbox. One aim of the present invention is to provide an adaptor unit for a games console which includes television signal receiving circuitry and which allows the games console to function as an interactive television receiver. In one embodiment, an adaptor is provided for a games console which allows users to gain access to interactive television services through the games console. The adaptor includes a television tuner for receiving broadcast television channels, a communications controller which controls communications between the adaptor and the games console and an interface for interfacing the adaptor to the games console. In a preferred embodiment, the adaptor also includes a hard disc for storing video data and for storing game history data. The adaptor may also include a modem via which the user can gain access to remote servers connected to a data network. An exemplary embodiment of the invention will now be described with reference to the following drawings in which: FIG. 1 is a schematic diagram illustrating an interactive television system; FIG. 2 is a block diagram illustrating the main components of an adaptor unit and a games console forming part of the system shown in FIG. 1; FIG. 3 is a block diagram illustrating the main components of a video player forming part of the games console shown in FIG. 2; and FIG. 4 is a block diagram illustrating the main functional components of a web browser forming part of the games' console shown in FIG. 2. OVERVIEW FIG. 1 is a schematic diagram illustrating an interactive television system. As shown in FIG. 1, the system includes, a number of user stations, two of which are shown and labelled 1-1 and 1-2. Each user station 1 includes an adaptor unit (AU) 3, which is connected to a television (TV) 5 through a games console (GC) 7. Each user station 1 also includes a personal computer (PC) 9 which is also connected to the adaptor unit 3. The adaptor unit 3 is arranged to receive broadcast video data from a broadcast media server transmitter 11 or from an overhead satellite 13 via an aerial 15 on the user station 1. The adaptor unit 3 can also receive video data from a media server 17 through a data network 19. In this embodiment, the games console 7 can also be connected to a remote game server 21 via the adaptor unit 3 and the data network 19. This allows the downloading of games and the like from the games server 21 to the games console 7 for play out with the user. Adaptor Unit and Games Console FIG. 2 is a block diagram illustrating in more detail the main components of the adaptor unit 3 and the games console 7. As shown, the adaptor unit 3 includes a television tuner 31 for receiving video signals from the overhead satellite 13 or the broadcast transmitter 11 via the television aerial 15. The adaptor unit 3 also includes an ADSL modem 33 for connecting the adaptor unit 3 to the data network 19 so that the adaptor unit 3 can receive video data from the remote media server 17. The ADSL modem 33 can also transmit messages received from a user via a remote control 35 and a remote control interface 37, back to the remote media server 17. These user requests may be requests to download or stream a specific video file or to control the streaming of an existing file being received. The adaptor unit 3 also includes a hard disk 39 into which received video files can be recorded for subsequent play out to the user on the television 5. The provision of a hard disk 39 in the adaptor unit 3 facilitates the provision of a personal video recorder (PVR) system in which the user can, for example, pause live television as it is being received, for subsequent play out from the hard disk 19. In this embodiment, this control of the received video stream is performed by the user via the remote control 35 and the remote control interface 37. In this embodiment, the video data received by the television tuner 31 and the ADSL modem 33 is encoded MPEG video data that is encrypted using the 3DES encryption technique. The decryption key 41 (labelled Key 1) necessary for decrypting the received video streams is provided on a smart-card 43 which is read into the adaptor unit 3 via a smart-card reader 45. A central processing unit (CPU) 47 runs a decryption module 49 stored in a memory 51 using the decryption key 41 to decrypt the received video data. The adaptor unit CPU 47 then re-encrypts the decrypted video data using an encryption module 53 stored in the memory 51 together with an encryption key 53 (labelled Key 2) stored on the smart-card 43. In this embodiment, the encryption module re-encrypts the decrypted video data using an AES encryption technique. The re-encrypted video data is then passed to a games console communications controller 56 which outputs the encrypted video data to the games console 7 via a games console interface 57 (such as a USB port, an ethernet port, Firewire port etc.) and a connector 59. The encrypted video data is received at an adaptor unit interface 61 (such as a USB port, an ethernet port, Firewire port etc.) of the games console 7 and passed into the games console memory 63 where it is decrypted and decoded by a video player module 65 under control of the games console central processing unit 67. In order that the video player 65 can decrypt the received encrypted video data, it must have the decryption key corresponding to the encryption key 53. In this embodiment, this decryption key is stored in the smart-card 43 and is labelled Key 3 and referenced 54. Further, in this embodiment, it is not possible to decrypt the encrypted video data using only the decryption key 54. Instead, the decryption key 54 must be combined with a secret 73 which is embedded within the compiled version of the video player 65, to generate the code words necessary to decrypt the video data. Since only the video player module 65 knows the secret 73, it is only the video player 65 which can perform the decryption. Consequently, even though the personal computer 9 may have access to the decryption key 54 and to the encrypted video data via the connector 59, it cannot decrypt the video data to regenerate the decrypted video frames. Video Player FIG. 3 shows in more detail the functional components of the video player module 65. As shown, the video player module 65 includes a decryption key requesting unit 81 which operates, upon the initial receipt of encrypted video data from the adaptor unit 3, to transmit a request via the adaptor unit interface 61, the connector 59 and the games console interface 57, to the adaptor unit 3 for the appropriate decryption key 54 for decrypting the received video data. This request is dealt with by the games console communications controller 71 within the adaptor unit memory 51, which retrieves the appropriate decryption key 54 from the smart-card 43 via the smart-card reader 45. The games console communications controller 71 then transmits the decryption key 54 back to the decryption key requesting unit 81 via the games console interface 57, the connector 59 and the adaptor unit interface 61. The decryption key requesting unit 81 then passes the received decryption key 54 to a code word generator 83 which combines the received decryption key 54 with the secret 73, to generate the code words which can be used to decrypt the encrypted received video data. As shown in FIG. 3, the code words generated by the code word generator 83 are then passed to a decryption engine 85 which uses them to decrypt the encrypted video data received from the adaptor unit 3. The decrypted video data is then passed to an MPEG decoder 87 which decodes the MPEG video data to generate the decoded video data. Web Browser In this embodiment, the decoded video data generated by the video player module 65 is output to a web browser module 89 running in the games console memory 63. In this embodiment, it is the web browser module 89 which generates the appropriate television frames which are output to the television 5 via a television interface 91. In particular, the web browser 89 is used to combine the video frames generated by the video player module 73 with menu frames providing the user with different menu options relating to the interactive television system. FIG. 4 is a block diagram illustrating the main functional components of the web browser module 89. As shown, in this embodiment, the web browser module 89 includes an HTML receiver 92 which operates to receive HTML web pages from the remote media server 17 via the data network 19 and the adaptor unit 3. The HTML receiver 92 then passes the received HTML pages to an HTML interpreter 94 which processes the HTML file to generate the appropriate menu page for output to the television interface 91. In this embodiment, for some of the menu pages, video data will be displayed in a video window within the menu page. For these menu pages, the HTML interpreter 94 requests the appropriate video data from the video player module 65. The received video data is then combined with the menu page video data and output to the TV interface 91 for display to the user on the television 5. In this embodiment, the menu pages provide the user with different options such as the accessing of an electronic programme guide, the accessing of email, web services, video-on-demand etc. The user can then use the remote control 35 to browse through the menu pages and/or to select items from the menu pages. In this embodiment, the HTML menu pages received from the remote media server 17 include instructions for the web browser module 89 which associate key presses on the remote control 35 to the links for the other menu pages and/or the television services selected by the user. In this embodiment, the HTML interpreter 94 passes these instructions to a response generator 96. Subsequently, when a user presses a key on the remote control 35, the remote control interface 37 passes data identifying the key-press to the communications controller 71, which in turn passes the data to the web browser module 89 via the games console interface 57, the connector 59 and the adaptor unit interface 61. The key-press data is then passed to the response generator 96 which interprets the key-press based on the instructions associated with the current menu page being displayed. In this embodiment, these instructions associated with the menu page are Javascript instructions and the response generator 96 includes an appropriate Javascript command processor (not shown) for interpreting the instruction. The response generator 96 then takes the appropriate action based on the user's input, such as transmitting a request back to the remote media server 17, via the adaptor unit 3 and the data network 19, requesting a new video stream. In this embodiment, the web browser module 89 and the video player module 65 are both generated by the adaptor unit 3 and downloaded, in compiled format, into the games console memory 63. In particular, in this embodiment, both the web browser module 89 and the video player module 65 are stored in uncompiled form within the hard disc 39 of the adaptor unit 3. These programs can then be updated from time to time by downloading new programs via the ADSL modem 33. The uncompiled programs are then compiled by a compiler module 98 run in the adaptor unit memory 51. During the compilation of the video player module 65, the compiler 98 inserts an appropriate secret 73 so that the video player 65 can decrypt the video data. In this embodiment, the compiled versions of the web browser module 89 and the video player module 65 are downloaded into the games console memory 63 during a set-up routine when the adaptor unit 3 is initially connected to the games console 7 via the connector 59. As those skilled in the art will appreciate, the transmission of the video player 65 in compiled format over the connector 59 is secure since the compiled version of the video player module 65 will not run on the personal computer 9. This is because, the personal computer 9 and the games console 7 operate with different processors and micro-instructions. Further, for added security, a new version of the video player module 65 can be downloaded into the games console memory 63 at regular intervals, in order to change the secret 73 embedded therein. In this case, a corresponding change of the AES encryption and decryption keys 53 and 54 will also be required to work with the new secret 73. In the event that the user wishes to play a game, the video data for the game is generated by a game controller module 95 from data received from a game CD-ROM 97 via a game interface unit 99. The controller module 95 also generates the video data for the game in dependence upon user inputs from a game pad 101 and a game controller interface 103. In this embodiment, the controller module 95 allows a user to save a current position in a game being played by storing the necessary game history data in the hard disc 39 of the adaptor unit 3. In particular, if the user presses a key on the game pad 101 in order to save the game at the current position, the game controller 95 transmits a request together with the appropriate game history data to the games console communications controller 71 in the adaptor unit 3 via the adaptor unit interface 61, the connector 59 and the games console interface 57. Upon receipt of the game history data, the games console communications controller 71 stores the history data in the hard disc 39. Subsequently, if the user inputs via the game pad 101 that they wish to resume playing the game, the game controller module 95 transmits another request to the games console communications controller 71 for the appropriate game history data. Again, this request is transmitted via the adaptor unit interface 61, the connector 59 and the games console interface 57. In response, the games console communications controller 71 retrieves the requested game history data from the hard disc 39 and transmits it back to the controller 95 via the games console interface 57, the connector 59 and the adaptor unit interface 61. The controller 95 then resumes playing the game using the stored history data and the game data from the CD-ROM 97. Additionally, in this embodiment, the user can request to download new games from a remote game server 21 connected to the data network 19. In particular, in this embodiment, the user can gain access to the remote game server 21 using the web browser module 89. In particular, one of the options on one of the menu pages generated by the web browser 89 includes the option to access the web page for the game server 21. Whilst accessing the game server 21, the user can play games online and/or download games via the data network 19 and the ADSL modem 33 and store the game in the hard disc 39. The user can then access the games stored in the hard disc 39, again through appropriate navigation through the menu pages generated and controlled by the web browser 89. Once a game has been selected for retrieval from the hard disc 39, the games console communications controller 71 reads the game from the hard disc 39 and transmits it via the games console interface 57, the connector 59 and the adaptor unit interface 61 to the game controller 95 which then controls the playing of the game. Modifications and Alternatives In the above embodiment, the video player and the web browser were downloaded in compiled format into the games console and the compiled video player included a secret that was used to decrypt the video data received from the adaptor unit. Because the secret is only available within the games console, the adaptor unit can act as the hub of an ethernet LAN network within the user station. In this case, the connector connecting the adaptor unit to the games console would form part of the LAN connections, with other computer devices, such as the personal computer being coupled to the LAN via this connector. In the above embodiment, both a video player and a web browser were downloaded into the games console from the adaptor unit. The use of a web browser in addition to the video player allowed the user to interact and gain access to services provided by remote servers coupled to the data network. However, as those skilled in the art will appreciate, the use of such a web browser is not essential. The menu pages may be pre-stored within the games console or the adaptor unit and accessed by the user pressing an appropriate key on the game pad or on the remote control. In such an embodiment, only the video player would be downloaded from the adaptor unit into the games console. In the above embodiment, the user navigated through the menu pages using the remote control. In an alternative embodiment, the user may use the game pad in addition to or instead of the remote control to navigate through the menu pages. In the above embodiment, the adaptor unit and the games console were connected together by a connector. This connector may be any appropriate connector, such as one or more wires or a wireless interface. The adaptor unit may also be arranged in the form of a cartridge which can be inserted into an appropriate slot of the games console. In the above embodiment, the adaptor unit included both a television tuner and an ADSL modem. As those skilled in the art will appreciate, in an alternative embodiment one of these video receivers may be omitted. In the above embodiment, a remote control interface was provided in the adaptor unit. Alternatively, the remote control interface may be omitted or provided within the games console. In the above embodiment, the video player and the web browser were downloaded in compiled format from the adaptor unit. In an alternative embodiment, the video player and/or the web browser may be provided in compiled format on a CD-ROM and read into the games console via the game interface. However, such an embodiment is not preferred because of the ease with which CD-ROMs can be copied. In the above embodiment, the received video data was initially decrypted within the adaptor unit and then re-encrypted using a different encryption technique. This is because the video data must be encrypted using a user-specific encryption code so that it can only be decrypted by a video player having the above-described secret. However, as those skilled in the art will appreciate, this is not essential. The encrypted video data received by the adaptor unit may be passed directly to the games console. In this case, the decryption key used to decrypt the received video data would preferably be processed by the adaptor unit with the user's secret to generate an appropriate intermediate decryption key which can be passed from the adaptor unit to the games console over the connector. The games console can then use the user's secret to transform the intermediate decryption key into the decryption key necessary to decrypt the received video data. Again, since the games console only knows the user's secret, other devices (such as the personal computer) coupled to the connector cannot decrypt the received video data. In the above embodiment, the decoded video data and the games video data were output to a television interface. If the television is a digital television, then this television interface may comprise a frame buffer. However, if the television is an analogue television, then the television interface will include an appropriate analogue video signal generator which generates an appropriate video signal from the digital video data. In the above embodiment, a secret was embedded within the video player so that encrypted video data could be transmitted over an unsecured communications link which connected the adaptor unit to the games console. As those skilled in the art will appreciate, a similar secret may be embedded within the web browser in order to keep secret any communications transmitted between the adaptor unit and the browser in the games console. This may be used, for example, in order to provide a secure communications channel between the games console and the remote game server. This allows the game server to be able to encrypt the games which are downloaded to the games console via the adaptor unit so that they cannot be accessed by a device also connected to the connection between the adaptor unit and the games console. Such a secure communication link between the games console and the remote game server can also be used, for example, to control micropayments for playing a downloaded game. For example, the secure communication link may be used by the user to pay for a game before it is downloaded. Alternatively, each time the game is played the browser may signal this to the adaptor unit which can either increment a charge based on how long the game has been played or send a message to the remote game server where the appropriate charge is made. In addition to providing the games console with an interface to remote game servers, the adaptor unit also provides the games console with an interface to other users via the data network to which the adaptor unit is attached. The user of the games console can therefore take part in network gaming in which users of different games consoles can simultaneously play a game with multiple users distributed at different physical locations on the data network. In the main embodiment described above, the encryption and decryption keys for the video data were stored on a smart-card which could be inserted into the adaptor unit. As those skilled in the art will appreciate, it is not essential to store these keys on a smart-card. A separate “smart processor” may be built onto the mother-board of the adaptor unit. However, the use of a smart-card or the like is preferred because it is easy to replace the smart-card if it is believed that the security of the encryption and/or decryption keys has been compromised.
20060615
20171114
20061109
85319.0
A63F924
2
GARNER, WERNER G
Games console adaptor unit
UNDISCOUNTED
0
ACCEPTED
A63F
2,006
10,537,216
ACCEPTED
Interference compensation optically synchronized safety detection system for elevator sliding doors
A method for detecting interference energy in a sliding door safety system includes the steps of disposing at least one emitter along a first vertical surface, disposing at least one receiver corresponding to the at least one emitter along a second vertical surface, activating the at least one receiver, activating the at least one emitter to emit an energy beam that includes a modulated square wave of a predetermined frequency, sampling an energy intensity received by the activated at least one receiver a predetermined number of times recording each time a received energy intensity to form a plurality of recorded energy intensities, selecting the lowest magnitude one of the plurality of recorded energy intensities to form a lowest recorded energy intensity, comparing the lowest recorded energy intensity to a threshold value and determining a source of the energy intensity to be external when the lowest recorded energy intensity is less than the threshold value.
1. A method for detecting interference energy in a sliding door safety system comprising the steps of: disposing at least one emitter along a first vertical surface; disposing at least one receiver corresponding to said at least one emitter along a second vertical surface; activating said at least one receiver; activating said at least one emitter to emit an energy beam comprising a modulated square wave of a predetermined frequency; sampling an energy intensity received by said activated at least one receiver a predetermined number of times recording each time a received energy intensity to form a plurality of recorded energy intensities; selecting the lowest magnitude one of said plurality of recorded energy intensities to form a lowest recorded energy intensity; comparing said lowest recorded energy intensity to a threshold value; and determining a source of said energy intensity to be external when said lowest recorded energy intensity is less than said threshold value. 2. The method of claim 1 comprising the additional steps of: performing statistical analysis upon said plurality of recorded received energy intensities to determine a measure of consistency amongst said plurality of recorded received energy intensities when said source of said energy intensity has not previously been determined to be external; and determining a source of said energy intensity to be external if said measure of consistency is sufficiently low. 3. The method of claim 2 comprising the additional step of modulating the energy beam with a predefined binary code. 4. The method of claim 3 comprising the additional step of: sampling an energy signal received by said activated at least one receiver a predetermined number of times recording each time a received energy signal to form a plurality of recorded energy signals; and verifying the presence of said predefined binary code in at least one of the sampled plurality of recorded energy signals. 5. The method of claim 1 wherein disposing said at least one emitter along a first vertical surface comprises disposing said at least one emitter along an elevator door. 6. The method of claim 1 wherein disposing said at least one receiver corresponding to said at least one emitter along a second vertical surface comprises disposing said at least one receiver along an elevator door. 7. The method of claim 1 wherein said energy beam comprises IR energy.
BACKGROUND OF THE INVENTION (1) Field of the Invention The present invention relates to a method for detecting energy interference in an optically synchronized safety detection system for sliding elevator doors and compensating for such interference. (2) Description of Related Art In optically synchronized elevator detection and safety systems, consisting of separate emitter and receiver arrays, the energy produced by an emitter array is produced in a fixed sequence or pattern, and the receiver array predictively enables or activates individual receivers according to the fixed sequence produced by the emitters. When an activated receiver detects sufficient energy from the emitter array, a “connect” is logged for the individual beam being sampled (composed of the specific emitter and its corresponding receiver). The receiver array then disables the currently enabled receiver and activates the next receiver in the scanning sequence. This process continues as long as beams connect. Broken beams (those for which an individual receiver does not detect emitted energy within a specified maximum wait time) cause the detection system to signal a door controller to reopen the doors due to the detection of an obstruction in the path of the closing doors. A drawback of one such optically synchronized detection system is the potential presence of various external sources of light energy or electrical noise which can interfere with the optical and synchronization, or sync, functionality of the scan. If the energy produced by these external sources is modulated similarly to the energy transmitted by the door safety system, the external energy can be received by the system and interpreted as detection scanning beam energy produced by the emitter array and cause false indexing of receivers to check the next beam in the scan sequence. Such false indexing causes loss of sync between the emitter array and the receiver array, resulting in false obstruction detections and false reversals of the elevator doors. Sources of interference light energy include fluorescent lighting systems, strobe lights associated with fire alarm systems, and beacons atop emergency vehicles. Sources of external, impulse type, electrical noise include relay type elevator controllers and electromechanical door operators. What is therefore needed is a safety detection system for sliding doors which ensures proper operation of in the presence of impulse type electrical noise and light sources, which produce light similar to that produced by the safety detection system for scanning purposes. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method for detecting energy interference in an optically synchronized safety detection system for sliding elevator doors and compensating for such interference. In accordance with the present invention, a method for detecting interference energy in a sliding door safety system comprises the steps of disposing at least one emitter along a first vertical surface, disposing at least one receiver corresponding to the at least one emitter along a second vertical surface, activating the at least one receiver, activating the at least one emitter to emit an energy beam comprising a modulated square wave of a predetermined frequency, sampling an energy intensity received by the activated at least one receiver a predetermined number of times recording each time a received energy intensity to form a plurality of recorded energy intensities, selecting the lowest magnitude one of the plurality of recorded energy intensities to form a lowest recorded energy intensity, comparing the lowest recorded energy intensity to a threshold value and determining a source of the energy intensity to be external when the lowest recorded energy intensity is less than the threshold value. In accordance with the present invention, the aforementioned method additionally comprises the steps of performing statistical analysis upon the plurality of recorded received energy intensities to determine a measure of consistency amongst the plurality of recorded received energy intensities when the source of the energy intensity has not previously been determined to be external, and determining a source of the energy intensity to be external if the measure of consistency is sufficiently low. In accordance with the present invention, the aforementioned method additionally comprises the additional steps of modulating the energy beam with a predefined binary code, sampling an energy signal received by the activated at least one receiver a predetermined number of times recording each time a received energy signal to form a plurality of recorded energy signals, and verifying the presence of the predefined binary code in at least one of the sampled plurality of recorded energy signals. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 A diagram of an elevator sliding door system to which the present invention is directed. FIG. 2 A diagram of a modulated square wave for use in the elevator sliding door system of the present invention. FIG. 3 A diagram of a modulated binary code square wave for use in the elevator sliding door system of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S) With reference to FIG. 1 there is illustrated a vertically arranged array of emitters 11 located along the right door 21 of an elevator sliding door system 10 and a matched, vertically arranged, array of receivers 17 located along the left door 23 of an elevator sliding door system 10. While illustrated with reference to a plurality of emitters 11 and receivers 17 arranged vertically and programmed to emit and receive a plurality of energy beams in a predefined sequence, the present invention is not so limited. Rather, the present invention is broadly drawn to encompass any and all configurations of emitters and receivers arranged to perform a safety scan in an environment wherein spurious, external, electromagnetic signals may interfere with emitted energy beams. A representation of the energy beam 23 produced by a single active emitter 15 is shown. In a preferred embodiment, the energy beam 23 comprises IR energy. A single active emitter 15 is turned on and a receiver 17 directly across from the emitter is activated to form an active receiver 13 is turned on and remains on until it detects the energy beam's 23 signal. After detecting the energy beam 23, the active receiver 13 is disabled and the next receiver 17 in the scan sequence in activated to become the active receiver 13 and to receive the energy beam 23. When the next emitter 11 in the sequence is turned on to become the active emitter 15, and the light path to the active receiver 13 is not blocked, the received energy beam 23 signal triggers the next receiver 17 in the sequence to be activated, and so on. This pattern repeats for each emitter/receiver pair. With the present invention, as the area in the path of the closing doors is scanned for obstructions, techniques are applied which enable the safety system to discriminate between the pickup of energy produced by the safety system to detect objects in the entryway, and energy produced by some external source. In a preferred embodiment of the present invention, each beam is sampled multiple times in each door scan frame. The sampling is accomplished by modulating the energy transmitted with a continuous stream of square waves, at a specified frequency. Each beam is sampled successively up to a pre-set maximum number of times. The value of the smallest amplitude sample so acquired is the value actually stored and used as the beam intensity for that beam. If, at any time, during the sampling of a particular beam, no energy is detected, the beam intensity is set to zero. After sampling the pre-set number of times, the stored beam intensity is compared to a predetermined threshold value. If the stored beam intensity is less than the predetermined threshold value, the presence of impulse type energy from an external source is confirmed. This is possible because impulse energy is out of phase with the frequency at which the sampling is performed. As a result, over a number of samples, at least one sample resulting from impulse energy will exhibit a low magnitude. In this way, impulse type energy from external sources can be quickly and easily ignored. In an alternate embodiment of the present invention, each beam is sampled multiple times in each door scan frame. The sampling is accomplished by modulating the energy transmitted with a continuous stream of square waves 21 at a specified frequency as illustrated in FIG. 2. Multiple sampling and impulse rejections is performed as described for the simplest embodiment above. However, if no sample for a particular beam results in a determination that the energy received originated external to the detection system, the resulting energy samples acquired for that beam are compared to determine if the detected energy represents the pickup of external energy or actual scanning energy being produced by the detection system. If the amplitude of the received energy is not consistent, from sample to sample, the determination is made that the received energy originated external to the safety system and is rejected. If the amplitude of the energy is consistent, from sample to sample, the determination is made that the energy was actually scanning energy produced by the detection system. In a preferred embodiment, a maximum amplitude deviation amongst all of the samples is computed and analyzed to determine if the samples, taken as a whole, are sufficiently consistent to confirm that the received energy came from the detection system. However, any number of forms of statistical analysis may be performed to determine the consistency of the samples. In yet another alternative embodiment of the present invention, each beam is sampled multiple times in each door scan frame. The sampling is accomplished by modulating the energy transmitted with a specific binary code 31 as illustrated in FIG. 3. As each sample is being acquired, and while the amplitude of the sample is being measured, the binary code expected to be modulating the received signal is verified. Multiple sampling and impulse rejection is performed, just as described above. However, if no sample for a particular beam results in a “no detect”, the resulting energy samples for that beam, are compared to determine if the detected energy represents the pickup of external energy or actual scanning energy being produced by the detection system. If the amplitude of the received energy is not consistent, from sample to sample, or the binary modulation code is not verified, the determination is made that the received energy originated external to the safety system and is rejected. If the amplitude of the energy is consistent, from sample to sample, or the binary modulation code is verified, the determination is made that the energy was actually scanning energy produced by the detection system. It is apparent that there has been provided in accordance with the present invention an optically synchronized safety detection system for sliding elevator doors capable of compensating for interference which fully satisfies the objects, means, and advantages set forth previously herein. While the present invention has been described in the context of specific embodiments thereof, other alternatives, modifications, and variations will become apparent to those skilled in the art having read the foregoing description. Accordingly, it is intended to embrace those alternatives, modifications, and variations as fall within the broad scope of the appended claims.
<SOH> BACKGROUND OF THE INVENTION <EOH>(1) Field of the Invention The present invention relates to a method for detecting energy interference in an optically synchronized safety detection system for sliding elevator doors and compensating for such interference. (2) Description of Related Art In optically synchronized elevator detection and safety systems, consisting of separate emitter and receiver arrays, the energy produced by an emitter array is produced in a fixed sequence or pattern, and the receiver array predictively enables or activates individual receivers according to the fixed sequence produced by the emitters. When an activated receiver detects sufficient energy from the emitter array, a “connect” is logged for the individual beam being sampled (composed of the specific emitter and its corresponding receiver). The receiver array then disables the currently enabled receiver and activates the next receiver in the scanning sequence. This process continues as long as beams connect. Broken beams (those for which an individual receiver does not detect emitted energy within a specified maximum wait time) cause the detection system to signal a door controller to reopen the doors due to the detection of an obstruction in the path of the closing doors. A drawback of one such optically synchronized detection system is the potential presence of various external sources of light energy or electrical noise which can interfere with the optical and synchronization, or sync, functionality of the scan. If the energy produced by these external sources is modulated similarly to the energy transmitted by the door safety system, the external energy can be received by the system and interpreted as detection scanning beam energy produced by the emitter array and cause false indexing of receivers to check the next beam in the scan sequence. Such false indexing causes loss of sync between the emitter array and the receiver array, resulting in false obstruction detections and false reversals of the elevator doors. Sources of interference light energy include fluorescent lighting systems, strobe lights associated with fire alarm systems, and beacons atop emergency vehicles. Sources of external, impulse type, electrical noise include relay type elevator controllers and electromechanical door operators. What is therefore needed is a safety detection system for sliding doors which ensures proper operation of in the presence of impulse type electrical noise and light sources, which produce light similar to that produced by the safety detection system for scanning purposes.
<SOH> SUMMARY OF THE INVENTION <EOH>Accordingly, it is an object of the present invention to provide a method for detecting energy interference in an optically synchronized safety detection system for sliding elevator doors and compensating for such interference. In accordance with the present invention, a method for detecting interference energy in a sliding door safety system comprises the steps of disposing at least one emitter along a first vertical surface, disposing at least one receiver corresponding to the at least one emitter along a second vertical surface, activating the at least one receiver, activating the at least one emitter to emit an energy beam comprising a modulated square wave of a predetermined frequency, sampling an energy intensity received by the activated at least one receiver a predetermined number of times recording each time a received energy intensity to form a plurality of recorded energy intensities, selecting the lowest magnitude one of the plurality of recorded energy intensities to form a lowest recorded energy intensity, comparing the lowest recorded energy intensity to a threshold value and determining a source of the energy intensity to be external when the lowest recorded energy intensity is less than the threshold value. In accordance with the present invention, the aforementioned method additionally comprises the steps of performing statistical analysis upon the plurality of recorded received energy intensities to determine a measure of consistency amongst the plurality of recorded received energy intensities when the source of the energy intensity has not previously been determined to be external, and determining a source of the energy intensity to be external if the measure of consistency is sufficiently low. In accordance with the present invention, the aforementioned method additionally comprises the additional steps of modulating the energy beam with a predefined binary code, sampling an energy signal received by the activated at least one receiver a predetermined number of times recording each time a received energy signal to form a plurality of recorded energy signals, and verifying the presence of the predefined binary code in at least one of the sampled plurality of recorded energy signals.
20050603
20060704
20060216
70075.0
G06M700
0
PYO, KEVIN K
INTERFERENCE COMPENSATION OPTICALLY SYNCHRONIZED SAFETY DETECTION SYSTEM FOR ELEVATOR SLIDING DOORS
UNDISCOUNTED
0
ACCEPTED
G06M
2,005
10,537,297
ACCEPTED
Vibrating beam accelerometer
Accelerometer micromachined in a plane plate comprising a base, and at least one measurement cell including a moveable seismic mass connected to the base and capable of moving translationally along the sensitive y axis of the accelerometer under the effect of an acceleration γ along this y axis, a resonator cell that comprises a resonator that can vibrate and be subjected to a tensile or compressive force depending on the direction of the acceleration γ and is placed symmetrically with respect to an axis of symmetry S of the structure, this axis S being parallel to the y axis and passing through the center of gravity of the seismic mass, the measurement cell furthermore including amplification means for amplifying the acceleration force, which means comprise at least one anchoring foot for anchoring to the base, two rigid terminations of the resonator cell and two pairs of micromachined arms symmetrical with respect to the axis S, each pair comprising a first arm connecting a termination to the seismic mass, and a second arm connecting the same termination to the anchoring foot, the angle α between the Ox axis and the first arm being small enough for the tensile or compressive force exerted on the resonator to be greater than the acceleration force exerted on the seismic mass.
1. An accelerometer micromachined in a plane plate having a base, comprising a measurement cell including a moveable seismic mass connected to the base and capable of moving translationally along a sensitive Oy axis; of the accelerometer under the effect of an acceleration γ along this Oy axis, a resonator cell comprising a resonator that can vibrate and be subjected to a tensile or compressive force depending on the direction of acceleration γ and is placed symmetrically with respect to an axis of symmetry S of the structure, this axis S being parallel to the Oy axis and passing through the center of gravity of the seismic mass; the measurement cell furthermore including amplification means for amplifying the acceleration force that generates the translation, which means include an anchoring foot for anchoring to the base, two rigid terminations of the resonator cell and two pairs of micromachined arms, the pairs being symmetrical with respect to the axis S, each pair comprising a first arm connecting a first point of attachment to a termination and a second point of attachment to the seismic mass, and a second arm connecting a third point of attachment to the same termination and a fourth point of attachment to the anchoring foot, the angle α between the Ox axis perpendicular to the Oy axis and the line joining the first and second points of attachment being symmetrical with respect to the axis connecting the terminations via their mid-point, of the angle between the Ox axis and the line joining the third and fourth points of attachment and sufficiently small for the tensile or compressive force exerted on the resonator to be greater than the acceleration force exerted on the seismic mass, wherein the resonator cell comprises two rigid embedding elements for embedding the ends of the resonator and two pairs of secondary micromachined arms, these pairs being symmetrical with respect to the axis S, each pair comprising a first secondary arm connecting a first point of attachment to an embedding element and a second point of attachment to a termination of the cell, and a second secondary arm connecting a third point of attachment to the other embedding element and a fourth point of attachment to the same termination of the cell, the angle β between the Oy axis and the line joining the first and second points of attachment being symmetrical with respect to the axis passing through the mid-points of the embedding elements, of the angle between the Oy axis and the line joining the third and fourth points of attachment and low enough for the tensile or compressive force exerted on the resonator to be greater than the acceleration force exerted on the seismic mass. 2. The accelerometer as claimed claim 1, wherein the pairs of arms are straight or curved. 3. The accelerometer as claimed in claim 1, wherein the first point of attachment of the first arm is located further away from the axis of symmetry S than its second point of attachment. 4. The accelerometer as claimed in claim 1, wherein the first point of attachment of the first arm is located closer to the axis of symmetry S than its second point of attachment. 5. The accelerometer as claimed in preceding claim 1, wherein the pairs of arms are straight or curved. 6. The accelerometer as claimed in claim 1, wherein the seismic mass surrounds the amplification means. 7. The accelerometer as claimed in claim 1, wherein the first and second arms have a thickness that can vary along their length. 8. The accelerometer as claimed in claim 1, wherein it furthermore includes guiding arms for guiding the seismic mass, which arms lie along the Ox axis and are connected to a part fixed to the base. 9. The accelerometer as claimed in claim 1, wherein it comprises two measurement cells placed with respect to each other in such a way that, under the effect of an acceleration, the resonator of one measurement cell undergoes a tensile force while the resonator of the other measurement cell undergoes a compressive force. 10. The accelerometer as claimed claim 9, wherein the two measurement cells have a common seismic mass. 11. The accelerometer as claimed in claim 9, wherein the arms are placed in the same way for each of the measurement cells. 12. The accelerometer as claimed in claim 9, wherein the arms are not placed in the same way for each of the measurement cells. 13. The accelerometer as claimed in claim 1, wherein the resonator comprises a vibrating beam, or two vibrating beams forming a tuning fork, or at least three vibrating beams or a torsion bar. 14. The accelerometer as claimed in claim 2, wherein the first point of attachment of the first arm is located further away from the axis of symmetry S than its second point of attachment. 15. The accelerometer as claimed in claim 2, wherein the first point of attachment of the first arm is located closer to the axis of symmetry S than its second point of attachment. 16. The accelerometer as claimed in claim 3, wherein it furthermore includes guiding arms for guiding the seismic mass, which arms lie along the Ox axis and are connected to a part fixed to the base. 17. The accelerometer as claimed in claim 4, wherein it comprises two measurement cells placed with respect to each other in such a way that, under the effect of an acceleration, the resonator of one measurement cell undergoes a tensile force while the resonator of the other measurement cell undergoes a compressive force. 18. The accelerometer as claimed in claim 10, wherein the arms are placed in the same way for each of the measurement cells. 19. The accelerometer as claimed in claim 10, wherein the arms are not placed in the same way for each of the measurement cells. 20. The accelerometer as claimed in claim 9, wherein the resonator comprises a vibrating beam, or two vibrating beams forming a tuning fork, or at least three vibrating beams or a torsion bar.
The field of the invention is that of flat monolithic accelerometers. The flat structure allows simple and inexpensive fabrication, especially by chemical etching processes. In addition, the fabrication may be collective. A flat monolithic accelerometer conventionally comprises a body having a base and two measurement cells providing a differential measurement. A measurement cell typically comprises a seismic mass connected, on one side, to the base and, on the other side, to a force sensor, which is itself also connected to the base. When the accelerometer is subjected to an acceleration along the sensitive axis, which is the axis of the acceleration to be measured, the seismic mass is subjected to an inertial force, which is amplified and transmitted to the force sensor by means for amplifying the force or displacement transmitted. In patent application FR 0 102 573, the amplification is obtained by means of an arm called a lever arm, which extends the seismic mass. The displacement of the seismic mass is transmitted to the force sensor by means of this lever arm. More precisely, the arm is connected to the base via an articulation, allowing the mass to rotate about an axis perpendicular to the sensitive axis of the accelerometer, and is connected to the force sensor via a hinge. When the accelerometer is subjected to an acceleration along the sensitive axis, the seismic mass is subjected to a force which rotates it about the articulation, as therefore that part of the lever arm which is connected to the force sensor. The force sensor is a vibrating-beam sensor. The vibrating beam is connected to electrodes that allow it to vibrate at its resonant frequency and to a circuit for measuring the variation in its resonant frequency. The measurement cells are mounted so that when the accelerometer is subjected to an acceleration along the sensitive axis one of the beams is subjected to a tensile force, the other beam being subjected to a compressive force of the same value, these tensile or compressive forces varying the resonant frequency of the beam measured by the measurement circuit. Thus, a differential measurement is obtained, which makes it possible in particular to overcome certain nonlinear effects. The variation in the resonant frequency is directly related to the displacement of the force sensor induced by the rotation of that part of the lever arm which is connected to the force sensor. The end of the beam also undergoes a certain rotation, which often proves to be problematic, especially in the case of a tuning fork (i.e. rotation of two beams that form a tuning fork) in which the force transmitted to the two beams is not exactly identical. In addition, the quality of machining of the hinges and articulations is of paramount importance, and constitutes one of the industrial limitations of this accelerometer. Furthermore, since the displacement is proportional to the length of the lever arm, the overall size is greater the higher the desired amplification ratio to be obtained. An important object of the invention is therefore to propose an accelerometer that does not have a rotating lever arm as amplification means but comprises, in general, a resonator that may be a vibrating beam. To achieve this object, the invention proposes an accelerometer micromachined in a plane plate comprising a base, and at least one measurement cell including a moveable seismic mass connected to the base and capable of moving translationally along the sensitive Oy axis of the accelerometer under the effect of an acceleration γ along this Oy axis, a resonator cell comprising a resonator that can vibrate and be subjected to a tensile or compressive force depending on the direction of acceleration γ and is placed symmetrically with respect to an axis of symmetry S of the structure, this axis S being parallel to the Oy axis and passing through the center of gravity of the seismic mass, the measurement cell furthermore including amplification means for amplifying the acceleration force that generates the translation, which means comprise at least one anchoring foot for anchoring to the base, two rigid terminations of the resonator cell and two pairs of micromachined arms, the pairs being symmetrical with respect to the axis S, each pair comprising a first arm connecting a first point of attachment to a termination and a second point of attachment to the seismic mass, and a second arm connecting a third point of attachment to the same termination and a fourth point of attachment to the anchoring foot, the angle α between the Ox axis perpendicular to the Oy axis and the line joining the first and second points of attachment being symmetrical with respect to the axis connecting the terminations via their mid-point, of the angle between the Ox axis and the line joining the third and fourth points of attachment and sufficiently small for the tensile or compressive force exerted on the resonator to be greater than the acceleration force exerted on the seismic mass. Because of the symmetry of this structure, the displacements of the seismic mass, of the embedding terminations and of the resonator are perfectly axial. In addition, the performance of this structure, i.e. the amplification ratio obtained, is simply determined by the angle α; the geometry of the seismic mass, the center of gravity of which lies on the axis of symmetry S, does not play a role in the performance of the accelerometer. According to a first embodiment, the rigid terminations of the resonator are embedding elements for embedding the ends of the resonator; the resonator cell simply comprises the resonator itself. According to another embodiment, the resonator cell comprises two rigid embedding elements for embedding the ends of the resonator and two pairs of secondary micromachined arms, these pairs being symmetrical with respect to the axis S, each pair comprising a first secondary arm connecting a first point of attachment to an embedding element and a second point of attachment to a termination of the cell, and a second secondary arm connecting a third point of attachment to the other embedding element and a fourth point of attachment to the same termination of the cell, the angle β between the Oy axis and the line joining the first and second points of attachment being symmetrical with respect to the axis passing through the mid-points of the embedding elements, of the angle between the Oy axis and the line joining the third and fourth points of attachment and low enough for the tensile or compressive force exerted on the resonator to be greater than the acceleration force exerted on the seismic mass. This embodiment corresponds to a cascade configuration, with the aim of multiplying the amplification ratio of the accelerometer. Other features and advantages of the invention will become apparent on reading the detailed description that follows, given by way of nonlimiting example and with reference to the appended drawings in which: FIG. 1 shows schematically a first embodiment of a measurement cell structure for an accelerometer according to the invention, in which the seismic mass is located on one side of the amplification means, the pairs of arms being placed like a “butterfly”; FIGS. 2 to 5 show schematically a second embodiment of a measurement cell structure for an accelerometer according to the invention, in which the seismic mass surrounds the amplification means, the pairs of arms being placed like a “butterfly” in FIGS. 2 to 4 and as a “jack” in FIG. 5; in FIG. 2, the pairs of arms are located on the other side of the resonator with respect to the terminations; in FIG. 3, they are located on the same side as the resonator; and in FIG. 4 the terminations are U-shaped; FIG. 6 shows schematically an embodiment of a measurement cell structure for an accelerometer according to the invention, in which the arms are curved with a concave shape; FIG. 7 shows schematically an embodiment of a measurement cell structure for an accelerometer according to the invention, in which the arms are curved with a convex shape; FIG. 8 shows schematically an example of an accelerometer according to the invention, comprising two measurement cells; FIG. 9 shows schematically an example of an accelerometer according to the invention, comprising two measurement cells that share the same seismic mass located between their amplification means; FIG. 10 shows schematically an example of an accelerometer according to the invention, comprising two measurement cells that share the same seismic mass located on one side of the accelerometer; FIG. 11 shows schematically an example of an accelerometer according to the invention, comprising two measurement cells that share the same seismic mass located around their amplification means; and FIG. 12 shows schematically an example of an accelerometer according to the invention, in a cascade configuration. Hereafter, the example of a two-beam resonator forming a tuning fork will be given, these beams being made to vibrate in phase opposition by means of two electrodes. It is this tuning fork configuration that is shown in the figures. A resonator comprising one vibrating beam or several vibrating beams or a torsion bar may just as well have been used. The vibrating-beam accelerometer according to the invention preferably comprises two measurement cells that can be produced by machining a silicon-on-insulator (SOI) or quartz substrate, or a substrate of another material, but other methods are also possible. A silicon-on-insulator substrate consists of a stationary monolithic silicon substrate a few hundred microns (for example 450 μm) in thickness constituting the base of the accelerometer, which has on its front face a thin layer of silicon a few microns (for example 2 μm) in thickness, which is itself covered with a single-crystal silicon layer a few tens of microns (for example 60 μm) in thickness. The machining consists in etching the single-crystal silicon via its front face, until the oxide layer is reached, with a selective etchant that etches the silicon without significantly etching the oxide. The etching is stopped when the oxide layer is bared. This oxide layer may itself be removed by selective etching with another etchant so as to preserve only the silicon surface layer. The desired surface features may thus be etched into this layer by means of photoetching techniques or of another technique used in microelectronics in order in this way to obtain the desired moveable plane structure. Hereafter, a coordinate system O,x,y,z shown in the figures will be used, in which the plane of the figures is the O,x,y plane, the Oz axis representing the direction perpendicular to this plane. The axis Ox (respectively Oy, Oz) denotes an axis parallel to the Ox axis (respectively Oy, Oz) shown in the figures. From one figure to another, the same elements will be denoted by the same references. The moveable plane structure 10 of a measurement cell of the accelerometer, shown schematically in FIG. 1, comprises a moveable seismic mass 1 that can move translationally along the sensitive axis of the accelerometer, denoted by the axis Oy, which is the axis of the acceleration γ to be measured, and amplification means 2 for amplifying the force that generates this translation, said force being measured by means of two vibrating beams 30 placed along an Ox axis perpendicular to the Oy axis, which are subjected to a tensile or a compressive force depending on the direction of the acceleration. The beams are placed symmetrically with respect to an axis of symmetry S of the structure, this axis of symmetry being parallel to the Oy axis and passing through the center of gravity of the mass—the geometry of the seismic mass then plays no role in the performance of the accelerometer. The vibrating beams 30 are embedded at each end in a rigid termination 4. Each of these terminations 4 comprises a pair of micromachined arms. The two pairs are symmetrical with respect to the axis of symmetry S. A first micromachined arm 5 connects the termination 4 to the seismic mass 1. In order for the termination 4 not to “float” with respect to the base, that is to say with respect to the stationary monolithic silicon substrate, a second micromachined arm 6, symmetrical with the first arm with respect to the axis of the beam, connects the termination 4 to an anchoring foot 7 fixed to the base. These arms 5 and 6 are connected, respectively, to the seismic mass 1, to the termination 4 and to the anchoring foot 7, by points of attachment. The thickness of an arm 5 or 6 can vary over its length. Also shown schematically in FIG. 1 is a detail of part of the amplification means. The first arm 5 is articulated to the termination 4 via a point of attachment A. Part of an electrode E is also shown. The two vibrating beams 30 are embedded in the termination 4 so far as they are formed, for example, by etching the same layer of material. The hatching represents the material, for example single-crystal silicon in the case of a cell produced by machining an SOI. As indicated above, the surface features, such as the arms 5, the point of attachment A, the termination 4, the beams 30 and the electrode E, have been obtained by etching the single-crystal silicon and then by etching the oxide layer. The angle α made between the Ox axis and the line joining the points of attachment A and B of the first arm 5 which, because of the symmetry of the arms 5 and 6 with respect to the axis connecting the terminations via their mid-point, is symmetrical with the angle made between the Ox axis and the line joining the points of attachment of the second arm 6. This angle α is small enough for the tensile or compressive force exerted on the beam 30 to be greater than the acceleration force exerted on the seismic mass 1. These amplification means 2 furthermore allow the space around the vibrating beams 30 to be cleared, especially in order to place the electrodes in the case of electrostatic excitation. It will be recalled that the vibrating beams are set into vibration at their resonant frequency by means of electrodes placed facing these beams, or directly on the beams, depending on whether there is electrostatic or piezoelectric excitation. The seismic mass 1 is intrinsically guided translationally along the Oy axis owing to the symmetry of the structure. In order to preserve only this degree of freedom along Oy, the structure along Ox and Oz may optionally be further stiffened by guiding arms 8 oriented along the Ox axis, one end of which is fixed to the seismic mass 1 and the other to a part 9 fixed to the base. The force that generates the displacement of the seismic mass 1 along the Oy axis is transmitted via the first arms 5 to each of the terminations 4 which, depending on the direction of displacement, move closer together or further apart along the Ox axis, thus causing a tensile or compressive force on the vibrating beams 30. Since the structure 10 is symmetrical with respect to the axis S, and as regards the arms with respect to the axis of the beams, the displacements of the seismic mass 1, of the terminations 4 and of the beam 30 are perfectly axial. Thus, when the beams 30 form a tuning fork, the tensile or compressive forces are exerted in the same way on each of the beams of the tuning fork. The performance of this structure, that is to say the amplification coefficient obtained, is simply determined by this angle α. When the seismic mass 1 is subject to an acceleration γ along the −Oy direction, the inertial force My is amplified and transmitted by the amplification means 2 to the vibrating beams 30. The compressive force (which may be a tensile force for other configurations) in these beams then has an amplitude of Mγ/tanα. The ratio of the displacement of the seismic mass 1 along −Oy to the displacement along Ox of a termination is approximately equal to 2/tan α. Depending on its use, this structure may constitute a displacement or force amplification system. According to a preferred embodiment, the seismic mass 1 surrounds the vibrating-beam amplification means 2, as shown in FIGS. 2 to 5. Such a configuration allows a more compact structure to be obtained. The arms 5, 6 may be arranged in various ways. They may be arranged in “butterfly” (or in the form of an X), as shown in FIGS. 1, 2 and 4, this arrangement meaning that the first point of attachment A of the first arm 5 to the termination 4 is located closer to the axis of symmetry S than its second point of attachment B to the seismic mass 1. In this case, a displacement of the seismic mass 1 toward the beams 30 then generates a compressive force in the beams. As shown in FIG. 2, the arms 5 and 6 are located on the other side of the beams from the terminations. They may also be located on the same side as the beams, when the length L of the terminations 4 is greater than the distance E between the seismic mass 1 and the anchoring foot 7, as shown in FIG. 3. Another version of this butterfly arrangement is shown in FIG. 4, in which each termination 4 then has a U-shape. The arms 5, 6 may also be arranged like a “jack” as shown in FIG. 5, this arrangement meaning that the first point of attachment A of the first arm 5 is located further away from the axis of symmetry S than its second point of attachment B. A displacement of the seismic mass 1 toward the beam 3 then generates a tensile force in the beams. In these figures, the arms have been shown as straight. They may be curved with a concave shape or a convex shape, as shown in FIGS. 6 and 7, respectively, which illustrate an arrangement of the arms like a “jack”, corresponding to that of FIGS. 3 and 5, respectively. Of course, the accelerometer preferably comprises two moveable structures 10 and 10′ as described, these being placed with respect to each other so as to obtain a differential measurement of the acceleration. An example of this double structure is shown in FIG. 8, in which each structure 10 and 10′ adopts the configuration with U-shaped terminations of FIG. 4. Any other configuration may be used. Under the effect of an acceleration in the opposite direction to the Oy axis, the vibrating beams 30 of the structure 10 are subjected to a compressive force, while the vibrating beams 30′ of the structure 10′ are subjected to a tensile force. In one particular embodiment of the invention, the double structure 10 and 10′ comprises only one seismic mass, common to the two measurement cells, instead of comprising two seismic masses 1 and 1′. The main benefit of such an accelerometer is that the same mass/spring resonant frequency is obtained for both cells. A good approximation of the calculation of this frequency is f = tan ⁢ ⁢ α 2 ⁢ π ⁢ k x m , where m is the seismic mass and kx is the stiffness of the resonator along the Ox axis. If these are separate frequencies, dispersions in the frequency may be observed from one cell to another. The seismic mass may or may not be located between the two amplification means 2, 2′. It may also surround the two amplification means 2, 2′. The pairs of arms may or may not be placed in the same way from one cell to another. FIG. 9 shows an accelerometer comprising only one seismic mass 1 located at the mid-point of the two identical amplification means 2, 2′, the arms 5, 6, 5′ and 6′ of which are arranged like a “jack”. In this case, under the effect of an acceleration in the direction opposite to the Oy axis, the vibrating beams 30 are subjected to a tensile force whereas the other vibrating beams 30′ are subjected to a compressive force. The accelerometer in FIG. 10 comprises only one seismic mass 1 located on one side of the accelerometer, and first amplification means 2, the arms 5, 6 of which are placed like a “jack”, whereas the arms 5′, 6′ of the other amplification means 2′ are placed like a “butterfly”. In this figure, the arms 6 are not connected to an anchoring foot but are connected to the arms 5′ via a transmission element 100 for the displacement of the terminations 4 toward the terminations 4′. In this case, under the effect of an acceleration in the opposite direction to the Oy axis, the vibrating beams 30 are subjected to a tensile force, whereas the other vibrating beams 30′ are subjected to a compressive force. FIG. 11 illustrates the case in which the seismic mass surrounds both amplification means 2, 2′, the arms 5, 6, 5′ and 6′ of which are placed like a “jack”. In this case, under the effect of an acceleration in the opposite direction to the Oy axis, the vibrating beams 30 are subjected to a tensile force whereas the other vibrating beams 30′ are subjected to a compressive force. An accelerometer having the double structure as shown in FIG. 8 was produced with a resonant frequency of the tuning fork of about 30 kHz for a zero acceleration, a change in resonant frequency of the vibrating beams, measured by the measurement circuit, of about 3 kHz, and a displacement of the seismic mass along the y axis of about 10 nanometers per g, g being the Earth's acceleration, equal to 9.81 m/s2. By neglecting the stiffness of the amplification means along the Ox axis relative to the stiffness of the beam, the following amplification ratios 1/tan α at the beams as a function of angle α are obtained: Angle α 1° 2° 3° 4° 5° 10° Force amplification 57 29 19 14 11 6 According to another embodiment, the measurement cell structure may be used in cascade in order to multiply the amplification ratios. FIG. 12 illustrates the case in which two amplification stages are placed in cascade, while still keeping a space for the electrodes. The vibrating beams 30 shown in FIGS. 1 to 11 are then replaced more generally with a vibrating-beam cell which is also placed between the rigid terminations 4. In the case in FIG. 12, the vibrating-beam cell comprises two vibrating beams 30 placed on the axis of symmetry S (and therefore symmetric with respect to this axis S), said beams being embedded at each end in a rigid embedding element 40. Each of these embedding elements 40 comprises a pair of secondary micromachined arms. The two pairs are symmetrical with respect to the axis of symmetry S. A first secondary arm 50 connects the embedding element 40 to a first termination 4 of the cell. A second secondary arm 60, symmetrical with the first arm with respect to the axis of the beams 30, connects the embedding element 40 to the second termination 4 of the cell. These arms 50 and 60 are connected to the embedding element 40 and to the termination 4 of the cell, respectively, via points of attachment. The thickness of a secondary arm 50 or 60 may vary over its length. The angle β made between the axis parallel to the axis of the beam, in this case the Oy axis, and the line joining the points of attachment C and D of the first arm 50 which, because of the symmetry of the arms 50 and 60 with respect to the axis of the beams 30, is symmetrical with the angle made between the axis parallel to the axis of the beams and the line joining the points of attachment of the second arm 60, is small enough for the tensile or compressive force exerted on the beams 30 to be greater than the acceleration force exerted on the seismic mass 1. This cascade arrangement, which results in an increase in the amplification ratio, makes it possible to obtain a tensile or compressive force greater than that obtained with a noncascade configuration. Finally, the vibrating beams described in relation to FIGS. 1 to 11 are one particular case of a vibrating-beam cell. In this particular case, the rigid terminations 4 of the vibrating-beam cell coincide with the embedding elements 40. Various examples of embodiments have been presented, but of course other configurations are possible.
20050602
20061024
20060511
69820.0
G01P15097
0
KWOK, HELEN C
VIBRATING BEAM ACCELEROMETER
UNDISCOUNTED
0
ACCEPTED
G01P
2,005
10,537,427
ACCEPTED
Trailer for towing after a towing vehicle, a system comprising a trailer and a towing vehicle, and a method of steering a trailer around a turning point
The invention relates to trailer (1) for towing after a towing after a towing vehicle, said trailer (1) comprising a frame (3) configured for carrying a load and having a front end with a coupling (5) configured for connecting the trailer (1) to the towing vehicle and allowing that the trailer (1) and the towing vehicle are able to assume mutually angular positions during turning about a turning point O; and a rear end. The trailer also has a separate wheel frame (8) that is connected to the frame (3) by means (10) that allow a relative turning of the frame in relation to the wheel frame (8) during turning of the trailer about the turning point, said wheel frame (8) comprising oppositely arranged wheels (4) that support the trailer (1) during the towing and that are arranged at a distance from each other close to a respective longitudinally extending side of the frame (3); and actuator means (15) for producing said relative turning of the frame (3). The invention is characterized in that the connecting means (10) also allow a controlled transversal movement of the frame (3) in a direction towards or away from said turning point (O) simultaneously with said relative turning of the frame (3); and that the trailer (1)comprises actuator means (15) for producing said transversal movement of the frame (3).
1. A trailer (1) for towing after a towing vehicle, said trailer (1) comprising: a) a frame (3) configured for carrying a load and having: i) a front end with a coupling (5) configured for connecting the trailer (1) to the towing vehicle and allowing that the trailer (1) and the towing vehicle are able to assume mutually angular positions during turning about a turning point O; and ii) a rear end; b) a separate wheel frame (8) that is connected to the frame (3) by means of connecting means (10) that allow a relative turning of the frame (3) in relation to the wheel frame (8) during said turning about a turning point (O), said wheel frame (8) comprising oppositely arranged wheels (4) that support the trailer during the towing and that are arranged at a distance from each other close to a respective longitudinally extending side of the frame (3); and c) actuator means (15) for producing said relative turning of the frame (3); characterised in that the connecting means (10) also allow a controlled transversal movement of the frame (3) in relation to the wheel frame (8) in a direction towards or away from said turning point (O) simultaneously with said relative turning of the frame (3); and that the trailer (1) comprises actuator means (15) for producing said transversal movement of the frame (3). 2. A trailer according to claim 1, characterised in that the wheels (4) are arranged at the rear end of the trailer (1) opposite the coupling (5). 3. A trailer according to claim 1 or 2, characterised in that the wheel frame (8) is arranged behind the rear end of the frame (3) in order to thus constitute the rear end of the trailer (1). 4. A trailer according to any one of the preceding claims, characterised in that the wheel frame (8) carries an agricultural implement, in particular a fold boom sprayer (20). 5. A trailer according to any one of the preceding claims, characterised in that the load is a liquid container. 6. A trailer according to claim 5, characterised in that the container extends until or beyond the rear end of the frame (3); and that the wheels (4) are arranged at the rear end of the trailer (1) opposite the coupling (5). 7. A trailer according to any one of the preceding claims, characterised in that said wheels (4) are also arranged for turning about a vertical or essentially vertical axis in relation to the wheel frame (8); and that actuator means (15′″) are coupled to the wheel frame (8) to produce this turning. 8. A trailer according to any one of the preceding claims, characterised in that the connecting means (10) are constituted of at least two arms (10′, 10″) that are pivotally connected to the frame (3) and the wheel frame (8), respectively, and that constitute a trapezoidal mechanism for controlling the movement of the frame (3) along a curve track in relation to the wheel frame (8). 9. A trailer according to any one of the preceding claims 1-7, characterised in that the connecting means (10) comprise a journaling for the wheel frame (8) with slide steering for controlling the movement of the frame (3) along a curve line in relation to the wheel frame (8). 10. A trailer according to any one of the preceding claims, characterised in a control unit with a memory that produces, via the actuator means (15), a predetermined fixed setting of the frame (3) in relation to the wheel frame (8) in correspondence with the angle position between the towing vehicle and the wheel frame (8). 11. A trailer according to any one of the preceding claims, characterised in that the actuator means (15) are connected to the frame (3), to the wheel frame (8) and/or to the connecting means (10). 12. A system comprising a towing vehicle and a trailer (1) according to any one of the preceding claims 1-11, characterised in a control unit with a memory that produces, via the actuator means (15), a predetermined fixed setting of the frame (3) in relation to the wheel frame (8) in correspondence with the angle position between the towing vehicle and the wheel frame (8). 13. A system according to claim 12, characterised in that the mutual distances transversal to the direction of driving between the wheels of the towing vehicle and between the wheels (4) of the trailer (1) are essentially identical. 14. A system according to claim 12 or 13, characterised in that the control unit is configured for ensuring that at least one set of wheels on the towing vehicle and the wheels (4) of the trailer (1) move(s) along the same curve line during turning about a turning point O. 15. A method of steering a trailer (1) around a turning point (O), said trailer being towed by a towing vehicle, wherein the trailer (1) comprises: a) a frame (3) configured for carrying a load and having: i) a front end with a coupling (5) configured for connecting the trailer (1) to the towing vehicle and allowing that the trailer (1) and the towing vehicle are able to assume mutually angular positions during turning about a turning point O; and ii) a rear end; b) a separate wheel frame (8) that is connected to the frame (3) by means of connecting means (10) that allow a relative turning of the frame (3) in relation to the wheel frame (8) during the steering, said wheel frame (8) comprising oppositely arranged wheels (4) that support the trailer (1) during the towing and that are arranged at a distance from each other close to a respective longitudinally extending side of the frame (3); and c) actuator means (15) for producing said relative turning of the frame (3); characterised in that, by means of actuator means (15), a transversal movement of the frame (3) is produced in relation to the wheel frame (8) in a direction towards or away from said turning point (O) simultaneously with a relative turning of the frame (3) in relation to the wheel frame (8).
The present invention relates to a trailer for towing after a towing vehicle as defined in the preamble to claim 1. Thus, as a starting point the trailer according to the invention comprises a frame configured for carrying a load and having a front end with a coupling for connecting the trailer to the towing vehicle in such a manner that the trailer and the towing vehicle are able to assume mutual angle positions during turning around a turning point, and a rear end. Besides, the trailer comprises a separate wheel frame that is connected to the frame by means of connecting means that allow a relative turning of the frame in relation to the wheel frame during said turning around a turning point. This wheel frame comprises oppositely arranged wheels that support the trailer during the towing and are arranged at a distance in relation to each other near a respective longitudinally extending side of the frame. Additionally, the trailer has actuator means for producing said relative turning of the frame. It being difficult to define the notion of actual parallel longitudinally extending sides of the frame, said longitudinally extending sides can be perceived as areas situated to each side of a longitudinally extending line of symmetry for the frame that extends from the front end of the frame to the rear end of the frame. Trailers of this type are already known from eg BE 473 218 and EP 350 008. It is a common feature of these trailers that it is possible to actively influence and modify the movement of the trailer, when the trailer is moved through curves by means of the towing vehicle. For instance, there may be a need for performing such influence when a towing vehicle and a trailer are to move along parallel tracks on a field and when, to this end, the towing vehicle and the trailer have to turn at the end of the field. In particular in that context it is important that the wheels of the trailer do not interfere with an extra track on the field, which may harm the crop, but rather that the wheels of the trailer accurately follow the wheel tracks that were initially established in the field or generated during driving by the preceding towing vehicle. The mutual spacing transversally to the driving direction between the wheels on the trailer is, of course, as a starting point selected to be in correspondence with the corresponding space between the wheels of the towing vehicle, thereby avoiding the generation of an additional wheel track during straight-ahead operation. However, during the turning an active influence has to be exerted on the trailer to avoid generation of additional wheel tracks. By the construction of such trailers it is necessary to take into account the stability problems that may arise, in particular in case the trailer is to carry a high load. The problems are further exacerbated if the load is constituted by a high tank containing liquids that may splash to the effect that the risk of the trailer toppling on its side during the turning is further increased. This problem is of particular relevance when the trailer constitutes a field sprayer and a fold boom sprayer. Since the distance between the wheels on the trailer is, as mentioned, determined by the corresponding distance between the wheels of the towing vehicle, the system chosen for influencing the turning of the trailer around the turning point may impose limitations to the options available to the constructer when the shape of the frame is to be determined. This will also be the case inasmuch as the load of the trailer is concerned, including eg the configuration of the liquid tank, where a field sprayer may be concerned that constitutes the load. The liquid tank and the frame must thus be shaped specifically for allowing space for the movement of the wheels during turning of the wheel frame. It follows from this that the tank of such trailers must be made even narrower at the bottom than is shown in FIG. 1 of EP 862 855, where the wheel axles of the trailer are fixedly mounted. In order to compensate for such reduction in dimensions at the bottom of the tank, the constructor will often strive to increase the height of the liquid tank, which may, however, lead to quite serious problems with stability, in particular during turning around a turning point. It is an object of the invention to provide a trailer that can be steered though curves and that reduces the limitations that may be imposed on the shape of the load. This is accomplished as featured in claim 1 in that the connecting means mentioned above are configured such that they also allow a controlled, transversal movement of the frame in relation to the wheel frame in a direction towards or away from said turning point, ie transversally to the direction of driving, simultaneously with said relative turning of the wheel frame taking place; and that the trailer comprises actuator means for producing said transversal movement of the frame. It will be understood that the trailer may be provided with more than one wheel frame of the type described, albeit at present a configuration with one wheel frame is preferred. Advantageous embodiments will appear from the dependent claims. The trailer can thus be an integral part of a tool, such as an agricultural implement, where the load is a receptacle for spraying liquid that extends very closely to the rearmost end of the trailer, the wheels being arranged at the rear end of the trailer, opposite the coupling. The connecting means may in a simple manner be configured as at least two arms that are pivotally connected to the frame and the wheel frame, respectively, and that constitute a trapezoidal mechanism for controlling the movement of the wheel frame along a curve track. The invention also relates to a system comprising a combination of the trailer and a towing vehicle and a method of steering a trailer through curves. In the following, the invention will be explained in further detail with reference to the drawing, wherein FIGS. 1a and 1b show how the wheels on a trailer can be steered when the trailer is towed after a towing vehicle and when it is desired that the trailer should follow the track of the towing vehicle; FIGS. 2a, 2b and 2c show respective positions for the trailer according to the invention during movements through curves having different radii; and FIG. 3 shows an alternative embodiment of the trailer, wherein the wheels have a further degree of freedom. In FIGS. 1a and 1b, two solutions known from BE 473 218 are represented for controlling the wheels of a trailer and it will appear how, in order to ensure that the wheel tracks of the trailer follow the wheel tracks of the towing vehicle, it is necessary to see to it that the wheels on the wheel frame are at any time perpendicular to a straight line that extends to the turning point O. By the present invention the latter condition must also be complied with in those cases where it is desired that the wheel tracks of the trailer are to follow the wheel tracks of the towing vehicle during turning around a turning point O, and it can be ensured by providing, either on the towing vehicle or on the trailer, a control unit with a memory that will, via actuator means, produce a predetermined setting of the frame in relation to the wheel frame, as will be explained below. FIGS. 2a, 2b and 2c show a trailer 1 according to the invention. Preferably the trailer 1 is connected directly to the towing hook on the towing vehicle via a coupling in the form of a tow ring at the front end of the frame 3. The wheel frame 8 of the trailer 1 that carries the wheels that support the trailer is movably mounted on the frame 3 at the rear end thereof, in such a manner that the frame may—in relation to the wheel frame 8—be forced to turn and simultaneously forced to swing sideways and outwards transversally to the direction of driving towards or away from the turning point O in relation to the wheel frame 8. When the combined vehicle drives straight ahead, the wheels 4 are, of course, parallel with the wheels (not shown) of the towing vehicle, and the wheel frame 8 extends in extension of the frame 3 behind same. When the towing vehicle turns and it is thus time to swing around a turning point O, the frame 3 will be conveyed to the side, while simultaneously the frame turns in relation to the wheel frame 8. In order to obtain this translatory and rotary movement of the frame 3, the frame 3 is preferably connected to the wheel frame 8 via connecting means 10 in the form of a trapezoidal connection comprising two arms of equal lengths. 10′, 100″, each of which is pivotally connected to the frame 3 and the wheel frame 8, respectively. Hereby the frame 3 is controlled by the particular pattern of movement that follows from the freedom of movement of the trapezoidal connection. FIG. 2a shows that the arms 10′, 10″ converge in a direction towards the frame 3, but it may very well be an option to have an alternative configuration, wherein the arms 10′, 10″ converge in a direction towards the wheel frame 8. It may in some cases entail a favourable increase of the trailer stability during turning. When the towing vehicle starts to move, actuator means 15 in the form of eg hydraulic cylinders 15″, 15″ control the movement of the frame 3, to the effect that the frame 3 adapts to the desired position. The control of the hydraulic cylinders 15′, 15″ may occur in correspondence with a detected angle between the towing vehicle and the wheel frame 8. When, in particular in connection with field sprayers, where the frame 3 carries a large liquid tank, it is a point of interest to accomplish a swinging of the frame 3 and not merely a turning of the wheel frame 8 or of the axle 8′ of the wheels 4, it is due to the fact that such turning on its own may limit the dimensions of the tank transversally to the frame 3 at the bottom at the wheels 8 and on the connecting rods (19) between the wheel frame 8 and the beam 20, as the wheels may bump against the tank and/or the connecting bars 19. It is preferred that the axes of rotation of the wheels 4 in relation to the wheel frame 8 are fixed as shown in FIGS. 2a-2c, and that thus the freedom of movement resides primarily in the movability of the wheel frame 8 in relation to the frame 3. In some situations, as shown specifically in FIG. 3 it may be expedient to build in a system for turning the wheels 4 in relation to the wheel frame 8, eg if the remaining constructive elements on the frame 3 prevent a sufficiently large slewing of the wheel frame 8. This turning movement may be generated eg by means of a system of actuator means as shown by the reference numeral 15″′, in addition to the actuator means 15′, 15″ (not shown in FIG. 3). In FIGS. 2a-c and FIG. 3, the wheel frame 8 is shown with an elongate beam 20 at the rear. This beam 20 may in a convenient manner support a boom sprayer optionally with an associated air blower device, as shown in WO 95/16347.
20051219
20090714
20060615
69696.0
B60D114
0
BOEHLER, ANNE MARIE M
TRAILER FOR TOWING AFTER A TOWING VEHICLE, A SYSTEM COMPRISING A TRAILER AND A TOWING VEHICLE, AND A METHOD OF STEERING A TRAILER AROUND A TURNING POINT
UNDISCOUNTED
0
ACCEPTED
B60D
2,005
10,537,436
ACCEPTED
CIRCUIT BOARD CONNECTOR
A circuit board connector includes a main body portion, a first connecting portion for connection to a first circuit board, and a second connecting portion for connection to a second circuit board. The circuit board connector is obtained by cutting a conductive plate material provided with plating layers on front and back sides thereof, and thereafter forming the second connecting portion into a shape having an annular transverse cross section in such a manner that one of the plating layers forms an outer circumferential surface of the second connecting portion.
1. A circuit board connector, comprising a main body portion, a first connecting portion for connection to a first circuit board, and a second connecting portion for connection to a second circuit board, characterized in that: the circuit board connector is obtained by cutting a conductive plate material provided with plating layers on front and back sides thereof and thereafter forming the second connecting portion into a shape having an annular transverse cross section in such a manner that one of the plating layers forms an outer circumferential surface of the second connecting portion. 2. The circuit board connector according to claim 1, characterized in that cut surfaces at both edges of the second connecting portion oppose each other. 3. The circuit board connector according to claim 2, characterized in that a gap is provided between the cut surfaces at both edges of the second connecting portion that oppose each other. 4. The circuit board connector according to claim 3, characterized in that a lead portion is provided between the main portion and the second connecting portion, and the lead portion is subjected to a bending process for reinforcement. 5. The circuit board connector according to claim 4, characterized in that the bending process is such as to form the lead portion to have an O-shaped or C-shaped transverse cross section. 6. A circuit board connector, comprising a first connecting portion for connection to a first circuit board and a second connecting portion connected to a second circuit board, characterized in that: the circuit board connector is obtained by cutting a conductive plate material provided with plating layers on front and back sides, and thereafter forming the second connecting portion so as to have an annular transverse cross section and bending the second connecting portion so that cut surfaces are located inside the annular cross-sectional shape. 7. The circuit board connector according to claim 6, characterized in that the circuit board connector comprises a lead portion between the main body portion and the second connecting portion, and the lead portion is subjected to a bending process. 8. The circuit board connector according to claim 7, characterized in that the bending process is such as to form the lead portion to have an O-shaped or C-shaped transverse cross section. 9. A method of manufacturing an electronic apparatus, characterized by comprising: mounting an electronic device furnished with a first circuit board to which the first connecting portion of the circuit board connector according to claim 1 is connected, uprightly onto a second circuit substrate arranged in the electronic apparatus. 10. A method of manufacturing an electronic apparatus, characterized by comprising: mounting an electronic device furnished with a first circuit board to which the first connecting portion of the circuit board connector according to claim 6 is connected, uprightly onto a second circuit substrate arranged in the electronic apparatus.
TECHNICAL FIELD The present invention relates to circuit board connectors for connecting two circuit boards together. BACKGROUND ART There are two types of circuit board connectors for connecting two circuit boards each other; one type is a socket housing type that can be dismantled even after product assembling and the other is a type that is fixed by soldering during product assembling. Among the latter type, which is fixed by soldering, the one as described below is known. This circuit board connector comprises, as illustrated in FIG. 13, a main body portion 2, a first connecting portion 1 for connection to a first circuit board, a second circuit board connection 4 for connection to a second circuit board, and a lead portion 3 located between the second connecting portion 4 and the main body portion 2. The main body portion 2 comprises an auxiliary connecting portion 21 formed from a portion of the main body portion 2, so that the connecting strength is improved by making connection with the first circuit board at two points, at the first connecting portion 1 and the auxiliary connecting portion 21. As illustrated in FIG. 14, when connected to a circuit board of an electronic apparatus such as a VTR, an electronic device 7 such as a tuner is arranged uprightly in order to reduce the mounting area of the circuit board. This necessitates the second connecting portion 4 to be drawn out from a narrow surface of the circuit board that is arranged, in the electronic device, parallel to a wide surface in the electronic apparatus, and therefore, the first connecting portion 1 and the auxiliary connecting portion 21 are bent when connected to a circuit board within the electronic device. The outer shape of the above-described circuit board connector is, as illustrated in FIG. 15, formed by press cutting a single sheet of conductive plate material 5 the front and back sides of which have plating layers 6 of tin, nickel, or the like that have been formed thereon in advance. Thus, the transverse cross sections of the first connecting portion 1, the second connecting portion 4, and the auxiliary connecting portion 21 are formed to be rectangular. However, cut surfaces 11 created by the press cutting are not provided with the plating layers and therefore have lower solder wettability than those in which a plating layer is formed on the entire surfaces. Moreover, there is a certain length of time until an electronic device equipped with the circuit board connector is shipped to the user and mounted onto a circuit board of an electronic apparatus. During that time, the second connecting portion of the circuit board connector is oxidized or rusted, and consequently a problem arises that solder wettability reduces. In order to solve the foregoing problem, a method has been proposed in which re-plating is carried out for the circuit board connector after the press-cutting so that a plating layer is formed on the entire surface. Re-plating the terminal, however, adds an extra manufacturing step and also increases cost. Moreover, the re-plating process usually adopts a barrel plating method, which involves putting samples to be plated into a barrel-shaped container containing a plating solution and revolving the barrel-shaped container, and in the course of this process, the terminals deform or get tangled, reducing the yield and leading to a further increase in cost. Furthermore, if a thin conductive plate material is used for cost reduction, the mechanical strength of the circuit board connector degrades, resulting in breakage during the manufacturing process and the mounting process to a circuit board, which also reduces the manufacturing yield. The present invention has been accomplished to solve such problems, and it provides a circuit board connector with which good soldering is possible even without performing a re-plating process. DISCLOSURE OF THE INVENTION A circuit board connector of the present invention comprises a main body portion, a first connecting portion for connection to a first circuit board, and a second connecting portion for connection to a second circuit board; and the circuit board connector is obtained by cutting a conductive plate material provided with plating layers on front and back sides thereof, and thereafter forming the second connecting portion so as to have an annular transverse cross section in such a manner that one of the plating layers forms an outer circumferential surface of the second connecting portion. In a circuit board connector of the present invention, cut surfaces at both edges of the second connecting portion oppose each other in addition to the foregoing configuration. Moreover, in a circuit board connector of the present invention, a gap is provided between the cut surfaces at both edges of the second connecting portion that oppose each other. In addition, a circuit board connector of the present invention is such that a circuit board connector comprising a first connecting portion for connection to a first circuit board and a second connecting portion connected to a second circuit board, wherein: the circuit board connector is obtained by cutting a conductive plate material provided with plating layers on front and back sides, and thereafter forming the second connecting portion so as to have an annular transverse cross section and bending the second connecting portion so that cut surfaces are located inside the annular cross-sectional shape. By allowing one of the plating layers of the second connecting portion to form the outer circumferential surface, solder wettability can be improved without performing an extra plating process. Moreover, by processing the second connecting portion so as to have an annular cross section, the mechanical strength of the circuit board connector can be improved, and therefore, a conductive plate material that is thinner than that in conventional products can be used; thereby, cost can be reduced. Since the cut surfaces at both edges of the second connecting portion oppose each other, the cut surfaces, which are not plated, are not present in the outer circumferential surface; thus, solder wettability can be improved. Moreover, by providing a gap between the cut surfaces at both edges of the second connecting portion, solder comes into the gap by capillary action, making it possible to improve solder wettability. By forming the second connecting portion so as to have an annular transverse cross section and bending the second connecting portion so that the cut surfaces are located inside the annular shape, the cut surfaces that are not plated are kept away from the outer circumferential surface that is to be soldered. Therefore, rusting that develops on the cut surfaces over time does not easily reach the outer circumferential surface, making it possible to conduct good soldering. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a manufacture view and a side view of a circuit board connector according to an embodiment of the present invention; FIG. 2 shows an enlarged view of a portion A in FIG. 1 and a top view thereof; FIG. 3 is a cross-sectional view taken along the line B-B in FIG. 2; FIG. 4 is a cross-sectional view taken along the line D-D in FIG. 2; FIG. 5 shows a front elevational view of a circuit board connector according to a second embodiment and a top view thereof; FIG. 6 is a cross-sectional view taken along the line B-B in FIG. 5; FIG. 7 is a cross-sectional view taken along the line D-D in FIG. 5; FIG. 8 is a cross-sectional view illustrating process steps of a second connecting portion in a third embodiment; FIG. 9 is a cross-sectional view illustrating a second connecting portion in another embodiment; FIG. 10 is a cross-sectional view illustrating the state in which the second connecting portion of the first embodiment is inserted into a connecting socket of a circuit board; FIG. 11 is a cross-sectional view illustrating the state in which the second connecting portion of a conventional product is inserted into a connecting socket of a circuit board; FIG. 12 is a transverse cross-sectional view of a second connecting portion in another embodiment of the present invention; FIG. 13 is a front elevational view and a side view of a conventional press-formed type terminal; FIG. 14 is a view illustrating an arrangement of a first circuit board arranged on a second circuit board; and FIG. 15 is a perspective view showing a conventional conductive plate material (a) before a step of press-cutting and (b) after the step of press-cutting. BEST MODE FOR CARRYING OUT THE INVENTION A circuit board connector according to the present invention comprises a main body portion 2, a first connecting portion 1 for connection to a first circuit board in an electronic device, a second circuit board connection 4 for connection to a second circuit board in an electronic apparatus, a lead portion 3 between the second connecting portion 4 and the main body portion 2, and an auxiliary connecting portion 21 formed from a part of the main body portion. The circuit board connector of the present invention is formed by cutting a conductive plate material provided with plating layers on its front and back sides, and thereafter forming the second connecting portion into a shape having an annular cross section so that one of the plating layers forms the outer circumferential surface of the second connecting portion. Herein, the term “annular shape” used in the present invention is intended to describe the shape that forms an inner hollow 16, and the outer shape is not particularly limited. Examples of annular cross-sectional shapes that may be adopted include, as illustrated in FIG. 12, a circular shape (a), an elliptical shape (b), and an elongated elliptical shape (c). The outer shape may be changed as appropriate depending on the shape of the terminal sockets of the second connecting circuit. There are no particular limitations on the plating layers used for the conductive plate material in the present invention as long as their materials have high electrical conductivity, and usable materials include gold, silver, copper, nickel, and palladium. In the following embodiments, a tin-plated conductive plate material was used. The circuit board connector according to the present invention is fabricated as follows. As illustrated in FIG. 1, the outer shape of the circuit board connector was formed by press-cutting a conductive plate material 13, which was a steel plate or the like the front and back sides of which are provided with tin plating layers, so that the interval (P) between the terminals was 4 mm. Thereafter, as illustrated in FIG. 3, the cut surfaces 11 of the second connecting portion 4 were opposed so that one of the plating layers forms the outer circumferential surface of the second connecting portion, and thus the terminal was processed to have an annular cross section. Further, as illustrated in FIG. 4, the cut surfaces 11 of the lead portion 3 were opposed and the lead portion was processed to have an O-shaped transverse cross section, and thus, a circuit board connector as shown in FIG. 2 was completed. In addition, because the second connecting portion 4 needed to be drawn out in a vertical direction from the circuit board arranged horizontally in the electronic device, the first connecting portion 1 and the auxiliary connecting portion 21 of the terminal were subjected to a bending process such as to be bent at right angles with respect to the second connecting portion. FIG. 5 is a front elevational view and a top view illustrating a second embodiment of the circuit board connector according to the present invention. The second circuit board connector was obtained as follows: the outer shape of the circuit board connector was formed using press-cutting as in the first embodiment; thereafter, as illustrated in FIG. 6, a gap was provided such that cut surfaces 11 at both edges of the second connecting portion do not come into close contact with each other and that it has a cross-sectional shape so that the plating layer forms the outer circumferential surface of the second connecting portion. Thereafter, the cut surface of the lead portion was processed into a C-shaped transverse cross section as illustrated in FIG. 7 for reinforcement, and thus a circuit board connector was completed. A circuit board connector of a third embodiment according to the present invention was obtained as follows. The outer shape was formed by press cutting a conductive plate material as in the first embodiment. Thereafter, the second connecting portion was processed as illustrated in FIG. 8 in the following manner. First, both ends of the second connecting portion near cut surfaces were bent at an acute angle, and thereafter, the second connecting portion was gradually processed through several manufacturing steps so as to have an annular cross section, so that the cut surfaces were brought inside the annular shape. Thereafter, the cut surface of the lead portion was processed into a C-shaped transverse cross section as illustrated in FIG. 7 for reinforcement, and thus a circuit board connector was completed. In the above-described embodiments of the present invention, when the circuit board connector is in use, the first connecting portion 1 and the auxiliary connecting portion 21 are fixed onto the first circuit board by soldering and the second connecting portion 4 is fixed onto the second circuit board by soldering. With the above-described configurations, the cut surfaces 11 of the conductive plate material 13 after the press-cutting are not present on the outer circumferential surface of the second connecting portion 4 of the terminal that is to be soldered, and therefore, solder wettability can be improved over conventional products. Moreover, the terminal of the second embodiment is provided with a small gap between the cut surfaces 11 at both edges of the second connecting portion 4; therefore, solder comes into the gap by capillary action, making it possible to improve solder wettability. Furthermore, the terminal of the third embodiment has the cut surfaces 11 of the second connecting portion 4 that are bent so as to come inside the annular shape, making it possible to keep the cut surfaces 11 that are not plated away from the outer circumferential surface that is to be soldered. Consequently, even when rusting develops on the cut surfaces 11 over time and corrosion due to the rusting reaches the plated surface, the rust does not easily reach the outer circumferential surface of the second connecting portion, and therefore, it is possible to conduct good soldering. To obtain this effect, it is sufficient that the cut surfaces come inside the annular shape, and for example, the same effect can be attained with a shape as illustrated in FIG. 9, in which the cut surfaces of the portion to be soldered of the second connecting portion are processed to be rounded to come inside the annular shape. As illustrated in FIG. 11, when a conventional circuit board connector in which the portion to be soldered to a circuit board is rectangular is inserted into a circular terminal connecting socket 14 of a circuit board, the gap between the portion to be soldered and the circular terminal connecting socket is not uniform, producing distant portions; therefore, the connecting strength is weak. In contrast, the second connecting portion 4 of the terminal of the present invention is shaped to have an annular cross section, as illustrated in FIG. 10; therefore, the gap 15 to the circular terminal connecting socket 14 is uniform, making it possible to improve the connecting strength. In addition, the terminal in which the second connecting portion 4 is formed to have an annular transverse cross section as in the embodiments can improve the mechanical strength of the second connecting portion over the conventional product that is not subjected to a bending process. For this reason, it is possible to use a conductive material that is thinner than that in conventional products, leading to cost reduction. Furthermore, the mechanical strength of the terminal can be further improved by applying a bending process an O-shaped or C-shaped cross section or the like to the lead portion, as in the embodiments. The embodiments used one having an auxiliary connecting portion formed from a portion of the main body portion and the first connecting portion and the auxiliary connecting portion was bending-processed at right angles with respect to the second connecting portion; however, the number and shape of the first connecting portion(s) are not limited to the foregoing and may be varied within the scope of the claims. When the first connecting portion of a terminal of the present invention as described above is used for an electronic device that is arranged uprightly, such as a tuner, it is possible to make effective use of the space on the circuit and to prevent occurrences of rusting and oxidation of the second connecting portion of the terminal. Consequently, good soldering can be conducted even when a certain time has elapsed after shipment of the electronic device until mounting of the electronic device onto an electronic apparatus. INDUSTRIAL APPLICABILITY With the circuit board connector of the present invention, good soldering is possible since a plating layer is formed on the outer circumferential surface of the second connecting portion. Moreover, it is possible to use a conductive plate material that is thinner than was conventionally possible because the mechanical strength of the second connecting portion is improved. Therefore, cost reduction can be achieved.
<SOH> BACKGROUND ART <EOH>There are two types of circuit board connectors for connecting two circuit boards each other; one type is a socket housing type that can be dismantled even after product assembling and the other is a type that is fixed by soldering during product assembling. Among the latter type, which is fixed by soldering, the one as described below is known. This circuit board connector comprises, as illustrated in FIG. 13 , a main body portion 2 , a first connecting portion 1 for connection to a first circuit board, a second circuit board connection 4 for connection to a second circuit board, and a lead portion 3 located between the second connecting portion 4 and the main body portion 2 . The main body portion 2 comprises an auxiliary connecting portion 21 formed from a portion of the main body portion 2 , so that the connecting strength is improved by making connection with the first circuit board at two points, at the first connecting portion 1 and the auxiliary connecting portion 21 . As illustrated in FIG. 14 , when connected to a circuit board of an electronic apparatus such as a VTR, an electronic device 7 such as a tuner is arranged uprightly in order to reduce the mounting area of the circuit board. This necessitates the second connecting portion 4 to be drawn out from a narrow surface of the circuit board that is arranged, in the electronic device, parallel to a wide surface in the electronic apparatus, and therefore, the first connecting portion 1 and the auxiliary connecting portion 21 are bent when connected to a circuit board within the electronic device. The outer shape of the above-described circuit board connector is, as illustrated in FIG. 15 , formed by press cutting a single sheet of conductive plate material 5 the front and back sides of which have plating layers 6 of tin, nickel, or the like that have been formed thereon in advance. Thus, the transverse cross sections of the first connecting portion 1 , the second connecting portion 4 , and the auxiliary connecting portion 21 are formed to be rectangular. However, cut surfaces 11 created by the press cutting are not provided with the plating layers and therefore have lower solder wettability than those in which a plating layer is formed on the entire surfaces. Moreover, there is a certain length of time until an electronic device equipped with the circuit board connector is shipped to the user and mounted onto a circuit board of an electronic apparatus. During that time, the second connecting portion of the circuit board connector is oxidized or rusted, and consequently a problem arises that solder wettability reduces. In order to solve the foregoing problem, a method has been proposed in which re-plating is carried out for the circuit board connector after the press-cutting so that a plating layer is formed on the entire surface. Re-plating the terminal, however, adds an extra manufacturing step and also increases cost. Moreover, the re-plating process usually adopts a barrel plating method, which involves putting samples to be plated into a barrel-shaped container containing a plating solution and revolving the barrel-shaped container, and in the course of this process, the terminals deform or get tangled, reducing the yield and leading to a further increase in cost. Furthermore, if a thin conductive plate material is used for cost reduction, the mechanical strength of the circuit board connector degrades, resulting in breakage during the manufacturing process and the mounting process to a circuit board, which also reduces the manufacturing yield. The present invention has been accomplished to solve such problems, and it provides a circuit board connector with which good soldering is possible even without performing a re-plating process.
<SOH> BRIEF DESCRIPTION OF THE DRAWINGS <EOH>FIG. 1 shows a manufacture view and a side view of a circuit board connector according to an embodiment of the present invention; FIG. 2 shows an enlarged view of a portion A in FIG. 1 and a top view thereof; FIG. 3 is a cross-sectional view taken along the line B-B in FIG. 2 ; FIG. 4 is a cross-sectional view taken along the line D-D in FIG. 2 ; FIG. 5 shows a front elevational view of a circuit board connector according to a second embodiment and a top view thereof; FIG. 6 is a cross-sectional view taken along the line B-B in FIG. 5 ; FIG. 7 is a cross-sectional view taken along the line D-D in FIG. 5 ; FIG. 8 is a cross-sectional view illustrating process steps of a second connecting portion in a third embodiment; FIG. 9 is a cross-sectional view illustrating a second connecting portion in another embodiment; FIG. 10 is a cross-sectional view illustrating the state in which the second connecting portion of the first embodiment is inserted into a connecting socket of a circuit board; FIG. 11 is a cross-sectional view illustrating the state in which the second connecting portion of a conventional product is inserted into a connecting socket of a circuit board; FIG. 12 is a transverse cross-sectional view of a second connecting portion in another embodiment of the present invention; FIG. 13 is a front elevational view and a side view of a conventional press-formed type terminal; FIG. 14 is a view illustrating an arrangement of a first circuit board arranged on a second circuit board; and FIG. 15 is a perspective view showing a conventional conductive plate material (a) before a step of press-cutting and (b) after the step of press-cutting. detailed-description description="Detailed Description" end="lead"?
20050603
20070626
20060119
57513.0
H01R400
0
NGUYEN, CHAU N
CIRCUIT BOARD CONNECTOR
UNDISCOUNTED
0
ACCEPTED
H01R
2,005
10,537,524
ACCEPTED
Oxygen supply system
A method of providing gas to a system which separates from a pressurised supply gas, product gas, includes conditioning the supply gas by both cooling and drying the supply gas.
1. A method of providing gas to a system which separates from a pressurised supply gas, product gas the method including conditioning the supply gas by both cooling and drying the gas. 2. A method according to claim 1 wherein the supply gas is cooled sufficiently to remove moisture from the supply gas by condensation. 3. A method according to claim 2 wherein a gas supply is separated into system gas, and supply gas, and the supply gas is fed to a condenser where the supply gas is cooled by a coolant and moisture is removed from the supply gas to dry the supply gas, and the system gas is passed to a cooling device where the system gas is cooled, and then the cooled system gas is used as the coolant in the condenser. 4. A method according to claim 3 wherein the cooling device is a turbine over which the system gas is expanded. 5. A method according to claim 4 wherein the gas supply is hot highly pressurised gas and energy recovered from the hot pressurised gas by the turbine is utilised by the conditioning apparatus to drive a compressor to compress and warm the system gas after the system gas has been used as a coolant in the condenser. 6. A method according to any one of the preceding claims wherein the supply gas, after drying, is further conditioned in a heat exchanger to bring the temperature of the supply gas to within an optimal operating range for the downstream separating system. 7. A method according to claim 6 wherein the further conditioning includes warming the supply gas with a warming fluid. 8. A method according to claim 7 where dependant upon claim 5 wherein the warming fluid is compressed system gas from the compressor driven by the turbine. 9. A method according to claim 6 or claim 7 or claim 8 which includes sensing the temperature of the supply gas downstream of the heat exchanger, to provide an input to a controller which opens and closes a valve in response, to control the flow of the warming fluid to the heat exchanger. 10. A method according to any one of claims 3 to 9 where dependant upon claim 3 and claim 6 which includes compressing the expanded system gas after using the expanded system gas as a coolant in the condenser, warming the supply gas after drying, in the heat exchanger with the compressed system gas, and then exhausting the system gas. 11. A method according to any one of the preceding claims wherein the method includes utilising ambient air as a coolant in a pre-cooler heat exchanger, to cool the gas supply prior to conditioning the supply gas. 12. A method of providing gas substantially as hereinbefore described with reference to the accompanying drawing. 13. In combination a system which separates from supply gas, product gas, and a conditioning apparatus to cool the supply gas for use in the separating system, the conditioning system including a condenser in which the supply gas is cooled and dried. 14. A combination according to claim 13 having any of the features of the apparatus described for use in the method of claims 1 to 12. 15. A combination a system which separates from supply gas, product gas, and a conditioning apparatus to cool the supply gas for use in the separating system. 16. An aircraft having a combination of a system which separates from supply gas, product gas, and a conditioning apparatus to cool the supply gas for use in the separating system according to claim 13 or claim 14 or claim 15. 17. Any novel feature or novel combination of features described herein and/or as shown in the accompanying drawing.
DESCRIPTION OF INVENTION This invention relates to a method of providing gas to a system which separates from a gas supply, product gas. Systems are known for separating from a pressurised gas supply, such as compressed air, product gas such as oxygen enriched gas for breathing. In one exemplary arrangement, the pressurised gas supply is hot and compressed air bled from a gas turbine engine, and the separating system includes at least one, usually a plurality of, molecular sieve beds which include molecular sieve bed material which in a first mode of operation, adsorbs from the compressed air supply, non-product gas, and in a second mode of operation when the sieve bed is opened to ambient pressures, the adsorbed non-product gas is purged from the molecular sieve bed material. Thus oxygen enriched product gas is separated out of the supply air. Such a system is known as an OBOG (on-board oxygen generating) system. OBOGS are used in aircraft to produce oxygen enriched gas for breathing purposes. For an aircraft, weight is a critical factor for any installed system. The provision of a such system which is able to provide a breathable gas avoids the need to carry large volumes of compressed breathable gas, in heavy containers. However, OBOG efficiency depends on many factors, one of which is the temperature of the air supply fed to it, and another of which is the amount of moisture in the air supply. An OBOG operates most efficiently to adsorb non-product gas, when the air supplied to it is within a certain temperature range, and because moisture in the air supply tends to be adsorbed by the molecular sieve bed material, overly wet supply air detracts from the efficiency of operation of the OBOG too. It is known in an aircraft to cool the hot compressed air supply to a relatively small extent prior to feeding the air supply to the separation system, utilising ambient air which is used as a coolant in a heat exchanger, the ambient air typically being so-called ram air which flows through the heat exchanger by virtue of the movement of the aircraft through the air, although on the ground, such coolant ambient air may be introduced by a fan. Another consideration for an aircraft, particularly a military aircraft is the temperature of exhausted non-product gas, but even for a civil aircraft the exhaustion of hot non-product gas is a waste of energy. According to one aspect of the invention we provide a method of providing gas to a system which separates from a pressurised supply gas, product gas the method including conditioning the supply gas by both cooling and drying the gas. Thus utilising the method of the invention, problems of existing systems, particularly OBOG type systems, are at least reduced in that the temperature of the supply gas fed to the OBOG(S) may be controlled to be within a temperature range at which the OBOG(S) operate(s) most efficiently, and the wet supply gas is dried. Although to condition the supply gas will involve the provision of conditioning apparatus which will contribute weight, this will be counterbalanced as a smaller, lighter gas separation system than otherwise would be required, may be provided. In one example, the method includes cooling the supply gas sufficiently to remove moisture from the supply gas by condensation. Thus the method of the invention may include separating a gas supply into system gas, and supply gas, the supply gas being fed to a condenser where the supply gas is cooled by a coolant and moisture is removed from the supply gas to dry the supply gas, and passing the system gas to a cooling device where the system gas is cooled, and then using the cooled system gas as the coolant in the condenser. The cooling device conveniently is a turbine over which the system gas is expanded. Where the gas supply is hot highly pressurised gas, such as air bled from a gas turbine engine, energy recovered from the hot pressurised gas by the turbine may be utilised by the conditioning apparatus, for example, to drive a compressor to compress and warm the system gas after the system gas has been used as a coolant in the condenser. The supply gas, after drying, may be further conditioned in a heat exchanger to bring the temperature of the supply gas to within an optimal operating range for the downstream separating system. Such further conditioning may include warming the supply gas in the heat exchanger with a warming fluid, for example with the compressed system gas from the compressor driven by the turbine, where provided. The method may include sensing the temperature of the supply gas downstream of the heat exchanger, to provide an input to a controller which opens and closes a valve to control the flow of the warming fluid to the heat exchanger, so that the temperature of the supply gas supplied to the separating system may be controlled. The method may thus include compressing the expanded system gas after using the expanded system gas as a coolant in the condenser, warming the supply gas after drying, in the heat exchanger with the compressed system gas, and then exhausting the system gas. In this way, there is a minimal wastage of energy in the gas supply and the temperature of the exhausted air need not be significantly above ambient temperature. The method of the invention may include utilising ambient air as a coolant in a pre-cooler heat exchanger, to cool the gas supply prior to conditioning the supply gas. According to a second aspect of the invention we provide in combination a system which separates from supply gas, product gas, and a conditioning apparatus to cool the supply gas for use in the separating system. The system of the second aspect of the invention may have any of the features of the apparatus described for use in the method of the first aspect of the invention. According to a third aspect of the invention we provide an aircraft having a combination of a system which separates from supply gas, product gas, and a conditioning apparatus to cool the supply gas for use in the separating system, according to the second aspect of the invention. The invention will now be described with reference to the accompanying drawing which an exemplary illustrative diagram of a combination of a system which separates from supply gas, product gas, and a conditioning apparatus to cool the supply gas for use in the separating system, operable by the method of the invention. Referring to the drawing there is shown a combination of a system 10 for separating from a supply gas, product gas, and a conditioning apparatus 12 for use in an aircraft. A pressurised gas supply 14 is provided, which in this example is hot compressed air bled from a gas turbine engine of the aircraft. This is pre-cooled in a pre-cooler heat exchanger 15 by a coolant which is ram air 16 which passes through the pre-cooler heat exchanger 15 due to the movement of the aircraft through the air and/or by the operation of a fan. The hot compressed air supply 14 is thus cooled to some extent, but generally not sufficiently for optimal use in the gas separation system 10 downstream. Thus the pre-cooled but still hot and compressed air is then divided to provide supply air along a supply duct 17, which supply air is fed to the conditioning apparatus 12, and system air which is led along a system air duct 18. The system air in duct 18 is fed to a turbine 20 over which the system air is expanded substantially to cool the system air. The cooled system air is then fed via a duct 21, to a condenser 22 where the cooled system air is used as a coolant to cool the supply air from duct 17 and thus to cause water present in the supply air, to be condensed out of the supply air, so that the supply air is dried as well as cooled. Although not shown, a downstream water separator may additionally be provided to enable condensed water to be removed from the supply air. The cooled supply air is then fed, via an optional further heat exchanger 24 to the product gas separating system 10, which in this example includes a plurality of OBOGS 25, 26 (only two of which are shown for illustrative purposes) which in use, separate from the supply air, oxygen enriched product gas for use in a downstream breathing system by crew/passengers of the aircraft. The system air which was used as a coolant in the condenser 22, is fed subsequently to a compressor 28, which for maximum efficiency is, in this example, carried on a common shaft 29 with the turbine 20, so that energy recovered from the hot compressed supply air is used to drive the compressor 28. Thus the system air is heated by being compressed before being fed into a duct 30. If after drying the supply air in the condenser 22, the temperature of the air is below the temperature range in which the OBOGS optimally operate, the temperature of the supply air may be raised in the optional further heat exchanger 24, by using the compressed and thus heated system air from duct 30 to warm the supply air. In order to ensure that the temperature of the supply air is not overly raised in the heat exchanger 24, and is raised to bring the temperature of the supply air to within the optimal temperature range for the OBOGS, a by-pass line 32 may be provided for the heated compressed system air, so that the system air or at least a proportion of it, may be exhausted to ambient at 35, without passing through the optional further heat exchanger 24. The flow of system air along the by-pass line 32 is controlled by a valve 34 which is an electrically operated valve, operated by a controller 38 in response to an input from a temperature sensor 39 which is positioned to sense the temperature of the conditioned supply air just prior to the supply air passing into the separating system 10. Thus the valve 34 may be opened and closed by the controller, and if desired proportionally, to ensure that the supply air is warmed only to a desired temperature in the optional further heat exchanger 24. Various modifications may be made without departing from the scope of the invention. For example, although the invention has been described particularly for use with an oxygen concentration system 10 for an aircraft, the invention may be used for other gas systems and in other environments to an aircraft. Thus the gas supply 14 need not be hot and compressed air, but may be an ambient air supply although in this case, energy may be required to drive the turbine 20 and compressor 28 where provided. Although it is preferred for there to be provided the further heat exchanger 24 to warm the dried air/gas as required, if desired an alternative means for warming the supply air/gas to an optimal temperature for use by the separating system 10 may be provided. For example, hot compressed gas from the gas supply 14 may be mixed with the dried supply gas, or used in a further heat exchanger to warm the supply gas instead of the compressed system air. The features disclosed in the foregoing description, or the following claims, or the accompanying drawings, expressed in their specific forms or in terms of a means for performing the disclosed function, or a method or process for attaining the disclosed result, as appropriate, may, separately, or in any combination of such features, be utilised for realising the invention in diverse forms thereof.
20051107
20090203
20060706
85337.0
B01D5300
0
HOPKINS, ROBERT A
OXYGEN SUPPLY SYSTEM
UNDISCOUNTED
0
ACCEPTED
B01D
2,005
10,537,578
ACCEPTED
Transducer and electronic device
The transducer (1) comprises an electrically conductive resonator element (20) extending in a longitudinal direction having a length (l). It can be elastically deformed by an electrically conductive actuator (30) such that the elastic deformation comprises a change of the length (dl). The resonator element (20) is electrically connected to a first contact area (25) and a second contact area (26) thereby constituting a circuit In this circuit the resonator element (20) constitutes a resistor with an ohmic resistance (R) which is a function of the length (l+dl). The transducer (1) further comprises a measurement point (28) electrically connected to the circuit for providing an electrical signal which is a function of the resistance (R).
1. An electromechanical transducer (1) for transducing an electrical input signal into an electrical output signal, the transducer comprising: a substrate (10), an electrically conductive resonator element (20) attached to the substrate (10), the resonator element (20) extending in a longitudinal direction having a length (l), an electrically conductive actuator (30) able to receive an electrical actuation potential difference with respect to the resonator element for inducing an elastic deformation of the resonator element (20), the actuation potential difference being a function of the input signal, the elastic deformation comprising a change (dl) of the length (l), the resonator element (20) comprising a resistor with an ohmic resistance which is a function of the change (dl) of the length (l), the output signal being a function of the resistance. 2. A transducer (1) as claimed in claim 1, wherein the resonator element (20) comprises a first part (201) having a first length in longitudinal direction, and a second part (202) having a second length in longitudinal direction, the elastic deformation comprising a change of the first length which is counteracted by a first elastic force (F1), and a change of the second length which is counteracted by a second elastic force (F2), the first elastic force (F1) and the second elastic force (F2) substantially compensating each other (F1+F2≈0) in a deformation-free part (203) of the resonator element (20), the resonator element (20) being attached to the substrate (10) in a support area (204) comprised in the deformation-free part (203). 3. A transducer (1) as claimed in claim 2, wherein the support area (204) comprises a first resonator contact (250) and a second resonator contact (260) that is electrically connected to the first resonator contact (250) by a conductive path comprised in the resonator element (20), the conductive path comprising a point (P) outside the deformation-free part (203). 4. A transducer (1) as claimed in claim 3, wherein the resonator element (20) has an outer end in longitudinal direction, the point (P) being at the outer end. 5. A transducer (1) as claimed in claim 3, wherein the resonator element (20) comprises a first material with a first electric conductivity constituting the conductive path, and a second material with a second electric conductivity which is smaller than the first electric conductivity, every path from the first resonator contact (250) to the second resonator contact (260) which is free from the point (P) comprising the second material. 6. A transducer (1) as claimed in claim 5, wherein the second material comprises a dielectric material. 7. A transducer (1) as claimed in claim 1, wherein the resonator element (20, 20a) is included in a Wheatstone-type electric circuit, the Wheatstone-type electric circuit comprises a first contact area (25) and a second contact area (26), the first contact area (25) being electrically connected to the second contact area (26) via a first connection and via a second connection arranged parallel to the first connection, the first connection comprising the resonator element (20, 20a) in series with a second resonator element (20b), the second connection comprising a third resonator element (20c) in series with a fourth resonator element (20d), the resonator element (20a) and the second resonator element (20b) being connected by a first electrical connector comprising a measurement point (28), and the third resonator element (20c) and the fourth resonator element (20d) being connected by a second electrical connector comprising a reference point (29), the output signal comprising an electrical potential difference between the measurement point and the reference point, the second resonator element (20b), the third resonator element (20c) and the fourth resonator element (20d) each being substantially identical to the resonator element (20a). 8. A transducer (1) as claimed in claim 7, wherein: the resonator element (20a) is situated between the first contact area (25) and the second resonator element (20b), the third resonator element (20c) is situated between the second contact area (26) and the fourth resonator element (20d), and a second electrically conductive actuator (30c) for elastically deforming the third resonator element (20c) is present. 9. A transducer (1) as claimed in claim 8, wherein: a third electrically conductive actuator (30b) for elastically deforming the second resonator element (20b) is present, and a fourth electrically conductive actuator (30d) for elastically deforming the fourth resonator element (20d) is present. 10. A transducer (1) as claimed in claim 1, wherein: the resonator element (20) comprises a first resonator element (20e) and a second resonator element (20f), the first resonator element (20e) and the second resonator element (20f) being mechanically coupled by a coupling element (16), the actuator (30) is able to induce an elastic deformation of the first resonator element (20e), and the second resonator element (20f) constitutes a resistor with an ohmic resistance which is a function of the change (dl′) of the length (l′) of the second resonator element (20f), the output signal being a function of the resistance of the second resonator element. 11. An electronic device (50) comprising: a signal processor (51) operating with a clock signal, and a transducer (1) as claimed in claim 1 for providing the clock signal.
The invention relates to an electromechanical transducer for transducing an electrical input signal into an electrical output signal, the transducer comprising a substrate, an electrically conductive resonator element attached to the substrate, the resonator element extending in a longitudinal direction having a length l, an electrically conductive actuator able to receive an electrical actuation potential difference with respect to the resonator element for elastically deforming the resonator element, the actuation potential difference being a function of the input signal, the elastic deformation comprising a change dl of the length, the resonator element being part of a circuit which is able to provide the output signal, the output signal being a function of the change dl of the length l. The invention further relates to an electronic device comprising a signal processor operating with a clock signal, and a transducer according to the invention for providing the clock signal. The article “A 12 MHz micromechanical bulk acoustic mode oscillator” by T. Mattila et al., Sensors and Actuators A, volume 101, page 1-9, 2002 discloses an electromechanical transducer. Such a transducer is able to transduce an electrical input signal into an electrical output signal. It comprises a resonator element which is a beam extending in a longitudinal direction having a length l of μm dimensions. The beam is clamped to the substrate at its central part and, except for this central part, is free to move with respect to the substrate, i.e. it can be deformed in, e.g., the longitudinal direction. The motions of the beam away from its equilibrium position are counteracted by an elastic force. This elastic force and the mass of the resonator element determine the eigenfrequency of the resonator element. The known transducer comprises an electrically conductive actuator for inducing an elastic deformation of the resonator element. The actuator has two electrodes with surfaces facing the beam at its outer ends in the longitudinal direction. The actuator can be provided with an electrical actuation potential difference with respect to the resonator element, the actuation potential difference being a function of the input signal. In the known transducer, the actuation potential difference comprises an AC component and a DC component, the AC component being the input signal. The surface of the electrodes and the outer ends of the resonant element constitute a capacitor. When an actuation potential difference is applied, they therefore exert an electrostatic force on each other leading to an elastic deformation of the beam. This elastic deformation comprises a change dl of length l. Due to this elastic deformation the distance between the electrodes and the outer ends of the beam constituting the capacitor, which is often referred to as the gap g, changes and additional charges are induced on the outer ends of the beam. The resonator element is part of a circuit in which these induced charges are measured in order to generate an electrical output signal which is a function of the change dl of length l. The amount of induced charges and thus the amplitude of the output signal depends on the size of the gap g and, therefore, on the deformation of the beam: the smaller the gap, the larger the signal. Therefore, the output signal can be used to capacitively measure the change dl of length l. Periodically changing the electrical actuation potential difference leads to a periodical deformation of the beam. When the electrical actuation potential difference is changed with a frequency that substantially matches an eigenfrequency of the beam, the beam is brought into mechanical resonance, which leads to a relatively large deformation and a correspondingly large output signal. It is a disadvantage of the known transducer that the output signal is relatively small. It is an object of the invention to provide a transducer, which is able to provide a relatively large output signal. The invention is defined by the independent claims. The dependent claims define advantageous embodiments. According to the invention the object is achieved in that the resonator element constitutes a resistor with an ohmic resistance R which is a function of the change dl of length l, the output signal being a function of resistance R. The transducer according to the invention has a circuit which comprises the resonator element constituting a resistor. The resistor has a resistance R which is a function of the elastic deformation dl. It may comprise, e.g., any type of piezoresistive material. The circuit is able to provide an output signal which is a function of the resistance R and hence, of the change dl of the length l. The output signal may be obtained, e.g., by measuring the resistance R. The resistance R may be measured by various techniques known in the art. In one embodiment the voltage drop V over the resistor is measured by monitoring the electrical potential difference between a measurement area that is electrically connected to the circuit, and a reference area. The positions of the measurement area and the reference area are not critical as long as their mutual electric potential difference is at least partly determined by the voltage drop over the resistor. In another embodiment the circuit is provided with a constant voltage and the current I through the resistor is measured. In the transducer according to the invention the resonator element can be deformed by capacitively coupling it to the actuator analogously to the known transducer. In contrast to the known transducer, the transducer according to the invention uses the piezoresistive effect for measuring the deformation. This capacitive excitation-resistive detection scheme is more sensitive than the known capacitive excitation-capacitive detection scheme, in particular for transducers with a relatively high eigenfrequency. It may be shown that the output signal of a transducer according to the invention is larger than that of the known transducer by more than a factor of 100 provided that both transducers have the same dimensions and that both are provided with the same actuation potential difference as the known transducer. When designing a transducer with a higher eigenfrequency, the resonator element has to be smaller and stiffer. In this case, the output signal of the known transducer becomes smaller because it scales linearly with the width and the height of the resonator element. In contrast to this, the relative change of the ohmic resistance dR/R and hence the output signal of the transducer according to the invention are independent of the resonator dimensions as long as the shape of the resonator element, i.e. the ratios of the length to thickness and of the length to width are maintained. This feature of the transducer according to the invention forms an important additional advantage, because it allows for manufacturing a relatively high-frequency transducer that is able to provide a relatively large signal. The transducer according to the invention further has the advantage that the output signal is less dependent on the size of the gap g: the output signal of the known transducer scales with 1/g4, whereas the output signal of the transducer according to the invention scales with 1/g2. Therefore, in the transducer according to the invention often larger gaps can be used. It should be noted that the invention is not limited to beam-shaped resonator elements as will be shown by examples discussed below. Neither is it essential that the resonator element is attached to the substrate in the central part. The only requirements for a resonator element of a transducer according to the invention are that it extends in a longitudinal direction having a length l, the elastic deformation comprises a change dl of the length l, and that the resonator element is part of a circuit in which it constitutes a resistor with an ohmic resistance R which is a function of the change dl of the length l. The invention utilizes the insight that the output signal in the resistive detection scheme is particularly large when the resonator element extends in a longitudinal direction having a length l and when the elastic deformation comprises a change of length, the ohmic resistance R being a function of the change dl of the length l. In this case the elastic deformation comprises a bulk mode of the resonator element. The ohmic resistance is in first order a linear function of the change of the length and hence of the elastic deformation. This results in a relatively large output signal. In contrast to this, the output signal is relatively small for resonator elements that are operated in a so-called flex mode. In this case, the resonator element may be attached to the substrate, e.g., at one outer end, the other outer end being free. When such a resonator element is bent, the length of the resonator is in first unchanged order and the signal is therefore relatively small. Alternatively, the resonator element may be attached to the substrate at two points, e.g., its two outer ends. In this case the length does change with the elastic deformation, but the transversal elongation x is not linearly proportional to the electrostatic force F. It can be shown that the force F is related to the transversal elongation x via F=k1·x+k3·x3 where k1 describes the bending which analogously to the single-sided clamped beam does not contribute to the change in the ohmic resistance, and k3 describes the change of the length, which does change the resistance of the resonator element. This shows that a double-clamped resonator element operated in a flex mode can be read out in the resistive detection scheme only in the nonlinear regime, i.e. the output signal scales with x3. As a consequence of the nonlinear operation, the output signal is relatively small and the energy loss is relatively high resulting in a relatively small Q factor. The Q factor is an important parameter as it determines how well-defined the eigenfrequency of the resonator element is: the larger the Q factor, i.e. the lower the energy loss, the better defined the eigenfrequency. It also determines the amplitude of the periodic deformation: the larger the Q factor, the larger the deformation. Thus, a relatively large Q factor yields a relatively large output signal at a relatively well-defined frequency. From the article “CMOS chemical microsensors based on resonant cantilever beams” by D. Lange et al., Proceedings of the SPIE conference on smart electronics and MEMS, vol. 3328, p. 233-243, 1998, it is known to exploit the piezoresistive effect for measuring the deformation due to bending of a cantilever in a chemical sensor. The cantilever of the chemical sensor is bent for inducing an elastic deformation, i.e. the elastic deformation comprises a flexural mode. In first order the length of the cantilever is not changed during bending, resulting in only a relatively small change of the resistivity and a corresponding relatively small signal. In an embodiment of the transducer the resonator element is constituted by a first part having a first length in the longitudinal direction and a second part having a second length in the longitudinal direction, the elastic deformation comprising a change of the first length which is counteracted by a first elastic force, and a change of the second length which is counteracted by a second elastic force, the first elastic force and the second elastic force substantially compensating each other in a deformation-free part of the resonator element, the resonator element being attached to the substrate in a support area comprised in the deformation-free part. In such a transducer the amount of mechanical energy flowing from the resonator element via the support area into the substrate, i.e. the energy loss, is relatively low because the resonator element is attached to the substrate in a support area which is substantially free of deformations. Therefore, this transducer has a relatively large Q factor and correspondingly a relatively large output signal at a relatively well-defined frequency. It is often advantageous if the resonator element is substantially mirror-symmetric with respect to an imaginary plane perpendicular to the longitudinal direction and comprised in the deformation-free part. In this case it is possible to use a mirror-symmetric actuator to induce a deformation such that the first elastic force and the second elastic force substantially compensate each other in the deformation-free part. It is also advantageous if the resonator element has a width in a width direction perpendicular to the longitudinal direction, the length being larger than the width. It is further advantageous if the first resonator element has a height in a height direction perpendicular to the longitudinal direction and to the width direction, the length being larger than the height. The larger the length with respect to the width and the height, the better defined is the eigenmode of the resonator element in which the first length and the second length vary while the other dimensions are unchanged. It is then relatively easy to excite the resonator element in this eigenmode without at the same time exciting other eigenmodes involving the variation of other parameters of the resonator element. In a variation of the embodiment described above, the support area comprises a first resonator contact and a second resonator contact that is electrically connected to the first resonator contact by a conductive path comprised in the resonator element, the conductive path comprising a point outside the deformation-free part. In such a transducer the resonator element constituting the resistor can be contacted conveniently because it is not necessary then to electrically contact the resonator element in an area outside the deformation-free part for obtaining a resistance that is a function of the variation of the length. This yields a relatively simple transducer. It is particularly advantageous if the resonator element has an outer end in the longitudinal direction, the point being at the outer end. In such a transducer the conductive path has a component in the longitudinal direction which is substantially equal to or even larger than the first length or the second length, respectively. Therefore, the change in the first length or the second length, respectively, leads to a relatively large change in the length of the conductive path and thus to a relatively large signal. It is advantageous if the resonator element has a further outer end in the longitudinal direction, the conductive path comprising the point and a further point that is at the further outer end, in that order. In this transducer the change in the first length and the second length leads to an even larger change in the length of the conductive path and thus to an even larger signal. In an embodiment the resonator element comprises a first material with a first electric conductivity constituting the conductive path and a second material with a second electric conductivity which is smaller than the first electric conductivity, every path from the first resonator contact to the second resonator contact which is free from the point comprising the second material. The resistance of the resonator element is due to all paths connecting the first resonator contact to the second resonator contact. The resistance of a particular path in relation to the resistances of all other paths determines how much this particular path contributes to the total resistance: a path with a relatively small resistance contributes to a relatively large extent to the total resistance, whereas a path with a relatively large resistance contributes to a relatively small extent to the total resistance. By using a second material with a relatively low conductivity, the resistances of the paths which do not comprise the point is increased resulting in a relatively small contribution to the total resistance. These paths which do not comprise the point comprise among other things those paths that are entirely enclosed in the deformation-free part and therefore do not lead to a resistance which is a function of the deformation. By using the second material, the contribution of the latter paths is reduced and the sensitivity of the transducer is increased. The lower the conductivity of the second material, the smaller the contribution of the paths which do not comprise the point outside the deformation-free part. It is therefore particularly advantageous if the second material comprises a dielectric material. Preferably, the second material comprises of a dielectric material such as, e.g., silicon dioxide or any other dielectric used in semiconductor device manufacturing. Alternatively, the second material may comprise a gaseous material or vacuum. Such materials have good isolating properties and are easy to include in the resonator element. The first material may comprise any material that has a conductivity that depends on its deformation. It may comprise all types of metals such as, e.g., copper, aluminum or tungsten. Favorable results are obtained with silicon and other semiconducting materials because these materials have a resistivity which varies relatively strongly as a function of the change of length. In another embodiment the resonator element is included in a Wheatstone type of electric circuit. This circuit electrically connects a first contact area to a second contact area via a first connection and via a second connection arranged parallel to the first connection, the first connection comprising the resonator element in series with a second resistor, the second connection comprising a third resistor in series with a fourth resistor, the resonator element and the second resistor being connected by a first electrical connector comprising the measurement area, and the third resistor and the fourth resistor being connected by a second electrical connector comprising the reference area. Such an electric device is similar to a Wheatstone bridge in which one of the four resistors comprises the resonator element. It allows for sensitively measuring the voltage drop over the resonator element. Preferably, the resistances of the four resistors are similar because then the output signal comprises a relatively small DC component and a relatively large AC component which directly measures the deformation. Ideally, the four resistances are substantially identical when the AC component of the electrical actuation potential difference is zero. It is advantageous if the Wheatstone-type electric circuit comprises the first contact area and the second contact area, the first contact area being electrically connected to the second contact area via a first connection and via a second connection arranged parallel to the first connection, the first connection comprising the resonator element in series with a second resonator element, the second connection comprising a third resonator element in series with a fourth resonator element, the resonator element and the second resonator element being connected by a first electrical connector comprising the measurement area, and the third resonator element and the fourth resonator element being connected by a second electrical connector comprising the reference area, the second resonator element, the third resonator element and the fourth resonator element each being substantially identical to the resonator element. In this embodiment the second resistor comprises a second resonator element, the third resistor comprises a third resonator element, and the fourth resistor comprises a fourth resonator element, the resonator element, the second resonator element, the third resonator element and the fourth resonator element being substantially identical. The output signal in the transducer may be subjected to drift of the resistance of any of the four resistors due to, e.g., temperature fluctuations. When all four resistors comprise substantially identical resonator elements, this part of each resistor is changed in a similar way by fluctuations and, therefore, the fluctuations of the output signal are relatively small. Preferably, the four resistors each comprise substantially identical resonator elements because then they have substantially identical resistances which fluctuate substantially in the same way. The signal difference is then substantially independent of the above mentioned fluctuations. In one embodiment the resonator element is situated between the first contact area and the second resonator element, the third resonator element is situated between the second contact area and the fourth resonator element, and a second electrically conductive actuator is present for elastically deforming the third resonator element. The second actuator is able to receive a second electrical actuation potential difference with respect to the third resonator element. Thereby the second actuator can be capacitively coupled to the third resonator analogously to the coupling between the resonator element and the actuator described above. In this embodiment the output signal is increased when the second electrical actuation potential difference and the electrical actuation potential difference have a common AC component. The deformations of the resonator element and the third resonator element are then in phase. The deformation of the resonator element modulates the potential of the measurement area, whereas the deformation of the third resonator element modulates the potential of the reference area. Because the resonator element is situated between the first contact area and the second resonator element, and the third resonator element is situated between the second contact area and the fourth resonator element, the modulations of the potential of the measurement area and of the potential of the reference area are in anti phase leading to a larger output signal. Preferably, the actuator and the second actuator are substantially identical and provided with the same actuation potential difference. In this case the output signal is increased by a factor of two. In a variation of this embodiment, a third electrically conductive actuator is present for elastically deforming the second resonator element, and a fourth electrically conductive actuator is present for elastically deforming the fourth resonator element. The third actuator and the fourth actuator are able to receive a third electrical actuation potential difference with respect to the second resonator element and a fourth electrical actuation potential difference with respect to the fourth resonator element, respectively. In this embodiment the amplitude of the output signal is increased further. Preferably, the actuator, the second actuator, the third actuator and the fourth actuator are mutually substantially identical. Preferably, the actuator and the second actuator are provided with substantially the same actuation potential difference, whereas the third actuator and the fourth actuator are provided with a further electrical actuation potential difference which is identical to the electrical actuation potential difference but phase-shifted by 90 degrees. In this case the output signal is increased by an additional factor of two. This embodiment combines a relatively high frequency with a relatively high output signal. It has the additional advantage that temperature fluctuations due to the heating of the resonator elements during operation average out. In general, a resonator element is heated during operation because it is mechanically deformed. This may change the resistance of the resonator element and lead to an uncontrolled change of the output signal. Since in this embodiment all four resonator elements are deformed in the same way, the effect of this heating is compensated and the uncontrolled change of the output signal is reduced. In one embodiment the transducer is provided with a positive feed-back loop. In operation, the electrical output signal is then locked to the eigenfrequency of the resonator element. This transducer may be used as an oscillator device able to produce an electrical signal with the eigenfrequency of the resonator element. This embodiment of the transducer is suited to replace bulk acoustic wave (BAW) generators such as quartz crystals or surface acoustic wave (SAW) generators. The transducer according to the invention used as an oscillator has the advantage that it is much smaller than the known oscillators and that it can be integrated in integrated circuits. It is particularly suitable for all applications where a small size of the device is important such as, e.g., mobile phones and wrist watches or where the oscillator is to be integrated in an integrated circuit, e.g. in a television set or a radio. In another embodiment the resonator element comprises a first resonator element and a second resonator element which is mechanically coupled to the first resonator element by a coupling element. The actuator is able to receive the actuation potential difference to elastically deforming the first resonator element. Due to the mechanical coupling, also the second resonator element is elastically deformed in operation. The second resonator element is part of the circuit which is able to provide the output signal. The output signal is a function of the change dl of the length l of the second resonator element. The second resonator element constitutes a resistor with an ohmic resistance R which is a function of the change dl of the length l of the second resonator element. The output signal is a function of the resistance R. Because the first resonator element and the second resonator element are coupled by the coupling element, this transducer has a resonance with two poles leading to a broader resonance. By coupling several resonator elements in series and detecting the elastic deformation of the last one, a rather broad resonance can be obtained. Such a transducer is suitable as a band-pass filter. It is advantageous to use the transducer according to the invention in an electronic device comprising a signal processor operating with a clock signal. The transducer is suitable for providing the clock signal and in this way it is possible to replace existing devices such as BAW and SAW generators providing the clock signal, thereby reducing the size of the oscillator and allowing for integration of the oscillator in an integrated circuit. Such an electronic device may be, e.g., a mobile or wireless telephone, a base station for a mobile telephone, a receiver for receiving electromagnetic signals comprising, e.g., a television signal or a radio signal, and a display device comprising a cathode ray tube such as, e.g. a television set or a monitor. All these electronic devices comprise a signal processor operating with a clock frequency. These and other aspects of the transducer according to the invention will be further elucidated and described with reference to the drawings, in which: FIG. 1 is a top view of an embodiment of the transducer; FIGS. 2A-2C are cross-sections of the transducer along II-II in FIG. 1 at various stages of the manufacturing process; FIG. 3 is a plot of the transmittance of the transducer according to the invention and that of the known transducer; FIG. 4 is a top view of another embodiment of the transducer; FIGS. 5A and 5B are top views of two other embodiments of the transducer; FIGS. 6A-6H are cross-sections of the transducer along VI-VI in FIGS. 5A and 5B at various stages of the manufacturing process; FIG. 7 is a schematic diagram of a further embodiment of the transducer; FIG. 8 is a schematic diagram of a yet another embodiment of the transducer; and FIG. 9 is a schematic diagram of an electronic device. The Figures are not drawn to scale. In general, identical components are denoted by identical reference numerals. The electromechanical transducer 1 shown in FIG. 1 comprises a substrate 10 which is a silicon wafer. Alternatively, substrate 10 may be a gallium arsenic wafer or it may comprise any other semiconducting, metal or dielectric material. For transducers 1 designed for operation at frequencies above 10 MHz it is advantageous to use a substrate 10 comprising a dielectric such as, e.g., glass, because this reduces the loss of electromagnetic energy dissipated in the substrate. The transducer 1 further comprises an electrically conductive resonator element 20 which extends in a longitudinal direction having a length l. It is attached to the substrate 10 via support elements 21 and 22 which are connected to anchor elements 23 and 24, respectively. The anchor elements 23 and 24 are affixed to the substrate 10 as is shown in FIG. 2C. The resonator element 20 and the support elements 21 and 22 are free from the substrate 10 except for the connection via the anchor elements 23 and 24. The transducer may be manufactured, e.g., using a technique well known in the field of micro electromechanical systems (MEMS). In short, the substrate 10 is first provided with an oxide layer 11 on top of which a silicon layer 12 is deposited, shown in FIG. 2A. The silicon layer 12 is covered by a photosensitive resist, not shown, which is patterned by, e.g., lithography. The patterned resist is then developed yielding the surface areas of the resonator element 20, the support elements 21 and 22, the anchor elements 23 and 24, and the actuator 30 shown in FIG. 1 covered by the resist while the remaining part of the surface is free from resist. The surface partly covered by the resist is then subjected to etching which selectively removes those parts of the silicon layer 12 that are not covered by the resist. The result of the etching is shown in FIG. 2B. Subsequently, the oxide layer 11 which is exposed due to the previous etching is etched in a second etching step. This etching step removes all exposed parts of oxide layer 11 and, moreover, some of the oxide adjacent to these parts. As a result of the second etching step, the central parts of silicon layer 12 in FIG. 2C are free from the substrate. They form the resonator element 20. At the same etching step also the oxide layer 11 under the support elements 21 and 22 is removed such that the resonator element 20 is attached to the substrate 10 only via the anchor elements 23 and 24. The resonator element 20 has two outer ends in the longitudinal direction. Each of the outer ends is faced by a respective electrode of the electrically conductive actuator 30. The actuator 30 is able to receive an actuation potential difference VIN with respect to the resonator element 20 for elastically deforming the resonator element 20. The actuation potential difference is a function of the input signal applied to the transducer 1. In addition to the input signal the actuation potential difference may further contain, e.g., a DC component. The elastic deformation comprises a change of the length l by an amount dl shown in FIG. 1. The resonator element 20 is part of a circuit which is able to conduct an electrical current through the resonator element 20. The resonator element 20 is electrically connected to the positive or negative pole of a DC voltage source VDC via an auxiliary resistor 27, the anchor element 24 and the support element 22. The resonator element 20 is further connected to ground via the support element 21 and the anchor element 23. Therefore, the resonator element 20 is able to conduct an electrical current I. It constitutes a resistor with an ohmic resistance R which causes a voltage drop V when the resonator element 20 conducts the electrical current I. The resonator element 20 constitutes a resistor with an ohmic resistance R which is a function of the change dl of the length l because the resonator element 20 comprises a central part 19 with open space. The resonator element 20 comprises two mutually parallel beams each of which is affixed to a support element 21 and 22, respectively. The two beams are connected with each other at the two outer ends by elements 205. The central part 19 has been created during the lithography step and the etching step described above. It prevents the current from flowing from the support element 22 to the support element 21 in a straight line. The current has to follow the conductive path formed by the resonator element 20. This conductive path extends in the longitudinal direction. The circuit is able to produce an output signal which is a function of the change dl of the length l and which is a function of the resistance R. To this end the circuit comprises a measurement point 28 which is electrically connected to the circuit. It is situated between the auxiliary resistor 27 and the anchor element 24, and in operation it produces an electrical output signal which is the electrical potential difference Vout between the measurement point 28 and the reference point 29 which is connected to ground. In an alternative embodiment, not shown, the auxiliary resistor 27 is identical to the resonator element 20. This auxiliary resistor 27 is attached to the substrate 10 via anchor elements and support elements analogous to the resonator element 20. It is provided with an actuation potential difference by an actuator similar to the actuator 30. The actuation potential difference provided by this actuator with respect to the resonator element of the auxiliary resistor 27 is substantially identical to that provided by the actuator 30 with respect to the resonator element 20, but shifted in phase by 180 degrees. In this embodiment the measurement point 28 situated between the auxiliary resistor 27 and the anchor element 24 provides an output signal that is increased by a factor of two. In another alternative embodiment, not shown, the auxiliary resistor 27 is not situated between the voltage source and the anchor element 24, but instead between the anchor element 23 and ground. In this case the measurement point 28 is situated between the auxiliary resistor 27 and the anchor element 23. In yet another embodiment, not shown either, the DC voltage source VDC and the auxiliary resistor 27 are omitted. The anchor element 24 is connected to the positive pole of a current source and the anchor element 23 is connected to the negative pole of the current source. The measurement point 28 is situated between the positive pole of the current source and the anchor element 24, and the reference point 29 is situated between the anchor element 23 and the negative pole of the current source. Also in these embodiments the output signal is a function of the change dl of the length l as will be understood by those skilled in the art. The resonator element 20 is constituted by a first part 201 having a first length in longitudinal direction and a second part 202 having a second length in longitudinal direction. In the embodiment shown in FIG. 1 the first length is equal to the second length and given by 0.5·1. In another embodiment, not shown, the first length is different from the second length. It may be, e.g. 0.25·1. In yet another embodiment, not shown either, the second part 202 is omitted. The elastic deformation comprises a change of the first length which is counteracted by a first elastic force F1 and a change of the second length which is counteracted by a second elastic force F2. Because the actuator 30 comprises two substantially identical electrodes, each one is separated from an outer end of the resonator element 20 by substantially the same gap g, the first elastic force F1 and the second elastic force F2 substantially compensating each other in the deformation-free part 203 which is situated in the middle of the resonator element 20. The resonator element 20 is attached to the substrate 10 via the support elements 21 and 22 in the support areas 204 located in the deformation-free part 203. In this way the flow of mechanical energy is limited and the Q-factor is relatively high, leading to a relatively large signal. The support area 204 has a first resonator contact 250 and a second resonator contact 260 that is electrically connected to the first resonator contact 250 by a conductive path contained in the resonator element 20. This conductive path has a point P outside the deformation free part 203 and inside element 205. The resonator element 20 has an outer end in the longitudinal direction and the point P is at the outer end. The resonator element 20 shown in FIG. 1 comprises a first material with a first electric conductivity constituting the conductive path and a second material with a second electric conductivity which is smaller than the first electric conductivity. In this embodiment the first material is silicon and the second material comprises a dielectric material which is air. The silicon may comprise crystalline silicon with a crystal orientation [110], [111] or [100]. Alternatively, the transducer 1 may be encapsulated such that the second material comprises a low-pressure gas with a pressure below 1 Pa which has the advantage that the central part 19 is substantially free from any contamination which otherwise may lead to unwanted electrical short-circuits. In another embodiment described below the second material comprises a dielectric which is solid. Because of the central part 19, every path from the first resonator contact 250 to the second resonator contact 260 which is free from the point P comprises the second material. For a resonator element 20 with a length l=360 μm, a width b=8 μm and a thickness t shown in FIG. 1 of t=2.67 μm and a height h=10 μm, the eigenfrequency of the beam is approximately 12 MHz. The output signal normalized by the input signal, i.e. the transmittance of the transducer 1 according to the invention shown in FIG. 3 is larger than that of the known transducer also shown in FIG. 3 by more than a factor of 100. Both transmittances apply to a transducer with a gap g=1 μm and a DC component of the actuation potential difference of 100 V. In the embodiment of the transducer 1 shown in FIG. 4, the resonator element 20a, which is identical to the resonator element 20 of FIG. 1, is included in a Wheatstone type of electric circuit. The Wheatstone type of electric circuit comprises the first contact area 25 and the second contact area 26. The first contact area 25 is electrically connected to the second contact area 26 via a first connection and via a second connection arranged parallel to the first connection. The first connection comprises the support elements 21a and 22a and the resonator element 20a in series with a second resistor which is constituted by a second resonator element 20b. The second connection comprises a third resistor which is constituted by a third resonator element 20c in series with a fourth resistor which is constituted by a fourth resonator element 20d. The resonator elements 20a, 20b, 20c and 20d are attached to the substrate 10 via the anchor element 27a and 27b and the respective support elements 21a, 21b, 21c and 21d, and 22a, 22b, 22c, 22d. The resonator element 20a and the second resonator element 20b are connected by a first electrical connector formed by the support elements 21a and 22b and by the anchor element 27a. The first electrical connector comprises the measurement point 28. The third resonator element 20c and the fourth resonator element 20d are connected by a second electrical connector formed by the support elements 21c and 22d and by the anchor element 27b, the second electrical connector comprises the reference point 29. The second resonator element 20b, the third resonator element 20c and the fourth resonator element 20d are each substantially identical to the resonator element 20a. Ideally, the support elements 21a, 21b, 21c and 21d are substantially identical, and the support elements 22a, 22b, 22c and 22d are substantially identical as well. The resonator element 20a is situated between the first contact area 25 and the second resonator element 20b. The third resonator element 20c is situated between the second contact area 26 and the fourth resonator element 20d. A second electrically conductive actuator 30c, which is substantially identical to the actuator 30a, is present for elastically deforming the third resonator element 20c. The actuators 30a and 30c are able to receive substantially the same actuation potential difference with respect to the resonator elements 20a and 20c for elastically deforming the resonator elements 20a and 20c, respectively. The transducer 1 further comprises a third electrically conductive actuator 30b for elastically deforming the second resonator element 20b, and a fourth electrically conductive actuator 30d for elastically deforming the fourth resonator element 20d. The third actuator 30b and the actuator 30a, and the fourth actuator 30d and the second actuator 30c are connected to by connectors 31 which are designed to induce a delay of approximately 90 degrees for an AC signal with a frequency which is substantially identical to the eigenfrequency of the resonator element 20a. In another embodiment, not shown, the third actuator 30b and the fourth actuator 30d are omitted. In yet another embodiment, not shown either, the second actuator 30c is omitted as well. In a variation of the latter embodiment, the resonator elements 20b, 20c and 20d are replaced by ohmic resistors, each of which preferably having a resistance substantially identical to the ohmic resistance R of the resonator element 20a. In another embodiment shown in FIGS. 5A and 5B the resonator element 20 is attached to the substrate 10 via support elements 21 and 22 in a direction perpendicular to the main surface of the substrate 10. In these embodiments the central part 19 of resonator element 20 is filled with a dielectric such as, e.g., silicon oxide or silicon nitride. For relatively small central parts 19 with dimensions in the order of μm or smaller, it is often difficult to create the open space 19 by etching, without either leaving behind residuals of the etching agent or, when removing the etching agent, creating a contact between the two parallel beam forming the resonator element 20. By filling the central part 19 with a dielectric during the manufacturing process described below these difficulties can be avoided. In the embodiment shown in FIG. 5A the resonator element 20 has a circular shape with a radius r and it is radially surrounded by the actuator 30 constituting a ring-shaped gap g. The actuator 30 is able to receive an electrical actuation potential difference with respect to the resonator element 20 for elastically deforming the resonator element 20 in the radial direction, i.e. in a contour mode. It should be noted that also this type of resonator element 20 extends in a longitudinal direction having a length l: the longitudinal direction may be any radial direction and the length l in this direction is identical to the radius r. The elastic deformation comprises a change of the length dl, which is identical to the change in the radius dr. Such a resonator element is particularly suited for relatively high frequencies, e.g., above 10 MHz or even above 150 MHz. It has a relatively high Q-factor which may be above 7000 or even higher. The resonator element 20 is composed of circular mutually parallel plates 18a and 18b whose outer ends are mutually electrically connected by a ring-shaped element 205. Encapsulated by the circular elements 18a and 18b, and by the ring-shaped element 205 is a circular dielectric area which constitutes the central part 19 of the resonator element 20. The upper circular plate 18a and the lower circular plate 18b are electrically connected to conductor 17a and 17b by support elements 21 and 22, respectively. In this way the resonator element 20 constitutes an ohmic resistor with a resistance R which is a function of the actual radius r+dr which corresponds to the length l+dl. In an alternative embodiment shown in FIG. 5B the resonator element 20 is radial. It is composed of rectangular, mutually parallel plates 18c and 18d whose outer ends in longitudinal direction are connected by rectangular elements 205a. The parts of the rectangular plates 18c and 18d, which are free from the rectangular elements 205a, are separated by a central part 19 which comprises silicon nitride. In contrast to the embodiment shown in FIG. 5A the central part 19 is not entirely encapsulated here. Analogous to the embodiment shown in FIG. 5A the transducer 1 further comprises conductors 17a and 17b and support elements 21 and 22 for contacting the resonator element 20 to constitute a resistor. It further comprises actuators 30 similar to those shown in FIG. 1. The transducer 1 shown in FIGS. 5A and 5B may be manufactured by the following method. The transducer 1 according to VI-VI in FIGS. 5A and 5B is shown at various stages of the manufacturing process in FIGS. 6A-6H. The substrate 10 is first covered by a dielectric layer 11 which may comprise, e.g., silicon nitride. On top of dielectric layer 11 conductor 17b is formed, e.g., by depositing a layer of polycrystalline silicon which is patterned by lithography and etching. The result of these steps is shown in FIG. 6A. Subsequently, a further dielectric layer 102 of, e.g., silicon dioxide is deposited and an opening 103a in it, shown in FIG. 6B, is created to expose a part of conductor 17b. Then, a film 104 of polycrystalline silicon is deposited to cover dielectric layer 102 thereby filling the opening 103a and creating support element 21. On top of film 104 an additional dielectric layer is deposited of which the central part 19, shown in FIG. 6C, is formed using, e.g., lithography and etching. On top of this structure a further film 106 of polycrystalline silicon is deposited, shown in FIG. 6D. In a next step the resonator element 20 and the actuators 30 are formed from layers 104 and 106 and from the central part 19 by etching away the polycrystalline silicon in all regions free of the resonator element 20 and the actuators 30, thereby defining the gap g, shown in FIG. 6E. On top of this structure, a next dielectric layer 107 comprising silicon dioxide is deposited and an opening 103b in it, shown in FIG. 6F, is formed to expose a part of layer 106 which is part of the resonator element 20. Then, an electrically conducting film of, e.g., aluminum, tungsten, copper or polycrystalline silicon is deposited to cover dielectric layer 104 thereby filling the opening 103b and creating support element 22. From this metal film conductor 17a, shown in FIG. 6G, is then formed by lithography and etching. Finally, most parts of dielectric layers 102 and 107 are etched away, yielding the transducer 1 shown in FIGS. 5A and 5B, respectively. When manufacturing the transducer 1 shown in FIG. 5B, which has a central part 19 filled with a dielectric material, it is essential that this dielectric material be different from that of dielectric layers 102 and 107 and that the latter layers can be etched selectively with respect to the dielectric material of the central part 19. For this reason the central part 19 is made of silicon nitride, whereas layers 102 and 107 comprise silicon dioxide. The transducer 1 shown schematically in FIG. 7 comprises an amplifier 40 with an input terminal 41 which is electrically connected to the measurement point 28 of a transducer according to the invention. The amplifier 40 is able to amplify the AC component of the electrical signal provided by the measurement point 29 and to provide the amplified signal to the actuator 30. The amplifier 40 is provided with a phase shifter able to shift the phase of the amplified signal such that the amplified signal at the actuator 30 is in phase with the deformation of the resonator element 20. In this embodiment, the transducer 1 is thus provided with a positive feed-back loop. In operation, the electrical output signal is therefore locked on to the eigenfrequency of the resonator element 20. This transducer 1 may be used as an oscillator device able to produce an electrical signal with the eigenfrequency of the resonator element 20. The transducer 1 shown in FIG. 7 can be used for providing an electric signal with a predetermined frequency which is equal to the eigenfrequency of the resonator element 20. Alternatively, the transducer 1 shown in FIG. 1 or FIG. 5A or 5B may be used, in which the actuator 30 is provided with an actuation potential difference from a voltage source able to generate a signal VIN with an adjustable frequency where this frequency is adjusted via a feedback circuit connected to the measurement point 28. The transducer 1 shown schematically in FIG. 8 comprises a first resonator element 20e and a second resonator element 20f. Each of the resonator elements 20e and 20f is substantially identical to and attached to the substrate 10 in the same way as the resonator element 20 shown in FIG. 1. The first resonator element 20e and the second resonator element 20f are mechanically coupled by a coupling element 16 which is attached to these two elements and free from the substrate. The actuator 30 is arranged such that it is able to induce an elastic deformation of the first resonator element 20e. When the first resonator element 20e is brought into resonance by actuator 30, it induces a resonant motion of the second resonator element 20f because of the coupling elements 16. The resonant motion of the second resonator element 20f can be detected using the resistive detection scheme described above. To this end the second resonator element 20e is part of the circuit shown in FIG. 8 which is able to provide the output signal. The output signal is a function of the change dl′ of the length l′ of the second resonator element 20f. The second resonator element 20f constitutes a resistor with an ohmic resistance R′ which is a function of the change dl′ of the length l′ of the second resonator element 20f, analogous to the transducer shown in FIG. 1. The output signal is a function of the resistance R′. Because the first resonator element 20e and the second resonator element 20f are coupled by the coupling element 16, the transducer 1 has a broader resonance with relatively steep edges. By coupling several resonator elements 20 in series and detecting the elastic deformation of the last one, a rather broad resonance can be obtained. Such a transducer is suitable as a filter. When it is provided with an electric input signal VIN as the actuation potential difference, it produces a detectable electrical output signal at the measurement point 28 only for those input signal components having a frequency that is within the resonance of the transducer 1. For providing the electrical output signal the transducer 1 comprises an auxiliary resistor 27 analogous to the transducer 1 shown in FIG. 1. The electronic device 50 shown in FIG. 9 comprises a signal processor 51 operating with a clock signal. The clock signal is provided by the transducer 1 as shown in FIG. 1. Summarizing, the transducer 1 comprises an electrically conductive resonator element 20 extending in a longitudinal direction having a length l. It can be elastically deformed by an electrically conductive actuator 30 such that the elastic deformation comprises a change of the length dl. The resonator element 20 is electrically connected to a first contact area 25 and a second contact area 26 thereby constituting a circuit. In this circuit the resonator element 20 constitutes a resistor with an ohmic resistance R that is a function of the length l+dl. The transducer 1 further comprises a measurement point 28 electrically connected to the circuit for providing an electrical signal which is a function of the resistance R. It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the appended claims. In the claims, any reference signs placed between parentheses shall not be construed as limiting the claim. The verb “comprise” and its conjugations do not exclude the presence of other elements or steps than those listed in a claim. The word “a” or “an” preceding an element does not exclude the presence of a plurality of such elements.
20050606
20080603
20060601
98785.0
G02B2608
0
CHANG, JOSEPH
TRANSDUCER AND ELECTRONIC DEVICE
UNDISCOUNTED
0
ACCEPTED
G02B
2,005
10,537,878
ACCEPTED
Activity monitoring
An activity monitor is provided that reduces the amount of power consumed during a monitoring operation.
1. An activity monitor comprising: a measurement unit including a plurality of motion sensors operable to produce respective sensor signals indicative of motion experienced thereby; and a processor operable to receive the sensor signals from the measurement unit and to process the sensor signals in accordance with a predetermined method, characterized in that the activity monitor is operable to monitor and process the sensor signals discontinuously in time. 2. An activity monitor as claimed in claim 1, wherein the measurement unit is operable to output the sensor signals discontinuously in time. 3. An activity monitor as claimed in claim 1, wherein the processor is operable to monitor the sensor signals discontinuously in time. 4. An activity monitor as claimed in claim 1, wherein the processor is operable to monitor the sensor signals in turn. 5. An activity monitor as claimed in claim 1, wherein the processor is operable to enter a monitoring mode of operation in which the processor monitors the sensor signals and to enter a standby mode of operation in which no monitoring takes place. 6. An activity monitor as claimed in claim 5, wherein the processor is operable to enter the monitoring mode and the standby mode alternately. 7. An activity monitor as claimed in claim 6, wherein respective time periods for the monitoring and standby modes are variable. 8. An activity monitor as claimed in claim 6, wherein respective time periods for the monitoring and standby modes are fixed. 9. A method of monitoring activity using a plurality of motion sensors which are operable to produce respective sensor signals indicative of motion experienced thereby, the method comprising receiving sensor signals and processing the signals in accordance with a predetermined method, characterized in that the sensor signals are monitored and processed discontinuously in time. 10. A method as claimed in claim 9, comprising alternately monitoring the sensor signals and operating in a standby mode, in which no monitoring takes place, for respective time periods. 11. A method as claimed in claim 10, wherein the respective time periods are variable. 12. A method as claimed in claim 10, wherein the respective time periods are fixed. 13. A method as claimed in claim 9, wherein the sensor signals are monitored in turn.
The present invention relates to activity monitoring, and in particular, but not exclusively to, activity monitoring of a human being. The physical activity of a human being is an important determinant of its health. The amount of daily physical activity is considered to be a central factor in the etiology, prevention and treatment of various diseases. Information about personal physical activity can assist the individual in maintaining or improving his or her functional health status and quality of life. A known system for monitoring human activity is described in the article “A Triaxial Accelerometer and Portable Data Processing Unit for the Assessment of Daily Physical Activity”, by Bouten et al., IEEE Transactions on Biomedical Engineering, Vol. 44, NO. 3, March 1997. According to the known system a triaxial accelerometer composed of three orthogonally mounted uniaxial piezoresistive accelerometers is used to measure accelerations covering the amplitude and frequency ranges of human body acceleration. An individual wears the triaxial accelerometer over a certain period of time. A data processing unit is attached to the triaxial accelerometer and programmed to determine the time integrals of the moduli of accelerometer output from the three orthogonal measurement directions. These time integrals are summed up and the output is stored in a memory that can be read out by a computer. The output of the triaxial accelerometer bears some relation to energy expenditure due to physical activity and provides as such a measure for the latter. The known system allows for measurement of human body acceleration in three directions. Using state of the art techniques in the field of integrated circuit technology the accelerometer can be built small and lightweight allowing it to be worn for several days or even longer without imposing a burden to the individual wearing it. However, the known system has the considerable drawback that continuous monitoring of the accelerometer signals results in relatively high power consumption. High power consumption means that large and expensive batteries are required for a practical period of operation of the activity monitor. It is therefore desirable to provide an activity monitor that can overcome these disadvantages. According to one aspect of the present invention, there is provided an activity monitor comprising a measurement unit including a plurality of motion sensors operable to produce respective sensor signals indicative of motion experienced thereby, and a processor operable to receive the sensor signals from the measurement unit and to process the sensor signals in accordance with a predetermined method, characterized in that the activity monitor is operable to monitor and process the sensor signals discontinuously. FIG. 1 shows a block diagram schematically showing the components of a system embodying one aspect of the present invention; FIG. 2 schematically shows the orthogonal position of three accelerometers; and FIG. 3 shows a flow diagram of the steps of a method embodying another aspect of the present invention. FIG. 1 illustrates an activity monitor 1 embodying one aspect of the present invention. The activity monitor 1 comprises a measurement unit 11, a processor 12, and a memory unit 13. The measurement unit 11 is operable to produce data signals indicative of the motion of the activity monitor 1, and to supply those data signals to the processor 12. The processor 12 is operable to process the data signals output from the measurement unit, and is able to store the data signals, or the results of the processing in the memory unit 13. Data can be transferred between the processor and the memory unit 13. The processor 12 is also able to be connected to an external hose system 2, which can be a personal computer (PC) or other appropriate systems. The external hose system 2 can be used to perform additional processing of the data held in the activity monitor 1. In use, the activity monitor 1 is attached to the object to be monitored. For purposes of illustration in the following it is assumed that the object is a human individual, although it is clearly possible to apply such an activity monitor for any object. The activity monitor is attached to the individual or object for a certain time period. The measurement unit comprises three accelerometers, which are arranged in mutually orthogonal directions. The accelerometers output data signals, which are indicative of the respective accelerations experienced by the accelerometers. The three accelerometers are arranged orthogonal to one another in a conventional manner. On an individual, these directions are formed “antero-posterior”, “medio-lateral” and “vertical”, that are denoted as x, y and z, respectively. The accelerometers comprise strips of piezo-electric material that is uni-axial and serial bimorph. The strips are fixed at one end thereof. The piezo-electric accelerometers act as damped mass-spring systems, wherein the piezo-electric strips act as spring and damper. Movements of the strips due to movement of the individual generate an electric charge leading to a measurement of a data signal. In case of human movements the frequency of the data signals lies in the range of 0.1-20 Hz. The amplitude of the data signals lies between −12 g and +12 g. These numbers are discussed in more detail in the article mentioned earlier. Suitable piezo-electric materials to measure such data signals are known to a person skilled in the art. FIG. 2 illustrates the orthogonal output of the three accelerometers of the measurement unit 11. The outputs are termed ax, ay and az respectively in accordance with the present invention, and as illustrated in FIG. 3, the activity monitor operates such that the processor remains in a standby mode (step A) for a predefined period of time then inputs the measurement unit outputs and processes those signals (step B), storing the results (step C), in the memory unit 13, before returning to the standby mode. Thus, the monitoring of the measurement unit outputs is performed in a discontinuous manner over time. In many cases the use of the activity monitor is to find out about a total activity for a human being over a longer period of time, for example 24 hours. For this purpose, human activity normally will be monitored continuously in the frequency range of 1 to 8 Hz. This requires a sample frequency of at least 16 Hz. However, as a human person seldom changes the kind of activity that is being performed every few seconds, it is not necessary to do monitoring continuously. Accordingly, reduction in monitoring time to a few seconds with a variable time interval between monitoring periods, is beneficial for the power consumption of the activity monitor. This discontinuous monitoring activity can be achieved by programming the processor unit appropriately, so that the processor goes into a standby (or sleep) mode after a few seconds of monitoring. The moment the monitoring is started up again can be dependent upon various strategies; for example, the software could detect changes in the human behaviour and adopt the switch on, switch off strategy of the activity monitor. The ratio of time monitoring to time in standby mode can also have a fixed value, or could be variable dependent upon activity levels, or required settings. Further power reduction could be achieved by switching off the monitoring unit itself, such that the accelerometers or motion sensors are only active for a discontinuous amount of time. It will be readily appreciated that the accelerometers are merely preferred motion sensors, and that any appropriate motion sensor could be used in an embodiment of the present invention and achieve the advantages of the present invention. It is emphasised that the term “comprises” or “comprising” is used in this specification to specify the presence of stated features, integers, steps or components, but does not preclude the addition of one or more further features, integers, steps or components, or groups thereof.
20050607
20101207
20060413
98760.0
G01P1300
2
SHAH, SAMIR M
ACTIVITY MONITORING
UNDISCOUNTED
0
ACCEPTED
G01P
2,005
10,537,938
ACCEPTED
Apparatus for mixing
The present invention relates to an apparatus for mixing of a chemical medium in gaseous or liquid state with a pulp suspension. The apparatus comprises a housing having a wall (2) that defines a mixing chamber (4), a first feeder (6) for feeding the pulp suspension to the mixing chamber, a rotor shift (8, 204, 300, 406, 502), that extends in the mixing chamber, a drive device for rotation of the rotor shaft, a rotor body (10, 200, 407, 504), that is connected to the rotor shaft and arranged to supply kinetic energy to the pulp suspension flow, during rotation of the rotor shaft by the rotation of the drive device, such that turbulence is produced in a turbulent flow zone (12) in the mixing chamber, a second feeder (13) for feeding of the chemical medium to the mixing chamber, and an outlet for discharging the mixture of chemical medium and pulp suspension from the mixing chamber.
1-33. (canceled) 34. Apparatus for mixing of a chemical medium in gaseous or liquid state with a pulp suspension, comprising a housing having a wall that defines a mixing chamber, a first feeder for feeding the pulp suspension to the mixing chamber, a rotor shaft that extends in the mixing chamber, a drive device for rotation of the rotor shaft, a rotor body that is connected to the rotor shaft and arranged to supply kinetic energy to the pulp suspension flow during rotation of the rotor shaft by the rotation of the drive device, such that turbulence is produced in a turbulent flow zone in the mixing chamber, a second feeder for feeding the chemical medium to the mixing chamber, an outlet for discharging the mixture of chemical medium and pulp suspension from the mixing chamber, a flow-restraining disk in the outlet from the mixing chamber with one or more flow passages arranged to temporarily increase the flow velocity of the pulp suspension when the pulp suspension passes the flow-restraining disk, the second feeder comprising a chemical distribution element integrated with the rotor body and arranged to distribute the chemical medium to within a close vicinity of said turbulent flow zone and said rotor body comprising a number of rotor pins which extend from the rotor shaft on the upstream side of the flow-restraining disk. 35. Apparatus according to claim 34, wherein said chemical distribution element comprises at least one chemical outlet situated upstream of the rotor pins. 36. Apparatus according to claim 35, wherein said chemical distribution element comprises at least one distribution pipe that extends radially from the rotor shaft, whereby the chemical outlet is arranged on the distribution pipe. 37. Apparatus according to claim 34, wherein said chemical distribution element comprises at least one chemical outlet arranged on at least one of the rotor pins. 38. Apparatus according to claim 34, wherein said chemical distribution element comprises a plurality of chemical outlets arranged on at least one of the rotor pins, whereby at least one chemical outlet is directed in the opposite flow direction of the pulp suspension along the rotor shaft and at least one chemical outlet is directed radially outward form the rotor shaft. 39. Apparatus according to claim 35, wherein said second feeder comprises a stationary cylindrical body which is coaxial with the rotor shaft, and wherein said rotor body comprises a sleeve that sealingly surrounds the cylindrical body, whereby the cylindrical body is provided with a channel for the chemical medium that communicates with the chemical distribution element. 40. Apparatus according to claim 34, wherein each rotor pin is curved forwardly from the rotor shaft or backwardly relative to the rotational direction of the rotor body. 41. Apparatus according to claim 34, wherein each rotor pin has a width as seen in the rotational direction of the rotor body that increases along at least a part of the rotor body in a direction against the rotor shaft. 42. Apparatus according to claim 34, wherein said rotor shaft is provided with an axially flow generating element. 43. Apparatus according to claim 42, wherein said axial flow-generating element comprises a number of blades which are obliquely attached relative to the rotor shaft. 44. Apparatus according to claim 42, wherein said axial flow-generating element comprises a screw thread or a band thread which extends along the rotor shaft. 45. Apparatus according to claim 34, wherein each flow passage extends obliquely from the upstream side of the disk against the center shaft of the disk. 46. Apparatus according to claim 34, wherein the disk is stationarily arranged in the housing. 47. Apparatus according to claim 46, wherein said flow-restraining disk comprises channels for distribution of the chemical medium on the downstream side of the rotor body. 48. Apparatus according to claim 46, wherein said disk comprises a number of concentric rings which are coaxial with the rotor shaft and at least one radial bar that fixates the rings relative to each other and that are attached in the wall of the housing, whereby the flow passages are defined by the rings and the bar. 49. Apparatus according to claim 34, wherein said disk is integrated with the rotor shaft. 50. Apparatus according to claim 49, wherein said rotor body comprises a number of pins that extend from the rotor shaft, whereby the disk is fixed to the pins on the downstream side of the rotor body. 51. Apparatus according to claim 50, wherein said rotor body comprises an additional number of pins that extend from the rotor shaft on the downstream side of the disk, whereby the disk is also fixed to said additional pins. 52. Apparatus according to claim 50, wherein said disk comprises a number of concentric rings which are coaxial with the rotor shaft and the rotor pins fixate the rings in relation to each other, whereby flow passages are defined by the pins and the rings. 53. apparatus according to claim 49, including spacer elements arranged between the disk and the rotor pins.
The present invention relates to an apparatus for mixing of a chemical medium in gas gaseous or liquid state with a pulp suspension. In treatment of pulp suspensions there is a need for intermixture of different mediums for treatment, for example for heating or bleaching purposes. Therefore it is desirable to disperse the medium in the pulp suspension during simultaneous conveyance of the pulp suspension through a pipe. Patent EP 664150 discloses an apparatus for this function. For heating of pulp suspensions, steam is added which condense and therewith give off its energy content to the pulp suspension. A bleaching agent is added in bleaching that shall react with the pulp suspension. In connection Lo the treatment of recovered fibre pulp printing ink is separated by flotation, which means that air shall previously be disintegrated in the pulp suspension such that the hydrophobic ink, or the printing ink, may attach to the rising air bubbles. In this connection it is desirable that the medium for treatment, e.g. air, is evenly and homogeneously distributed in the pulp suspension, preferably with tiny bubbles to achieve a large surface against the pulp suspension. In all cases it is hard, with proportionately low addition of energy, to achieve an even intermixture of the medium in the flow of material. When heating pulp suspensions by supply of steam to a pulp pipe, problems often arise with large steam bubbles that are formed on the inside of the pipe, this as a consequence of a non-disintegrated gas with small condensation surface. When these large steam bubbles rapidly implodes, condensation bangs arises that causes vibration in the pipe and in following equipment. This phenomenon limits the amount of steam that can be added to the system and thus the desired increase in temperature. It is hard to achieve a totally even temperature profile in the pulp suspension when large steam bubbles exists. In order to remedy these problems, a large amount of energy can be supplied to carefully admix the steam in the pulp suspension. Another variant is to disintegrate the steam already at the supply in the pulp suspension. In intermixing of bleaching agent in a pulp suspension, relatively large amounts of energy are used in order to provide that the bleaching agent is evenly distributed and conveyed to all the fibres in the pulp suspension. The energy requirements are controlled by which bleaching agent that shall be supplied (rate of diffusion and reaction velocity) and also by the phase of the bleaching medium (liquid or gas). The geometry at supply of the bleaching agent in vapour phase is important in order to avoid unwanted separation immediately a the intermixture. The object with the present invention is to provide an apparatus for supplying and intermixing of a chemical medium in a pulp suspension in an effective way and that at least partly eliminates the above mentioned problem. This object is achieved with an apparatus for mixing of a chemical medium in gaseous or liquid state with a pulp suspension according to the present invention. The apparatus comprises a housing having a wall that defines a mixing chamber and a first feeder for feeding the pulp suspension to the mixing chamber. Further, the apparatus comprises a rotor shaft, that extends in the mixing chamber, a drive device for rotation of the rotor shaft and a rotor body that is connected to the rotor shaft. The rotor body is arranged to supply kinetic energy to the pulp suspension flow, during rotation of the rotor shaft by the rotation of the drive device, such that turbulence is produced in a turbulent flow zone in the mixing chamber. The apparatus also comprises a second feeder for feeding of the chemical medium to the mixing chamber and an outlet for discharging the mixture of chemical medium and pulp suspension from the mixing chamber. The apparatus is characterised by that the second feeder comprises a chemical distribution element integrated with the rotor body and arranged to distribute the chemical medium to or to close vicinity to said turbulent flow zone. In that respect, in accordance with present invention, an even and effective intermixing of the chemical medium in the pulp suspension is provided. Further features and advantages according to embodiments of the apparatus according to the present invention are evident from the claims and in the following from the description. The present invention shall now be described more in detail in embodiments, with reference to the accompanying drawings, without restricting the interpretation of the invention thereto, where FIG. 1A shows an apparatus in cross-section according to an embodiment of the present invention, FIG. 1B shows a cross-section A-A of the apparatus according to FIG. 1A, FIG. 2 shows a chemical distribution element according to an embodiment, FIG. 3 shows a chemical distribution element according to an alternative embodiment, FIG. 4 shows a chemical distribution element according to yet an alternative embodiment, FIG. 5A-C illustrates different alternative embodiments of rotor pins in cross-section of the rotor shaft, FIG. 6A-D illustrates different alternative cross-sections of rotor pins, FIG. 7A-C shows schematically alternative embodiments of a rotor shaft provided with axial flow-generating elements, FIG. 8A-D shows schematically alternative embodiments of flow passages in an axial direction of a flow-restraining disk, FIG. 9A-B shows alternative located patterns of flow passages for a flow-restraining disk, FIG. 9C shows in one embodiment a flow-restraining disk in axial direction comprising concentrically rings which are coaxial with a rotor shaft, FIG. 9D shows in a cross-section an embodiment of a flow-restraining disk comprising channels for chemical distribution, FIG. 9E shows the disk according to FIG. 9D in a front view, and FIG. 10A-D illustrates alternative embodiments of flow-restraining disks integrated with the rotor shaft. In FIG. 1A-B is shown an apparatus according to an embodiment of the present invention, for a mixture of a chemical medium in gas gaseous or liquid state with a pulp suspension. The apparatus comprises a housing with a wall 2 that defines a mixing chamber 4 and a first feeder 6 for supplying of pulp suspension to the mixing chamber. Further, the apparatus comprises a rotor shaft 8, which extends in the mixing chamber 4, a drive device 9 for rotation of the rotor shaft and a rotor body 10 that is connected to the rotor shaft 8. The rotor body is arranged to supply kinetic energy to the pulp suspension flow, during rotation of the rotor shaft by the rotation of the drive device, such that turbulence is produced in a turbulent flow zone 12 in the mixing chamber. The apparatus also comprises a second feeder 13 for feeding of the chemical medium to the mixing chamber and an outlet (not shown) for discharging the mixture of chemical medium and pulp suspension from the mixing chamber 4. The second feeder 13 comprises a chemical distribution element 14 integrated with the rotor body 10 and arranged to distribute the chemical medium to or to close vicinity to said turbulent flow zone 12. Preferably, the rotor body 10 comprises a number of rotor pins 11, which extends from the rotor shaft 8. The chemical distribution element 14 comprises at least one chemical outlet 16, suitably situated up-stream of the rotor pins. As evident from FIG. 2-4, a chemical distribution element may comprise of at least one distribution pipe 100 that extends radial from the rotor shaft 102, whereby chemical outlet(s) 104 is arranged on the distribution pipe 100. As illustrated in FIG. 4, the chemical outlets 104 may be directed (which is shown by the arrows in FIG. 4) against a rotor pin 106. According to an alternative embodiment, as shown in FIGS. 2 and 3, the chemical distribution element may also comprise at least one chemical outlet 104 arranged on at least one of the rotor pins 106. In that respect, the chemical outlet can be directed (as shown by arrows in FIGS. 2 and 3) in the opposite flow direction F of the pulp suspension along the rotor shaft 102, or directed transverse to the flow direction F of the pulp suspension (not shown). As evident from FIG. 2, the chemical distribution element can comprise a plurality of chemical outlets 104 arranged on at least one of the rotor pins 106, whereby at least one chemical outlet 104′ is directed in the opposite flow direction of the pulp suspension along the rotor shaft and at least one chemical outlet 104″ is transverse the flow direction of the pulp suspension from the rotor shaft 102. The chemical outlets 104 may be designed as cylindrical apertures. Other design, e.g. spray nozzle shape, can be used in order to improve the chemical distribution and prevent the pulp suspension from penetrating upstream in the chemical outlets 104. With reference again to FIG. 1A-B, the second feeder 13 may comprise a stationary cylindrical body 18, which is coaxial with the rotor shaft 8, and that the rotor body 10 comprises a sleeve 20 that sealingly surrounds the cylindrical body 18, whereby the cylindrical body is provided with a channel for the chemical medium that communicates with the chemical distribution element 14. The second feeder 13 can suitably comprise a connection pipe 22, that extends through the wall 2 of the housing to the stationary cylindrical body 18 and that is connected to the channel therein. FIG. 5A-C illustrates that a rotor body 200 according to the present invention may comprise a number of rotor pins 202, which extends from the rotor shaft 204 in its radial direction. Each rotor pin may be curved forward from the rotor shaft (FIG. 5A) or backward (FIG. 5B) relatively to the rotational direction of the rotor body (see arrow in FIG. 5A-C), which both embodiments aims to provide a radial conveyance of the mixture. According to an alternative embodiment shown in FIG. 5C, each rotor pin may have a width b, as seen in the rotational direction of the rotor body, that increase along at least a part of the rotor body in direction against the rotor shaft 204. The embodiment according to FIG. 5C decreases the opened area and by that the axial flow velocity increases. The rotor pins 202 can be provided with varying cross-sections as illustrated in FIG. 6A-D. Each rotor pin may be designed with a circular cross-section as shown in FIG. 6A, which is simple from a manufacturing viewpoint and a cost efficient design. The rotor pins 202 may also be provided with a triangular or quadratic cross-section, according to FIG. 6B-C, which geometry creates a dead air space at rotation of the rotor shaft. According to yet an embodiment the rotor pins may be provided with a shovel-shaped cross-section according to FIG. 6D, which results in a sling-effect at rotation of the rotor shaft. In addition, as evident from FIG. 6C, each rotor pin may be designed with a helix shape, suitably with quadratic cross-section, in the axial direction of the rotor pin. Which one of the various designs of the cross-sections of the rotor pins 202 that are most preferable depends on the current flow resistance. FIG. 7A-C shows alternative embodiments of a rotor shaft 300 provided with one or more axially flow generating elements 302. As is shown in FIG. 7A, the axial flow-generating element can comprise a number of blades 304, which are obliquely attached relatively to the rotor shaft. Rotation of the rotor shaft causes an axial flow. If the elements are of various rotational orientations along the rotor shaft as shown in FIG. 7A, different directions of flow are obtained as well. In addition, the axial flow-generating element can comprise a screw thread or a band thread 306, according to alternative embodiments shown in FIG. 7B-C, which extends along the rotor shaft 300, that aims to force the fluid closest to the hub of the rotor shaft towards some direction. For the feeding, the height of the band can suitably be about 5-35 mm. According to an alternative embodiment the axial flow-generating element can comprise a relatively thin elevation of about 3-6 mm on the surface of the shaft, suitably about 3.8 to 5.9 mm. This scale of lengths is suitably when it corresponds to the characteristic size of the fibre-flocks for kraft pulp at current process conditions. Thus, this should be variable in the process. The size of the flocks can be said to be in inverse proportion to the total work that is added to the fibre suspension. Preferably, the apparatus comprises a flow-restraining disk 400 with on or more flow passages, having constant axial area, arranged to temporarily increase the flow velocity of the pulp suspension when the pulp suspension passes the flow-restraining disk. The purpose of the disk is to create a controlled fall of pressure. The energy is used for static mixing and the disk is designed for varying pressure recovery depending on desired energy level. FIG. 8A-D shows different alternative embodiments of flow passages 402 in the axial direction of a flow-restraining disk 400. The flow area A of each flow passage increases or decreases in the direction of the flow, which in particular is shown in FIG. 8A-B. FIG. 8A shows a divergent opening, i.e. that an open area enlarges in axial direction. FIG. 8B shows a converging opening, i.e. where the open area diminish in axial direction- As shown in FIG. 8C-D, each flow passage can extend obliquely from the up-stream side of the disk against the centre axis C of the disk. The flow-restraining disk 400 is preferably provided with a plurality of flow passages 402 as shown in FIG. 9A-C, which passages can be arranged according to a number of alternative placement patterns, radially spread out on the flow-restraining disk. The disk is preferably circular or coaxial with the rotor shaft. The flow passages of the flow-restraining disk may for example form a Cartesian pattern (FIG. 9A) which provides asymmetrical jet streams, or a polar pattern (FIG. 9B). FIG. 9C shows an alternative embodiment where the flow passages 402 of the flow-restraining disk 400 in axial direction are formed of concentrically rings 404 that are coaxial with a rotor shaft 406, and its rotor body 407, which may comprise one or more rotor pins 408, arranged on distance from and ahead of disk 400. The flow-restraining disk is suitably stationary arranged in the housing and the disk may comprise a number of concentrically rings 404, which are coaxial with the rotor shaft 406, and at least one radial bar 410, that fixates the rings 404 relatively each other and that are attached in the wall of the housing, whereby the flow passages 402 are defined by the rings and the bar. According to an embodiment shown in FIG. 9D and 9E, the flow-restraining disk 400 may also comprise channels 412 for distribution of the chemical medium on the down-stream side of the rotor body, directed in the opposite flow direction F of the pulp suspension. Suitably is chemical supply 413 to the channels 412 provided via a radial extending connection pipe 414 in the disk. However, a flow-restraining disk 500 can be integrated with the rotor shaft 502. FIG. 10A-D illustrates alternative embodiments of flow-restraining disks 500 integrated with the rotor shaft 502. The rotor body 504 may suitably comprise a number of rotor pins 506, which extends from the rotor shaft 502, whereby the disk is fixed to the rotor pins 506 on the down-stream side of the rotor body as shown in FIG. 10A, or on its up-stream side as shown in FIG. 10B. As shown in FIG. 10C, the rotor body may comprise an additional number of pins 506′, that extends from the rotor shaft on the down-stream side of the disk, whereby the disk 500 also is fixed to said additional pins 506′. Preferably, the disk comprise a number of concentrically rings 508, which are coaxial with the rotor shaft, and the rotor pins 506, 506 ′ fixates the rings 508 in relation to each other, whereby flow passages 510 are defined by the pins and the rings. FIG. 10D shows rotor pins 506 and concentrically rings 500. Further, spacer elements 511 are arranged between the rotor pins 506 and the concentrically rings 500. The spacer elements are used in order to move the turbulent zone.
20051027
20080610
20060622
71982.0
B01F704
0
COOLEY, CHARLES E
APPARATUS FOR MIXING CHEMICALS HAVING A ROTOR BODY WITH PINS
UNDISCOUNTED
0
ACCEPTED
B01F
2,005
10,537,961
ACCEPTED
Side brush
A side brush for mounting on a body of a sweeping machine for use as a brush rotatable about a rotation axis. A plurality of individual bristle segments are detachably mountable to a base. Bristles included in the bristle segments are integrated for a solid unit with a frame member. The base includes a substantially planar disc assembly that is integrally provided with a coupling system for coupling the bristle segments therewith. The coupling system includes elongated channels disposed in the base in a substantially radial direction and extending through the base. The channels open all the way to the edge of the base and enable coupling the bristle segments immovably to the engagement with body of a sweeping machine with the base with fasteners interconnecting the same.
1. A side brush, which is adapted to be mounted on a body of a sweeping machine, for use as a brush rotatable about a rotation axis, and which comprises a base element and a plurality of individual bristle segments detachably mountable thereto, having bristles included therein integrated for a solid unit with a frame member joining the same, and the base element comprising a substantially planar disc assembly which is provided integrally with a coupling system for coupling the bristle segments therewith on a snap fit principle, wherein the coupling system is implemented by means of elongated channels disposed in the base element in a substantially radial direction and extending through the base element, opening all the way to the edge thereof, which enable coupling the bristle segments immovably to the engagement with the body of a sweeping machine by means of the base element with fasteners interconnecting the same. 2. The side brush as according to claim 1, wherein the bristle segments are adapted to be immovably stationary in a plane of the base element by means of interlocking snap fit arrangements between the frame members thereof and the base element, the channels present in the base element being provided with a necking formed in a radial direction at the base element's outer edge, whereby the bristle segment to be mounted on the base element firstly in a lateral direction by way of an open end of the channel and secondly from above, is clampable through the intermediary of a mating surface arrangement present in its frame member whose length is most preferably at least equal to that of the channel. 3. The side brush according to claim 1, wherein the substantially elongated and rectilinear bristle segment has its frame member composed of a fusion produced from the ends of the bristles. 4. The side brush according to claim 1, wherein the substantially elongated and rectilinear bristle segment has its frame member made of molded plastics, in which the bristle segment's bristles are anchored by one end thereof during its solidification process. 5. The side brush according to claim 1, wherein the substantially elongated and rectilinear bristle segment has its frame member manufactured from a chemically solidifying two-component material. 6. The side brush according to claim 1, wherein the side brush has its base element manufactured from a substantially rigid-structured plastic, metal, ceramic, and/or composite material. 7. The side brush according to claim 1, wherein the bristle segment has its bristles arranged at an angle relative to the frame member, deviating substantially from a perpendicular direction. 8. The side brush according to claim 1, wherein one or more bristle segments of the side brush are provided with bristles manufactured from a plastic-based material. 9. The side brush according to claim 8, wherein the bristle segment has its bristles composed of at least two types of plastic bristles cross-sectionally substantially different from each other. 10. The side brush according to claim 1, wherein one or more bristle segments of the side brush are provided with bristles manufactured from a metal material. 11. The brush ring according to claim 1, wherein coupling system effects attachment of the bristle segments in a screw clamping. 12. The side brush according to claim 5, wherein the two-component material comprises polyprourethane or epoxy. 13. The side brush according to claim 8, wherein the plastic-based material comprises polypropylene or polyamide. 14. The side brush according to claim 10, wherein the bristles are manufactured from steel.
The invention relates to a side brush, which is adapted to be mounted on the body of a sweeping machine, for use as a brush rotatable about a rotation axis, and which comprises a base element and a plurality of individual bristle segments detachably mountable thereto, having bristles included therein integrated for a solid unit with a frame member joining the same. The base element comprises a substantially planar disc assembly which is provided integrally with a coupling system for coupling the bristle segments therewith on a snap fit principle. Side brushes of the above type have been traditionally constructed by means of a base element, made for example from a flat plywood panel and having a radially sufficiently wide zone in its outer periphery extending from the center of the base element and provided with pairs of holes in an inclined position. Providing this type of side brush with bristles is effected by threading the bristles in one hole and out of the other, which is followed by clamping the bristles in place for example with a plywood or metal plate fastened to the back of the base element. A downside in this type of solution is particularly the inconvenience of its manufacture, since, first of all, a multitude of paired holes must be drilled in the base element, whereafter the bristles threaded therein must be further clamped in position by means of a back cover. Another notable drawback is that a side brush of the above type is a disposable item, because dismounting bristles from a base element is not economically viable but, instead, replacing the entire side brush with a new one is more convenient. On the other hand, the implementation of a so-called cassette principle in the above-mentioned context is presently known. This type of side brush solutions include a base element, which is fabricated e.g. of a rather thin metal sheet by form-bending, such that it is provided with a coupling system in a position inclined relative to the mounting plane of a side brush, which enables a detachable anchoring thereto of bristle segments manufactured in a prefabrication stage. The bristle segments used in this instance are currently manufactured in such a way that the bristles are bound together at one end thereof e.g. by a form-bendable base element of sheet metal, which is slippable in slots functioning as a coupling system. One optional solution in this respect is e.g. such that the base element is provided with holes through which the bristles are threaded, whereafter the base element's back face is fitted with an appropriate clamping plate for securing the bristles in place. Another alternative solution is described in U.S. Pat. No. 3,678,530, wherein the frame member holding each bristle segment together is constituted by a three-component frame structure, which is then secured to the base element of a side brush. This type of solutions, based on a so-called cassette principle, are not currently very functional either, firstly due to the fact that the fabrication of bristle segments is laborious and expensive because, first of all, the positioning of bristles in place requires an unacceptable amount of manual labour, in addition to which the bristles must, on the other hand, be manufactured with a quite high dimensional precision in order to fit the same in a respective coupling system by applying a force as little as possible. In practice, however, this causes all sorts of problems in an installation process because of rather large manufacturing tolerances existing in this type of construction for natural reasons. On the other hand, solutions of the above type do not enable recycling or the reuse of bristle segments included therein without unacceptably laborious/expensive dismounting operations, which is why it is generally necessary to ultimately discard such material to a waste disposal site. In addition, as a result of metal constructions used in association with arrangements of the above type, the base structures of bristle segments become unacceptably massive, wherefor the coupling and bracing systems included in a sweeping machine must also be of a highly robust design. Another solution has been disclosed in U.S. Pat. No. 4,236,269, wherein the base element of a vertical axis brush comprises a flat plate structure, which is integrally provided with a coupling system for attaching bristle segments thereto in a snap fit fashion. In this instance, the coupling system consists of clamps formed in the base element, between which the U-shaped bristle segments are attachable. A problem with this type of solution lies particularly in the fact that there is no way of providing a sufficiently reliable clamping for the bristle segments, since no actual locking can be implemented in this discussed solution. For this reason, the positions of bristle segments are also somewhat unstable in the vertical axis brush, firstly as a result of manufacturing tolerances in the bristle segments' U-shape and secondly because the clamps included in the plate or disc are subject to bending in extended use. This aspect in itself is of major importance in terms of holding a vertical axis brush together. Thus, in practice, it is not possible to assemble a sufficiently reliable side brush with the discussed type of solution. It is an object of a side brush according to the present invention to provide a decisive improvement regarding the above-discussed problems and thus to raise substantially the existing state of the art. In order to accomplish this object, a side brush of the invention is principally characterized in that the coupling system is implemented by means of elongated channels disposed in the base element in a substantially radial direction and extending through the base element, opening all the way to the edge thereof, which enable coupling the bristle segments immovably to the engagement with the body of a sweeping machine by means of the base element with fasteners interconnecting the same, such as by effecting the attachment in a screw clamping or suchlike fashion. Among the most important benefits gained by a side brush of the invention should be mentioned the simplicity and efficiency of its manufacture and construction, by virtue of which there is provided an extremely simple manufacturing process and an extremely user friendly installation and replacement of side brushes. In a preferred embodiment, the inventive side brush is provided with bristle segments whose frame members are manufactured from plastics in which the bristles of a bristle segment are secured at one end thereof in a totally fixed manner. In this respect, it is further possible to manufacture the frame members of bristle segments in a first aspect from a fusion produced from the ends of the bristles. Another possibility is naturally to manufacture the frame members from moulded plastics, in which the bristles of a bristle segment are anchored by one end thereof during its solidification, or else from e.g. a chemically solidifying two-component material, such as polyurethane, epoxy or the like. By virtue of the invention, it is thus possible to manufacture an entirely plastic-structured side brush, which in this context is further modifiable by compiling the bristle formations of its bristle segments for example from plastic bristles of thicknesses substantially different from each other, which are capable of replacing steel bristles used in traditional solutions. By virtue of the foregoing, the inherently reusable and, on the other hand and if necessary, also recyclable base element, being preferably a totally planar and substantially uniform thickness plate or disc assembly, further minimizes space demand with regard to a sweeping machine, as well as ensures a reliable operation of the side brush during rotation for a total elimination of rotational asymmetry, which is characteristic of traditional solutions. Another essential benefit gained by a side brush of the invention relates to its applicability in connection with presently available sweeping machines without any necessary modifications. Preferred embodiments for a side brush of the invention are disclosed in the dependent claims directed thereto. The invention will be described in detail in the following specification with reference to the accompanying drawings, in which: FIG. 1 shows in a perspective view of principle one preferred side brush of the invention, having bristle segments attached thereto, FIGS. 2a, 2b and 2c show one side brush of the invention in a cross-section along its center line (FIG. 2a) and a bristle segment included therein, in a plan view (FIG. 2b) and in a front view (FIG. 2c), FIG. 3 shows in a plan view one preferred base element included in a side brush of the invention, FIGS. 4a, 4b and 4c show one side brush embodiment which is alternative to that shown in FIGS. 1-3, especially with regard to a coupling system, in a halfway cross-section of the base element at its intact portion (FIG. 4a), in a halfway cross-section of the base element at a channel fitted with a bristle segment (FIG. 4b), and in a detail visualizing the base element in a plan view, one of the channels being fitted with a bristle segment, FIG. 5 shows in a plan view a base element included in the side brush shown in FIGS. 4a-4c, FIGS. 6a and 6b show one further alternative side brush embodiment, especially with regard to a coupling system, in a halfway cross-sectional view of the base element at its intact portion, and at a channel included in the base element and fitted with a bristle segment, FIG. 7 shows in a plan view a base element used in the embodiment of FIGS. 6a and 6b, and FIGS. 8a and 8b show, in an overhead view and a front view, respectively, a bristle segment useful in connection with base elements of the type shown especially in FIGS. 5 and 7. The invention relates to a side brush, which is adapted to be mounted on the body of a sweeping machine, for use as a brush rotatable w about a rotation axis y, and which comprises a base element 1 and a plurality of individual bristle segments 2 detachably mountable thereto, having bristles 2a′ included therein integrated for a solid unit with a frame member 2a″ joining the same. The base element 1 comprises a substantially planar disc assembly which is provided integrally with a coupling system for coupling the bristle segments 2 therewith on a snap fit principle. The coupling system is implemented by means of elongated channels U disposed in the base element 1 in a substantially radial direction R and extending through the base element, opening all the way to the edge thereof, which enable coupling the bristle segments 2 immovably to the engagement with the body of a sweeping machine by means of the base element 1 with fasteners 3 interconnecting the same, such as in a screw clamping or suchlike fashion. In reference especially to what is shown in FIG. 1, it is possible to use a side brush of the above type e.g. in such a way that screws 3; 3b, fitted in threaded holes 3; 3a present in the base element 1 on the body of a sweeping machine or, if necessary, in a separate mounting plate K, are unscrewed such that the base element 1 is able to descend downwards, whereafter the bristle segments 2 are removable one at a time from the channels U, after which, following the installation of new bristle segments, the base element 1 is still attachable by means of the screws 3b in its position, such that the back faces of the bristle segments' frame members 2a″ settle against the body of a sweeping machine/the mounting plate K. In a preferred embodiment, in reference especially to FIGS. 2a, 2b, 2c and 3, the bristle segments 2 are adapted to be immovably stationary in a plane x of the base element 1 by means of interlocking snap fit arrangements between the frame members 2a″ thereof and the base element 1, the channels U present in the base element 1 being provided with a necking U1 formed in a radial direction at the base element's 1 outer edge, whereby the bristle segment 2 to be mounted on the base element 1 firstly in a lateral direction by way of an open end of the channel U and secondly from above, is clampable through the intermediary of a mating surface arrangement V present in its frame member 2a″ whose length L is most preferably at least equal to that of the channel U. As a solution alternative to the foregoing, FIGS. 4a-4c and 5 illustrate an embodiment different from that described above, especially with regard to a coupling system, in the sense that, as shown in FIG. 4a, the base element 1 has its top surface provided with a recess arrangement SY for a mounting flange k1 set in the bristle segment's 2 frame member 2a″, said arrangement extending preferably in a continuous manner along the base element's 1 periphery, as shown in FIGS. 4c and 5. In this type of embodiment, the bristle segments 2 can be simply descended into position in each channel U at the above-mentioned recess arrangement SY in such a way that the mounting flanges k1 for said segments' frame members have their ends set against an end flange PL present at the base element's 1 outer edge and constituted by the recess arrangement. Thereafter the side brush is attachable in threaded holes present in the body of a sweeping machine or in a separate mounting plate K, as shown e.g. in FIG. 4b, or by means of other such arrangements. In a further solution alternative to those described above, FIGS. 6a, 6b and 7 illustrate a side brush embodiment different from those mentioned above, especially with regard to a coupling system, which is based on fastening the bristle segments 2, as depicted in FIG. 6b, by bracing the mounting flange k1 present in the segment's frame member 2a″ against the sides of the channel U present in the base element 1, whereafter the side brush is attachable in threaded holes present in the body of a sweeping machine or, as shown in FIG. 7b, in the separate mounting plate K, being supported by a radially directed retaining tab RT included therein. FIGS. 8a and 8b illustrate in a plan view and in a front view, respectively, a preferred bristle segment 2 useful especially in the base element of a side brush shown in FIGS. 5 or 7. In yet another preferred embodiment, the substantially elongated and rectilinear bristle segment 2 has its frame member 2a″ composed of a fusion produced from the ends of the bristles 2a′. In a further preferred alternative to the foregoing, the bristle segment 2 has its frame member 2a″ made of moulded plastics, in which the bristle segment's bristles 2a′ are anchored by one end thereof during its solidification process. In a further preferred embodiment alternative to the foregoing, the bristle segment 2 has its frame member 2a″ manufactured from a chemically solidifying two-component material, such as polyprourethane, epoxy or the like. On the other hand, the side brush has its base element 1, as shown e.g. in FIGS. 3, 5 or 7, manufactured from a substantially rigid-structured plastic, metal, ceramic, composite material and/or the like. In further reference to preferred embodiments as shown especially in FIGS. 1, 2a, 4b or 6b, the bristle segment 2 has its bristles 2a′ arranged at an angle a relative to the frame member 2a″, deviating substantially from a perpendicular direction. In a further preferred embodiment, one or more bristle segments 2 of the side brush are provided with bristles 2a′ manufactured from a plastic-based material, such as polypropylene, polyamide or the like. In further reference especially to what is shown in FIGS. 2a and 2c, the bristle segment 2 has its bristles 2a′ in zones I and II composed of at least two types of plastic bristles cross-sectionally substantially different from each other, which makes it especially possible to improve rigidity of the bristle segments' 2 bristles without using traditional steel bristles. Thus, it is possible to place plastic bristles of different thicknesses as shown for example in FIG. 2a, such that the stronger bristles are located at the outer end of a bristle segment, as viewed in a radial direction R, or else, as shown in FIG. 2c, such that the stronger bristles are located on the opposite sides of a bristle segment. On the other hand, in a solution alternative or complementary to the foregoing, it is possible to provide one or more bristle segments 2 of the side brush with bristles manufactured, as mentioned above, from a metal material, such as steel. It is obvious that the invention is not limited to the embodiments illustrated or described above, but it can be modified according to varying demands and operating conditions without departing from the basic inventive concept. Hence, it should be appreciated in the first place that the configuration of a base element may differ from what is described above, depending on its currently applied coupling with the brush body of a sweeping machine. Secondly, its dimensions and appearance are naturally subject to variations, depending on the dimensions of each manufactured cassette brush and a material used therefor. On the other hand, it is naturally also possible to provide the side brush with a brush pattern extending along the periphery of the side brush in a more discontinuous way than what is shown in the figures. Naturally, it is also clear that the coupling system may consist of mating surfaces with a wide variety of cross-sections, contours, and functions for achieving the locking of bristle segments to a base element.
20050609
20070417
20060601
91773.0
A46B708
0
REDDING, DAVID A
SIDE BRUSH
SMALL
0
ACCEPTED
A46B
2,005
10,538,024
ACCEPTED
Hydrophilic polyolefin materials and method of producing same
The invention relates to polyolefin materials, in particular fibers, and/or filaments, and/or nonwovens, and/or nonwoven products made from at least one polyolefin and a melt additive containing a fatty acid ester, wherein a subsequent activation of the fatty acid ester contained in the melt additive occurs on the surface of the polyolefin materials by applying a formulation, which contains a silicone compound and a quaternary ammonium compound.
1. Hydrophilic polyolefin materials, made from a mixture of at least one polyolefin and at least one melt additive containing a fatty acid ester of the general formula R—CO—O—CH2—CH2—O—R′, where R is a straight-chain or branched-chain alkyl residue with 23 to 35 carbon atoms, and where R′═H, —CH3, —C2H5, —C3H7, —C4H9, wherein the polyolefin materials include a subsequent activation of the fatty acid ester contained in the melt additive on the surface of the polyolefin material by applying a surface active substance in the form of a formulation which contains a silicone compound and a quaternary ammonium compound. 2. Polyolefin material of claim 1, wherein the silicon compound is cationically modified. 3. Polyolefin material of claim 1, wherein the quaternary ammonium compound is a quaternized ester of fatty acids and triethanol amine. 4. Polyolefin material of claim 1, wherein the formulation for the subsequent activation of the used fatty acid ester on a fiber surface is an aqueous preparation. 5. Polyolefin material of claim 1, wherein the formulation for the subsequent activation of the used fatty acid ester on a fiber surface is set on the surface physically. 6. Polyolefin material of claim 1, which contains 0.01 to 0.5% by weight, of the formulation for activating the used fatty acid ester on a fiber surface. 7. Fibers produced from a polyolefin material of claim 1. 8. Filaments produced from a polyolefin material of claim 1. 9. A nonwoven produced from a polyolefin material of claim 1. 10. (canceled) 11. The nonwoven claim 9, wherein it has repeated strike-through time measurements according to the EDANA test method ERT 154.0.00 of smaller than 5 seconds. 12. The nonwoven of claim 9, characterized in wherein it has in the determination of a repeated runoff according to the EDANA test method ERT 152.0-99, a repeated runoff of less than 25% by weight of the test fluid based on an applied quantity of fluid. 13. A nonwoven product containing a nonwoven of claim 9. 14. Method of producing hydrophilic polyolefin materials which consist of at least one polyolefin and a melt additive containing a fatty acid ester, wherein the polyolefin materials include a subsequent activation of the fatty acid ester contained in the melt additive on the fiber surface by applying a surface-active substance in the form of a formulation, which contains a silicone compound and a quaternary ammonium compound.
The present invention relates to hydrophilic polyolefin materials, in particular fibers and/or filaments, and/or nonwovens, and/or nonwoven products produced from a mixture of at least one polyolefin and at least one melt additive containing a fatty acid ester, with the polyolefin materials including a subsequent activation of the fatty acid ester contained in the melt additive on the surface of the polyolefin materials. Polyolefins, in particular polyethylene, polypropylene, as well as their copolymers have become established as materials for the production of nonwovens. Typical applications, in which nonwovens of polyolefins are used, include hygiene products (baby and female hygiene, incontinence products), as well as filter materials. When nonwovens are used, for example as top sheet in baby diapers, they will have to be permeable to body fluids, such as, for example, urine. Then, because of the distinctly hydrophobic character of the polyolefins, a hydrophilic treatment will be needed, which occurs preferably later in the form of a so-called topical treatment. In this process, it is common to use aqueous liquors, which contain amphiphilic surface-active substances, preferably cationic (quaternary ammonium salts), anionic (sulfates, phosphates), or nonionic (ethoxylates, esters, alcohols, silicones) components, or formulations from these substances. U.S. Pat. No. 6,008,145 discloses a formulation for the permanent hydrophilation of polyolefin fibers, polyolefin filaments, and textiles made therefrom with the use of quaternary ammonium compounds. According to U.S. Pat. No. 963,929 and DE 196 45 380, nonionic surfactants are used in combination with cationically modified polydimethyl siloxane. U.S. Pat. No. 6,028,016 discloses a formulation and a method for making nonwovens permanently wettable, with the formulation including a viscosity modifier for a purposeful adjustment of the viscosity of normally unusable, surface-active substances, in that an alkylated polyglycoside is used in combination with surface-active substances, for example, mixtures of modified castor oil and sorbitan monooleate. A further method of hydrophiling polyolefin fibers or polyester fibers is described in DE 198 51 688, which discloses a mixture of polyolefin or polyester, as well as a compound that includes at least one substance from the class of ethoxylated sugar esters. U.S. Pat. No. 6,211,101 discloses durable hydrophilic fibers and nonwovens made therefrom, which are intended for use preferably in medical and hygiene applications, and wherein the fiber treating agent contains an ampho-ionic surface-active betain and a dicarboxylic acid ester produced from high-molecular hydroxy-fatty acid esters. In practice, however, it is found that the topical treatment of nonwovens is connected with the following disadvantages: 1. In use, the surface-active substances are washed out by urine and other body fluids, whereby the hydrophilic properties are successively lost. 2. The washed-out surface-active substances interfere with absorption and fluid distributing processes in hygiene products. 3. The distribution of the surface-active substances on the nonwoven often proceeds only irregularly. To improve processability of polyolefins, one often uses so-called process auxiliaries as melt additive. In this connection, one uses as “external lubricants,” for example, fatty-acid derivatives which are provided with polar groups. (Ullannn's Encyclopedia of Industrial Chemistry, VCH Weinheim, 5th Ed., Vol. A20, p. 479.) However, until now such melt additives have not been widely used for a purposeful hydrophilation of polyolefin nonwovens. Because of phase incompatibility, hydrophilic residues migrate to the fiber surface. The migration in the semicrystalline fiber occurs not only in the course of the spinning process, but also after the spinning process. For the use of hydrophilic melt additives, U.S. Pat. No. 5,439,734 discloses nonwovens with a durable wettability, consisting of a polyolefin with hydrophilic additives, which comprise fatty acids esterified with dihydroxylated polyethylene glycols. Furthermore, U.S. Pat. No. 5,969,026 discloses wettable fibers and filaments consisting of polymers and incorporated wetting reagents, wherein the polymers are selected from the class of polyolefins, polyesters, and polyamides, and wherein the active substances essentially consist of a glyceride. U.S. Pat. No. 5,240,985, U.S. Pat. No. 5,272,196, U.S. Pat. No. 5,281,438, U.S. Pat. No. 5,328,951, and U.S. Pat. No. 5,464,691 disclose amphiphilic additives for modifying polyolefins, with the amphiphilic compounds consisting of an A-B-A combination of a central hydrophilic group, for example, polyethylene glycol, linked to two side groups, which are selected from the class of fatty acids or long-chain alcohols. Also known are from U.S. Pat. No. 5,696,191 and U.S. Pat. No. 5,641,822 surface-migrating, extrudable thermoplastic mixtures, consisting of at least one polyolefin and an additive, with the additive being a polysiloxane graft copolymer with polyalkene oxide side chains. By extruding the mixture, it is possible to produce wettable nonwovens, which continue to have the corresponding properties even after two years. Likewise known are from US 2002/0019184 polymers with improved hydrophilicity, which are produced by adding a corresponding quantity of an additive consisting of fatty acids esterified with polyethylene glycols. US 2001/0008965 discloses multicomponent fibers, wherein a first component consists of a hydrophobic polypropylene, and a second component of a blend of a hydrophobic polyolefin and a hydrophilic melt additive, with the second component being disposed at the surface of the fibers. WO 98/42767 A1, WO 98/42776 A1, and WO 98/42898 A1 disclose a process of making a polyolefin blend with improved compatibility to adhesives and/or coatings. The blend consists of a polyolefin, a migrating amphiphile and a transition metal. US 2002/0002242 A1 and WO 01/58987 A2 describe a possibility of increasing the surface energy of polymeric substrates by the use of new amphiphilic block copolymers, in that the block copolymers consisting of linear hydrophobic polymers or oligomers and a statistically hyperbranched polymer or oligomer, are treated in full or in part with lipophilic end groups. U.S. Pat. No. 5,582,904 describes a method and a resultant end product, wherein hydrophobic polyolefin nonwovens are imparted hydrophilic properties. To this end, one adds to the polymer melt a required content of an alkoxylated fatty acid amine, optionally in combination with as much as 60% by weight of a primary fatty acid amide. Furthermore, WO 00/71789 discloses polypropylene fibers and structures that can be produced therefrom. In this art, a fatty acid monoglyceride is added as melt additive to the polypropylene, and further additives are used in the form of hydrophilicity improvers and antimicrobial substances. Last but not least, WO 02/42530 discloses fibers, filaments, and nonwovens, which consist of a melt blend of polyolefin and an additive, with the additive being a chemical substance composed of an alkyl chain and a hydrophilic oligomer. The produced. nonwovens exhibit a durable wettability, preferably vis-a-vis body fluids. The hygiene nonwovens that are hydrophilated with melt additives distinguish themselves in particular by a high permanence of the hydrophilic groups on the fiber surface. However, the hydrophilicity level as is achieved by melt additives, is in many cases too low to meet the requirements of the hygiene industry. At this point the invention sets in. It is an object of the invention to provide hydrophilic polyolefin materials, in particular fibers, and/or filaments, and/or nonwovens, and/or nonwoven products, which purposefully and permanently exhibit respectively a level of hydrophilicity of the polyolefin materials as is required for the purpose of the application, and a permanence of the hydrophilic properties, and which include an initial wetting of the surface of the polyolefin materials. In accordance with the invention, this object is accomplished by claims 1-13, which define hydrophilic polyolefin materials, in particular fibers, and/or filaments, and/or nonwovens, and/or nonwoven products, consisting of a mixture of at least one polyolefin and a melt additive, containing a fatty acid ester of the general formula R—CO—O—CH2—CH2—O—R′, where R is a straight-chain or branched-chain alkyl residue with 23 to 35 carbon atoms, and where R′═H, —CH3, —C2H5, —C3H7, —C4H9, with the hydrophilic groups of the fatty acid esters including a subsequent activation on the fiber surfaces of the polyolefin materials by applying small quantities of a surface-active substance. The mixture consisting of a polyolefin and a melt additive containing a fatty acid ester for producing the polyolefin materials is extruded in a known manner. Subsequently, fibers and/or filaments, and in turn subsequently therefrom nonwovens and/or nonwoven products are produced by a standard method. Thereafter, a subsequent activation of the fatty acid ester occurs in accordance with the invention by applying a surface-active substance, a formulation in the form of an aqueous preparation, to the fiber surface of the polyolefin materials. Preferably, the polyolefin is selected from a group comprising homopolymers, copolymers, random polymers, and/or block (co)polymers of ethene and/or propene. However, also possible are copolymers with higher alkenes, in particular butene, hexene, and/or octene. Very suitable are in particular the following polymers: Poly(ethylene), such as HDPE (high density polyethylene), LDPE (low density polyethylene), VLDPE (very low density polyethylene), LLDPE (linear low density polyethylene), MDPE (medium density polyethylene), UHMPE (ultra high-molecular polyethylene) XLPE (crosslinked polyethylene), HPPE (high-pressure polyethylene), polypropylene, such as isotactic polypropylene; syndiotactic polypropylene; metallocene catalyzed polypropylene; impact-modified polypropylene, random copolymers based on ethylene, propylene, and higher 1-olefins, block copolymers based on ethylene and propylene; EPM (poly[ethylene-co-propylene]); EPDM (poly[ethylene-co-propylene-co-diene]). Also suited are graft copolymers, such as polymer blends, i.e., mixtures of polymers, which contain, among other things, the above-referenced polymers, for example, polymer blends based on polyethylene and polypropylene. Also preferred are copolymers of ethene and/or propene with higher olefins and/or diolefins. Especially preferred as polyolefin is a homopolymer of ethene or propene. In a preferred embodiment of the invention, the mixture contains 0.5 to 10% by weight, more preferably 0.5 to 3% by weight, most preferably 1 to 2.5% by weight of the melt additive. Furthermore, the mixture may contain titanium dioxide in an amount of 0.05% to 2% by weight, preferably 0.1 to 0.5% by weight. Preferred mixtures contain 96 to 99% by weight of homopolypropylene or homopolyethylene, 0 to 1% by weight of titanium dioxide, and 1 to 3% by weight of a melt additive. It has been possible to use such mixtures without problems for the production of a polyolefin material, such as, for example, a spunbond, and this despite the high temperatures prevailing in the thermoplastic melt in a range from 190 to 310° C. To produce the thermoplastic melt, the blend of the invention may first be mixed together in an unmelted state, and be subsequently melted, or, however, the melt additive and, if need be, additional additives, such as titanium dioxide may be supplied to the polymer melt in an extruder by means of lateral feed lines. The invention furthermore relates to hydrophilic polyolefin materials, such as, for example, fibers, and/or filaments, and/or nonwovens, and/or nonwoven products, which may also contain bicomponent fibers. For example, it is possible to create a core-sheath structure in the production of the fibers or filaments. According to one configuration, only the sheath of the polyolefin material contains a melt additive. The core contains no melt additive. Another configuration provides for a core containing a homopolypropylene and a sheath containing in turn a homopolyethylene, which is treated with the melt additive. Structures of this type permit providing the melt additive only in those regions, which need it for the development of its hydrophilic property. Besides a core-sheath structure, a fiber or filament cross section may also have different multicomponent distributions. These may be, for example, segmented structures, side-by-side structures, noncircular geometries, or other structures. A preferred realization of the invention for the subsequent activation of the fatty acid ester contained in the melt additive on the fiber surface of the polyolefin material is a formulation in the form of an aqueous preparation, which contains in accordance with the invention a cationically modified silicone compound and a quaternary ammonium compound which is a quaternized ester from fatty acids and triethanol amine. In this case, the formulation in the form of an aqueous preparation is set, preferably physically, on the fiber surface of the polyolefin material. In one embodiment of the invention, the blend from which the hydrophilic polyolefin materials are made contains 0.01 to 0.5% by weight, preferably 0.05 to 0.15% by weight of the formulation for activating on the fiber surface the fatty acid ester that is contained in the melt additive. The invention furthermore relates to a fiber, and/or filament, and/or nonwoven, and/or nonwoven products made from the polyolefin material of the invention. The polyolefin materials of the invention, in particular fibers, and/or filaments, and/or nonwovens, and/or nonwoven products, produced from a mixture of at least one polyolefin and at least one melt additive containing a fatty acid ester, with the polyolefin materials including a subsequent activation of the fatty acid contained in the melt additive on the surface of the polyolefin materials, can be used besides their application in a so-called “top sheet”, also in a so-called “acquisition layer.” Because of their permanent hydrophilic properties, such polyolefin materials can be used besides their application in hygiene and/or medical products, also where a rapid absorption of fluid matters, for example, in filtration applications. Thus, a filter layer may contain the hydrophilic polyolefin materials of the invention in the form of nonwovens, with the fluid being transported to a layer that extends farther below. Particles in the fluid may however be retained by the nonwoven. The rapid fluid absorption prevents fluid from collecting upstream of the nonwoven. According to one embodiment, the polyolefin material of the invention has repeated strike-through times according to the EDANA testing method ERT 154.0-00 of less than 5 seconds. It is further preferred that the polyolefin material has a repeated runoff, as determined by the EDANA test method ERT 152.0-99, of less than 25% by weight of the test fluid based on the applied quantity of the fluid. These objects and other advantageous realizations and further developments of the present invention are described in greater detail with reference to the following examples. The features described in this connection may lead with those described above to additional further developments, which are however not described in greater detail. In the drawing: FIG. 1 is a fragmentary view of a hygiene product; FIG. 2 is a fragmentary view of an oil absorption filter; and FIG. 3 is a fragmentary view of a fluid-absorbing product. FIG. 1 is a fragmentary view of a hygiene product 1. The hygiene product 1 comprises a top sheet 2, a distribution layer 3, and a core 4. The top sheet 2 is made from a nonwoven of hydrophilic polyolefin materials according to the invention. The hydrophilic nonwoven produced from the polyolefin materials of the invention absorbs fluid and passes it on to the distribution layer 3. From the distribution layer 3, the fluid can be passed on to the core 4. In the core 4, the fluid is stored. Besides the hydrophilic property of the top sheet 2, also the distribution layer 3 can be produced from the hydrophilic polyolefin materials, and thus be highly hydrophilic. However, it is also possible to make the distribution layer 3 from a different thermoplastic material. For example, the top sheet 2 is a spunbonded nonwoven, whereas the distribution layer 3 is a meltblown nonwoven. Preferably, the distribution layer 3 has a greater hydrophilicity than the top sheet 2, preferably greater than at least 10%, more preferably greater than at least 20%. In this manner, a suction effect is realized from a surface of the top sheet 2 toward the distribution layer 3. FIG. 2 is a fragmentary view of an oil filter 5. The oil filter 5 comprises a suction layer 6. The suction layer 6 is used on the one hand to absorb oil that comes into contact with the suction layer. On the other hand, the suction layer 6 also serves as a filter for particles contained in the oil and which are not allowed to move on. In the present embodiment, the suction layer 6 is followed by a further, not absolutely needed filter layer 7. The filter layer 7 is preferably finer pored than the suction layer 6. The suction layer 6 serves as a preliminary filter for the filter layer 7. The oil filter 5 can be intended, for example, for permanent use or, however, be also used only when need arises. The suction layer 6 is formed by a nonwoven produced from the hydrophilic polyolefin materials of the invention. The underlying filter layer 7 which may also have suction properties, can likewise be a nonwoven that is produced from the hydrophilic polyolefin materials of the invention. The suction layer 6 alone can also be used as an oil absorption material. This is used, for example, where oil leaking from machines or the like is to be collected. FIG. 3 illustrates a use of a nonwoven made from the hydrophilic polyolefin materials of the invention for absorbing fluids. In this embodiment, a hydrophilic nonwoven 8 is contained in a product 9, i.e., arranged between two further layers. The hydrophilic nonwoven 8 is in a position to absorb moisture in the product 9, and to store it in itself. For example, the product 9 can be used for releasing again the moisture stored in the hydrophilic nonwoven 8, when need arises. The release may occur, for example, by heating the product 9. In the following, the invention is described in greater detail with reference to examples. Different polyolefin mixtures were prepared, and polyolefin materials were produced therefrom by means of the Lurgi-Docan spunbonding process in the form of a nonwoven with a basis weight of 30 g/m2. In greater detail, the nonwovens were produced from the following materials. Reference As Reference a spunbond was produced from 100% by weight of homopolypropylene (manufacturer: Basell, Mople HP 460R), which contains a standard base stabilization for the extrusion process. Mixture 1 Mixture 1 contained 98% by weight of the homopolypropylene according to the Reference as well as in addition 2% by weight of the melt additive C25H51—CO—O—CH2—CH2—O—CH3. Mixture 2 Mixture 2 contained 97.6% by weight of the homopolypropylene according to the Reference, 2% by weight of the melt additive of Mixture 1, as well as in addition 0.4% by weight of a titanium dioxide master batch (manufacturer: Clariant, Remfin RCLAP, grain size 2.2 to 2.6 microns). Both the Reference and the Mixtures 1 and 2 were processed to a spunbond under identical process conditions. In accordance with the invention, the activation of the fatty acid esters on the fiber surface of the nonwovens made from Mixture 2 occurred with the use of a hand spray gun by applying a Formulation B in the form of an aqueous preparation containing, among other things, a silicone compound, which is cationically modified, and a quaternary ammonium compound, which is a quaternized ester from fatty acids and triethanol amine, to the nonwoven, and by subsequently drying it at room temperature for a period of 10 hours. For comparison, a nonwoven from Mixture 2 was treated in the same way with the use of a Formulation A in the form of an aqueous preparation. The Mixtures contain the following quantities respectively of Formulations A and Formulations B: Sample 8: 0.15 wt % of Formulation A Sample 9: 0.05 wt % of Formulation B Sample 10: 0.15 wt % of Formulation B As can be noted from Table 2, the mixtures of the Samples 2 to 5 of a 100% polypropylene nonwoven contain as Reference likewise different quantities of Formulations A and Formulations B. In addition, Sample 11 includes a treatment with pure water. With that, the activating effect of mere moistening is examined with the use of Formulation A or Formulation B. The hydrophilicity of the samples or permanence of the hydrophilic properties were determined by repeated strike-through time measurements according to the EDANA test method ERT 154.0-00 or repeated runoff measurements according to the EDANA test method ERT 152.0-99 (Tables 2 and 3). Moreover, the washout behavior of the spunbonds produced from Mixtures 1 and 2 was determined according to U.S. Pat. No. 5,945,175 (Table 1). The washout behavior was determined by means of the following test method: Before immersing the spunbond into water, one determines the surface tension thereof according to DIN 53914 [German Industrial Standard]. From the nonwoven, one punches out samples (appr. 2.5×22 cm, about 0.17 g) and immerses them into 80 ml water for 30 minutes. Subsequently, one measures again the surface tension of the water. TABLE 1 Surface Tension (mN/m) Mixture 1 Mixture 2 Before the test 72.5 72.5 After the test 65.5 66.8 In the case of polyolefins with a subsequent hydrophilic treatment, the surface tension normally falls clearly below 60 mN/m after the “washout” test. As shown by the test results for both Mixture 1 and Mixture 2, the surface tension remains, however, approximately constant in the case of the nonwovens produced in accordance with the invention. From that, one can draw the conclusion that a washout of the melt additive does not occur. Mixtures 1 and 2, as well as further mixtures in accordance with the invention enable a production of permanently hydrophilic nonwovens. In particular, the melt additive is added in such a quantity that after the washout test, the water has a surface tension that varies by less than 15% from the original surface tension. Preferably, the variation of the surface tension of the water is in a range below 2%. An advantageous surface tension of the water after washing out the nonwoven is in a range from 60 mN/m to 70 mN/m. The repeated strike-through time according to EDANA ERT 154.0.00 is shown in Table 2. The Reference nonwoven had hydrophilic properties as are typical of polyolefins. The applied synthetic urine (solution of 0.9% sodium chloride) was unable to penetrate the nonwoven. For this reason, the test was discontinued each time after 60 seconds. The nonwovens produced with the melt additive according to Mixtures 1 and 2, however, showed repeated strike-through times which were below 4 seconds. As can be noted from Table 2, the times of the nonwoven from Mixture 1 were somewhat less than the times of the nonwoven from Mixture 2. Whereas in the case of the nonwoven of Mixture 1, the hydrophilic properties of the nonwoven slightly decrease after the first gush, the hydrophilic property of the nonwoven from Mixture 2 increases in the further gushes. As can be noted from the times shown in Table 2, the nonwoven treated with the melt additive is capable of seeing to a rapid permeability of the applied synthetic urine not only in the first gush. Rather, this property moreover exists in the case of multiple wettings. This is especially important, when this type of nonwoven is used as top sheet in a diaper, napkin, or incontinence product. In their case, the product has to absorb and distribute not just a one-time fluid gush. Rather, it is required that such an absorption and distribution of fluid be also repeatable. To increase the wearing comfort of such a hygiene product for the user, the nonwoven has advantageously a repeated strike-through time, which is below 4 seconds even after three test runs. TABLE 2 Repeated Strike-Through Time Sample 6 7 8 9 10 11 1 2 3 4 5 Mixture Mixture Mixture Mistune Mixture Mixture Reference Reference Reference Reference Reference 1 2 2 2 2 2 Activation — 0.15 wt 0.05 wt 0.15 wt 0.3 wt — — 0.15 wt 0.05 wt 0.15 wt Water % FA % FB % FB % FB % FA % FB % FB 1st gush >60 1.8 >30 2.5 2.1 2.3 3.8 1.6 1.8 1.7 2.0 in sec. 2nd gush >60 >30 >30 14.8 7.3 2.9 3.3 3.0 2.6 2.4 2.9 in sec. 3rd gush >60 >30 >30 12.4 7.8 2.8 2.9 3.3 2.7 2.5 2.9 in sec. FA = Formulation A FB = Formulation B It is known that fatty acid esters can also be used as dispersants for inorganic fillers, for example pigments. EP 0 605 831 A1 discloses the corresponding addition of fatty acid esters to mixtures consisting of ethylene/olefin copolymers and inorganic fillers. However, as a comparison of the properties of the nonwovens made from Mixtures 1 and 2 shows, the melt additive does not act as dispersant, but obviously only as hydrophiling agent on the fiber surface. Likewise, when adding titanium dioxide (Mixture 2), low values are measured for the repeated strike-through time. As expected, Sample 1 shows the hydrophobic properties that are typical of the polyolefins, and which are characterized by long repeated strike-through times. The application of Formulation A in accordance with the invention to the surface of the polyolefin material (nonwoven: Sample 8) leads to a short-term improvement of the hydrophilicity level (low strike-through and runoff values) of the nonwoven that is treated with the melt additive. However, the runoff values deteriorate as the number of repetitions increases. Yet, the small quantity of Formulation A (0.05% by weight in the case of Sample 8), which does not show yet a hydrophiling effect on the 100% PP nonwoven (Sample 2), causes a significant improvement in the permanence of the hydrophilicity in combination with a hydrophiling melt additive (Sample 8). Surprisingly, it was found when small quantities of Formulation B (Samples 9-10) were applied in accordance with the invention to the fiber surface of the polyolefin material, that both the hydrophilicity level (low strike-through and runoff values) and the permanence of the hydrophilic properties are improved in comparison with a polyolefin material (nonwoven: Sample 7) that was modified only with the melt additive. Obviously, the Formulation B containing a cationically modified silicone and a quaternary ammonium compound, and which is subsequently applied in small quantities, serves as activator. Whereas Samples 3-5 show effective the second gush in the repeated strike-through and runoff measurements a strong decrease in hydrophilicity, which is due to a washout of Formulation B, Samples 9 and 10 show an improvement in the permanence of the hydrophilicity. As a result of activating a nonwoven that is modified with a melt additive, with the aid of small quantities of Formulation B, preferably 0.05 to 0.15% by weight, one obtains in accordance with the invention nonwovens according to Samples 9 and 10, which distinguish themselves by an excellent durable hydrophilicity. This property profile cannot be realized with Formulation B alone and not without the use of a melt additive. An application of Formulation B in a quantity of 0.3% by weight to a 100% PP nonwoven according to Sample 5 is too low to impart to the material a hydrophilicity and permanence of the hydrophilicity comparable to Samples 8 and 9. A comparison of both hydrophilicity and permanence of the hydrophilic properties of Sample 11 and Sample 7 shows that the treatment with pure water only causes no significant activating effects. Advantageously, nonwovens that are produced by subsequent activation of the hydrophilic melt additive distinguish themselves by a clearly improved hydrophilicity in comparison with a nonactivated nonwoven, in particular in the case of an initial wetting of the dry nonwoven. TABLE 3 Repeated Runoff Sample 6 7 8 9 10 11 1 2 3 4 5 Mixture Mixture Mixture Mistune Mixture Mixture Reference Reference Reference Reference Reference 1 2 2 2 2 2 Activation — 0.15 wt 0.05 wt 0.15 wt 0.3 wt — — 0.15 wt 0.05 wt 0.15 wt Water % FA % FB % FB % FB % FA % FB % FB Runoff 100 11 93 55 50 — 15 1 16 15 42 1st gush in wt % Runoff 100 51 93 654 47 — 13 2 7 4 17 2nd gush in wt % Runoff 100 80 73 73 — 48 24 11 5 51 3rd gush in wt % Runoff — — — — — — — 47 12 3 62 4th gush in wt % Runoff — — — — — — — 44 11 12 60 5th gush in wt % FA = Formulation A FB = Formulation B
20061121
20111018
20070719
98730.0
D02G300
0
HAMMER, KATIE L
HYDROPHILIC POLYOLEFIN MATERIALS AND METHOD OF PRODUCING SAME
UNDISCOUNTED
0
ACCEPTED
D02G
2,006
10,538,110
ACCEPTED
Electro-acoustic resonator
An electro-acoustic resonator (1, 8, 17) of the membrane or FBAR type (1) or the solidly-mounted or SBAR type (8), with electrodes comprising a single conducting layer or multiple conducting layers, i.e. sandwich construction (17) with an optimum coupling factor kr and thus an improved filter bandwidth. The optimum coupling factor kr is achieved by the arrangement that the top electrode (6, 15, 25) is thinner than the bottom electrode (4, 13, 23). The coupling factor is independent of the resonator's layout defined by the mask.
1. Electro-acoustic resonator (1, 8, 17) with a layer structure comprising a piezoelectric layer (5, 14, 24) and a top (6, 15, 25) and a bottom (4, 13, 23) electrode layer, with the thickness (T1, T2, . . . T6) of the two electrode layers being unequal, characterised in that the top electrode layer (T1, T3, T5) is thinner than the bottom (T2, T4, T6) electrode layer. 2. Electro-acoustic resonator (1, 8, 17) as claimed in claim 1, characterised in that the electro-acoustic resonator (1, 8, 17) is a solidly-mounted resonator or SBAR (8,17) or that it has a membrane structure FBAR (1). 3. Electro-acoustic resonator (1, 8, 17) as claimed in claim 1, characterised in that at least one of the electrode layers (25, 26 or 22, 23) is formed by a stack of conductive materials. 4. Electro-acoustic resonator (1, 8, 17) as claimed in claim 1, characterised in that between the electrode layers 22 and 23 and/or 25 and 26 a conductive thin diffusion barrier is formed. 5. Electro-acoustic resonator (1, 8, 17) as claimed in claim 3, characterised in that in the stack the conductive material (23, 25) that is in contact with the piezoelectric layer (24) has a higher acoustic impedance than the conductive material (22, 26) that is not in contact with the piezoelectric layer (24). 6. Electro-acoustic resonator (1, 8, 17) as claimed in claim 3, characterised in that in the stack the conductive material (23, 25) in contact with the piezoelectric layer (24) has a lower acoustic impedance than the conductive material (22, 26) that is not in contact with the piezoelectric layer (24). 7. Electro-acoustic (1, 8, 17) resonator as claimed in claim 5, characterised in that the conductive material with the lower acoustic impedance comprises Aluminium (Al). 8. Electro-acoustic resonator (1, 8, 17) as claimed in claim 5, characterised in that the conductive material with the higher acoustic impedance comprises platinum (Pt), wolfram (W), molybdenum (Mo), titan-wolfram (TixW1-x, 0<x<1), Gold (Au). 9. Electro-acoustic resonator (1, 8, 17) as claimed in claim 5, characterised in that the diffusion barrier between the electrode layers 22 and 23 and/or between the electrodes 25 and 26 consists of titanium nitride (TiN), or titanium (Ti), or consists of comminations of titanium nitride (TiN) and titanium (Ti). 10. Electro-acoustic resonator (1, 8, 17) as claimed in claim 1, characterised in that the electrode layers (4, 6, 13, 15, 23, 25) comprise Molybdenum (Mo) and that, for a resonant frequency in the region of 2 GHz, the thickness (T1, T3, T5) of the top Molybdenum layer (6, 15,25) is in the region of 200 nm and the thickness (T2, T4, T6) of the bottom Molybdenum layer (4, 13, 23) is in the region of 300 nm, these thicknesses scaling approximately inversely with resonant frequency. 11. Electro-acoustic resonator (1, 8, 17) as claimed in claim 1, characterised in that the electrode layers (4, 6, 13, 15, 23, 25) comprise platinum (Pt) and that, for a resonant frequency in the region of 2 GHz, the thickness (T1, T3, T5) of the top platinum layer (6, 15,25) is in the region of 50 nm and the thickness (T2, T4, T6) of the bottom platinum layer (4, 13, 23) is in the region of 150 nm, these thicknesses scaling approximately inversely with resonant frequency. 12. Use of an electro-acoustic resonator (1, 8, 17), especially an electro-acoustic resonator as claimed in claim 1, as a component of a radio frequency (RF) filter, or as a component used in a sensor, or used in an ultrasonic transducer, or used in an array of ultrasonic transducers.
The invention relates to an electro-acoustic wave resonator. Resonators are the basic building blocks of filters. Thin-film bulk acoustic wave (SAW) resonator filters are of growing interest particularly for radio frequency (RF) front-end selectivity in wireless applications, e.g. 2G and 3G handsets. This technology offers the best possibility for integration and miniaturisation. One of the important parameters of an electro-acoustic resonator is its coupling factor kr defined by kr2=[1-(fr/fa)2]. In this equation fr and fa are the resonator's resonance and antiresonance, i.e. the frequencies of minimum and maximum impedance. Maximum achievable filter bandwidth is proportional to kr2. A BAW resonator consists essentially of a layer sequence comprising two electrode layers adjacent to a piezoelectric layer. For RF applications the piezoelectric layer typically consists of a deposited layer of a material such as aluminium nitride (AlN). For reducing deposition time, resonators with a feasibly thin piezoelectric layer are desired. The disadvantage of thin-film piezoelectric materials is their rather low coupling coefficient kt. As resonator coupling factor kr is proportional to the coupling coefficient kt the design of the electro-acoustic resonator has to be optimised to compensate the rather low coupling coefficient kt of thin-film piezoelectric materials. For example, a high coupling factor kr is required for the 3G UMTS receive (RX) and transmit (TX) bands. WO 02/23720 A1 discloses a resonator that comprises a first electrode, a second electrode and a piezoelectric layer arranged between the above. A first acoustic compression layer is arranged between the piezoelectric layer and the first electrode with a higher acoustic impedance than the first electrode. For a warranty of a sufficiently low resistance of the electrodes that document reveals that the electrodes are at least 200 nm thick. There, the electrode preferably consists of Aluminium (Al) with a thickness of 300-600 μm. Such an electrode results in a low electrical resistance and effects only a small deterioration of the coupling coefficient achieved by the arrangement of an acoustic compression layer. U.S. Pat. No. 6,051,907 discloses a method for tuning a thin-film bulk acoustic wave resonator (FBAR) located on a wafer. The method is used for fine tuning if the centre frequency is different from a target value and is done by etching the top electrode. According to U.S. Pat. No. 6,051,907 the structure of thin-film bulk acoustic wave resonators formed on wafers is altered before the wafer is diced. That method effects that the FBAR exhibits a series or parallel resonant frequency that is within an acceptable error margin of a design series or parallel resonant frequency, respectively. In one example of U.S. Pat. No. 6,051,907 the top and the bottom electrode both comprise molybdenum (Mo) having a thickness of 300 nm. As the method for fine tuning in that document is based on thinning of the top electrodes of the FBARs, which results in increasing series resistance of the FBARs, there it is proposed to design top electrodes (of Mo) with a thickness of 400 nm and with a correspondingly thinner layer of piezoelectric material, in this case zinc-oxide (ZnO). The objective of the invention is to provide an electro-acoustic resonator which will give increased filter bandwidth. This objective is achieved by an electro-acoustic resonator with a layer structure comprising a piezoelectric layer and a top and a bottom electrode layer, with the thickness of the two electrode layers being unequal and with the top electrode layer being thinner than the bottom electrode layer. In this configuration maximum resonator coupling factor is achieved. The enhancement occurs due to an improved match, inside the piezoelectric layer, between the spatial distributions of the applied electric field (which is approximately constant in the direction normal to the layer) and the electric field directly coupled to the acoustic wave (which is approximately cosinusoidal about a plane midway between thin electrodes, but closer to constant for optimal electrode thickness). The electro-acoustic resonator may be a solidly-mounted thin-film resonator (SBAR) or may have a membrane structure, also referred to as a film bulk acoustic wave resonator (FBAR). The layer sequence of an FBAR is typically etch-stop layer/bottom electrode layer/piezoelectric layer/top electrode layer. The energy is confined by having a perfect reflector at the free-space interface above and below the resonator. The layer sequence of an SBAR is typically substrate/Bragg reflector/bottom electrode layer/piezoelectric layer/top electrode layer. The Bragg reflector comprises alternate high and low mechanical impedance layers and provides the required reflection below the resonator. A mass-loading layer above the top electrode is included in a subset of the resonators in a typical filter design. The mass-loaded resonators have slightly lower fr and fa than the non-mass-loaded resonators. In all cases the resonant frequency is approximately inversely proportional to the thickness of the piezoelectric layer. For typical RF applications all layer thicknesses are of the order of 100 nm to 2000 nm. The substrate thickness is typically of the order of 0.1 mm to 2 mm. At least one of the electrode layers of the electro-acoustic resonator can be formed by a stack of two (or more) conductive materials. Such a configuration is referred to here as a “sandwich” structure. The conductive materials have to be carefully chosen as they influence the electrical loss and the bandwidth. In one embodiment of the electro-acoustic resonator a conductive thin diffusion barrier is formed between the electrode layers. In a further embodiment the conductive material in the stack that is in contact with the piezoelectric layer has a higher acoustic impedance than the conductive material that is not in contact with the piezoelectric layer. In another embodiment the conductive material in the stack that is in contact with the piezoelectric layer has a lower acoustic impedance than the outer conductive material that is not in contact with the piezoelectric layer. Preferably, the outer conductive material is a noble metal such as gold (Au) or platinum (Pt) which protects the resonator's surface. The conductive material with the lower acoustic impedance preferably comprises aluminium (Al). The conductive material with the higher acoustic impedance comprises for example platinum (Pt), wolfram (W), molybdenum (Mo), titan-wolfram (TixW1-x, 0<x<1) or gold (Au). The diffusion barrier between the electrode layers and/or between the electrodes may consist of titanium nitride (TiN) or titanium (Ti) or may consist of combinations of titanium nitride (TiN) and titanium (Ti). For example, the inventive electro-acoustic resonator can be used in a filter with a centre frequency of 1.95 GHz. This is the centre frequency corresponding to the transmission (TX) band of the UMTS 3G standard. For this application the bandwidth required is very close to the maximum achievable using aluminium nitride for the piezoelectric layer. One preferred embodiment, for use in filters with centre frequency in the region of 2 GHz, is an electro-acoustic resonator whose electrode layers comprise molybdenum with, for a resonant frequency in the region of 2 GHz, the top layer's thickness being in the region of 200 nm and the bottom layer's thickness being the region of 300 μm, these thicknesses scaling approximately inversely with resonant frequency. Another preferred embodiment is an electro-acoustic resonator whose electrode layers comprise platinum with, for a resonant frequency in the region of 2 GHz, the top layer's thickness being in the region of 50 nm and the bottom layer's thickness being in the region of 150 nm, these thicknesses scaling approximately inversely with resonant frequency. The inventive electro-acoustic resonator may be used as a component of a radio frequency (RF) filter, or as a component used in a sensor, or used in an ultrasonic transducer, or used in an array of ultrasonic transducers. These and other aspects of the invention will become apparent from and will be elucidated with reference to the embodiments described hereinafter, where FIG. 1 illustrates a layer sequence in an FBAR, FIG. 2 illustrates a layer sequence in an SBAR, FIG. 3 illustrates a layer sequence in a sandwich SBAR, FIG. 4 illustrates a table with the coupling factor versus the thicknesses of top and bottom electrode for a non-mass-loaded SBAR, FIG. 5 illustrates a table with the coupling factor versus the thicknesses of top and bottom electrode for a mass-loaded SBAR, FIG. 6 illustrates a table with the coupling factor versus the thicknesses of top and bottom electrode for a non-mass-loaded sandwich SBAR, FIG. 7 illustrates a table with the coupling factor versus the thicknesses of top and bottom electrode for a mass-loaded sandwich SBAR. FIG. 1 illustrates a layer sequence in an FBAR 1 consisting of, from bottom to top, a substrate 2, an etch-stop layer 3, a bottom electrode layer 4, a piezoelectric layer 5, a top electrode layer 6 and a mass-loading layer 7. The FBAR 1 shows the electrode layers 4, 6 with unequal thicknesses with the top electrode 6 having a thickness of T1 and the bottom electrode 4 having a thickness of T2. According to the invention T1 is smaller than T2. This asymmetrical arrangement enables the resonator to achieve maximum coupling-factor, thus giving maximum filter bandwidth. FIG. 2 illustrates a layer sequence in an SBAR 8 consisting of, from bottom to top, a substrate 9, an acoustic mirror 10 like a Bragg reflector comprising alternate high 11 and low 12 mechanical impedance layers, a bottom electrode layer 13, a piezoelectric layer 14, a top electrode layer 15 and a mass-loading layer 16. The SBAR 8 shows electrode layers 13, 15 with unequal thicknesses with the top electrode 15 having a thickness of T3 and the bottom electrode 13 having a thickness of T4. According to the invention thickness T3 is smaller than thickness T4. FIG. 3 illustrates a layer sequence in a sandwich SBAR 17 consisting of, from bottom to top, a substrate 18, an acoustic mirror 19 like a Bragg reflector comprising alternate high 20 and low 21 mechanical impedance layers, a bottom outer electrode layer 22, a bottom inner electrode layer 23, a piezoelectric layer 24, a top inner electrode layer 25, a top outer electrode layer 26 and a mass-loading layer 27. The sandwich SBAR 17 shows outer electrode layers 22 and 26 of equal thickness, and inner electrode layers 23 and 25 of unequal thickness with the inner top electrode 25 having a thickness of T5 and the inner bottom electrode 23 having a thickness of T6. Between the electrodes 22 and 23 and/or between the electrodes 25 and 26 there may be a diffusion barrier consisting of a layer of e.g. TiN or a combination of layers of Ti and TiN. This diffusion barrier is to avoid inter-diffusion of the two electrode materials 22 and 23 or 25 and 26 respectively. The thickness of the thin diffusion barrier is between 10 and 30 nm and does not change the performance of the resonator substantially. The mass-loading layer (7 in FIG. 1, 16 in FIG. 2, 27 in FIG. 3) is included in a subset of the resonators in a typical filter. The remaining resonators are non-mass-loaded. The invention is illustrated by the example of a 1.95 GHz filter for the TX band of the UMTS 3G standard. For this application the bandwidth required is very close to the maximum achievable using aluminium nitride (AlN). In principle, a different optimum combination of layers is required for the mass-loaded and non-mass-loaded resonators. The optimum combinations are applicable to both ladder and lattice implementations of the filter. FIG. 4 illustrates a table with the coupling factor kr versus the thickness T3 of the top electrode 15 and versus the thickness T4 of the bottom electrode 13 of the filter's non-mass-loaded SBARs 8 as shown in FIG. 2. The electrode metal is molybdenum (Mo) which has about twice the acoustic impedance of aluminium nitride, and very high quality aluminium nitride layers can be grown on it. Tantalim pentoxide (Ta205) and silicon dioxide (SiO2) are employed as the high and the low impedance layers of the Bragg reflector. According to the table the optimum thicknesses of Molybdenum are seen to be in the region of T3=200 nm for the top electrode 15 and of T4=300 nm for the bottom electrode 13. For this combination the corresponding thickness of the aluminium nitride is 1410 nm, and the corresponding maximum value of kr is 0.226. FIG. 5 illustrates a table with the coupling factor kr versus the thickness T3 of the top electrode 15 and versus the thickness T4 of the bottom electrode 13 for the filter's mass-loaded resonators SBAR 8. The optimum thicknesses of the molybdenum also are seen to be in the region of T3=200 nm for the top electrode 15 and of T4=300 nm for the bottom electrode 13 resulting in a maximum value of kr of 0.222. The mass-loading layer thickness is 150 nm. Other layer thicknesses are the same as for the non-mass-loaded SBARs described in FIG. 4. The enhancement of the coupling factor kr using the described optimum unequal thicknesses T3 and T4 should be even higher when wolfram (W) is used instead of molybdenum as wolfram has a mechanical impedance some 70% higher than that of molybdenum. Filter implementation for the same centre frequency using sandwich SBARs is now considered. FIG. 6 illustrates a table with the coupling factor kr versus the thickness T5 of the top electrode 25 and versus the thickness T6 of the bottom electrode 23 for the filter's non-mass-loaded sandwich SBARs 17. The outer electrode layers 22, 26 are of aluminium and the inner electrode layers 23, 25 adjacent to the piezoelectric (AIN) layer 24 are of platinum (Pt). To achieve an adequately low electrical resistance it is proposed that the aluminium layers 22, 26 have the same thickness, here set to 200 nm. The top 25 and the bottom 23 electrode layers are the variables. Optimum coupling factor kr is obtained with values of about T5=50 nm for the top electrode 25 and of about T6=150 nm for the bottom electrode 23 respectively. Between the electrodes 22 and 23 and/or between the electrodes 25 and 26 there may be a diffusion barrier consisting of a layer of e.g. TiN or a combination of layers of Ti and TiN. This diffusion barrier is to avoid inter-diffusion of the two electrode materials 22 and 23 or 25 and 26 respectively. The thickness of the thin diffusion barrier is between 10 and 30 nm and does not change the performance of the resonator substantially. FIG. 7 illustrates a table with the coupling factor kr versus the thickness T5 of the top electrode 25 and versus the thickness T6 of the bottom electrode 23 for the filter's mass-loaded SBARs 17. Optimum coupling factor kr is again obtained with values of about T5=50 nm for the top electrode 25 and of about T6=150 nm for the bottom electrode 23 respectively. Other layer thicknesses are the same as for the non-mass-loaded sandwich SBARs described in FIG. 6. In both mass-loaded and non-mass-loaded sandwich SBARs optimum thicknesses of the inner Pt electrodes are almost independent of the thicknesses of the Al outer electrodes 22, 26. For optimum Pt layer thicknesses and Al layer thicknesses of 100 nm, 200 nm and 300 nm the coupling factor kr=0.220, 0.216 and 0.202 respectively. The invention may be summarised by a thin-film bulk acoustic wave resonator (1, 8, 17) of the membrane or FBAR type (1) or the solidly-mounted or SBAR type (8), either with single layer electrodes (1,8) or of the multiple-layer electrode sandwich construction (17), with an optimum coupling factor kr, and thus increased bandwidth in filters incorporating such resonators. The optimum coupling factor kr is achieved by the arrangement that the top electrode (6, 15, 25) is thinner than the bottom electrode (4, 13, 23). The coupling factor is independent of the resonator's layout.
20051214
20090421
20060622
93714.0
H01L4118
1
SUMMONS, BARBARA
ELECTRO-ACOUSTIC RESONATOR WITH A TOP ELECTRODE LAYER THINNER THAN A BOTTOM ELECTRODE LAYER
UNDISCOUNTED
0
ACCEPTED
H01L
2,005
10,538,254
ACCEPTED
Pressure sensor
The invention provides a pressure sensor with a housing for a pressure sensing arrangement, e.g. a semi-conductor arrangement. The housing consists of a bottom part and an intermediate member with a through hole forming a sidewall of a cavity for the pressure sensing arrangement. A membrane is attached to the intermediate member to cover an opening of the cavity, and to allow pressure from outside to propagate into a pressure transmitting medium contained inside the housing and thus to the pressure sensing arrangement therein. The invention also provides a method of making a pressure sensor with a housing of the above-described kind.
1. A pressure sensor comprising a housing with a bottom part and a sidewall extending upwardly and forming an opening in an upper surface of the housing, a pressure sensing arrangement, and a membrane covering the opening to provide a substantially closed cavity in the housing, wherein the housing comprises an intermediary member attached between the bottom part and the membrane and comprising an aperture forming at least a part of the cavity. 2. The sensor according to claim 1, wherein the intermediary member forms the sidewall of the cavity. 3. The sensor according to claim 1, wherein the aperture has a profile matching a profile of the pressure sensing arrangement when viewed in the same cross-sectional plane. 4. The sensor according to claim 1, wherein the intermediary member and the bottom part are joined in matching plane surfaces. 5. The sensor according to claim 1, wherein the intermediary member is attached to the bottom part by welding. 6. The sensor according to claim 1, wherein the membrane is fastened to the intermediary member. 7. The sensor according to claim 1, wherein the intermediary member is made from a plate shaped material in a stamping process. 8. The sensor according to claim 1, comprising a channel for filling the cavity with a pressure-transmitting medium, the channel being formed between the bottom part and the intermediary member. 9. The sensor according to claim 1, wherein the membrane is attached to a first contact flange of an upper surface of the intermediary member, the first contact flange forming a circumferentially extending elevation of the upper surface. 10. The sensor according to claim 9, further comprising a supporting ring having a second contact flange of a lower surface of the supporting ring, the second contact flange being attached to an outer surface of the membrane above the first contact flange, the second contact flange forming a circumferentially extending elevation of the lower surface. 11. A method of making a pressure sensor comprising a housing with a cavity having an opening in an upper surface of the housing, a pressure sensing arrangement placed in the cavity for sensing pressure, and a membrane covering the opening and attached to the housing to provide a substantially dosed space in the cavity, wherein a bottom part and an intermediary member is assembled to form the housing, and wherein the intermediary member is attached between the bottom part and the membrane and forms at least a part of the cavity. 12. The method according to claim 11, wherein at least one of the bottom part and the intermediary member is formed in a stamping process.
CROSS REFERENCE TO RELATED APPLICATIONS This application is entitled to the benefit of and incorporates by reference essential subject matter disclosed in international Patent Application No. PCT/DK2003/000849 filed on Dec. 10, 2003 and Danish Patent Application No. PA 2002 01907 filed on Dec. 12, 2002. FIELD OF THE INVENTION The present invention relates to a pressure sensor. BACKGROUND OF THE INVENTION Pressure sensors of the above described kind are used in numerous applications, e.g. in connection with operation of combustion engines, chemical process plants and refrigeration systems. In semiconductor based electronic pressure sensors, a silicon chip with a semiconductor membrane area constitutes the pressure-sensing element. An extensometer is mounted to the membrane area for registering deflection in the membrane area when it is exposed to the pressure of a medium. In the heretofore known pressure sensors, the silicon chip is typically mounted on a base made of glass. The chip arrangement, constituted by the silicon chip and the glass base, is mounted in a housing comprising a membrane for separation of the silicon chip from the medium. The separating membrane and housing form a sealed space surrounding the chip arrangement. This space is normally filled completely with a pressure-transmitting medium, e.g. silicon oil through which pressure can propagate. In order to transmit the pressure substantially without pressure-loss, the pressure-transmitting medium inside the housing must have a low compressibility. When the separating membrane is exposed to a pressure, the pressure will be transmitted to the silicon chip and cause a deflection of the semiconductor membrane, which deflection is detected by the extensometer. The required tolerances of the housing are narrow and, accordingly, expensive and time-consuming manufacturing processes have traditionally been used in making pressure sensors of the above-mentioned kind. Typically, the housing, and in particular the cavity therein, is made in a time consuming milling process wherein material is removed from a solid piece of a steel block, or the housing is made by sintering with subsequent machining. Inevitably, this occupies expensive production facilities for a relatively long time. Since the pressure-transmitting medium normally changes volume differently from the housing when exposed to a change in temperature, the pressure signal deriving from the semiconductor arrangement depends on the temperature. I.e. in response to a specific change in temperature, the volume of the chamber, and the volume of the pressure-transmitting medium changes differently. Since the chamber is completely filled with an incompressible medium, and since the chamber is sealed, the volumetric differences must be compensated by deflection of the flexible membrane thereby introducing a deviation in the pressure signal which deviation depends on the flexibility of the membrane and the temperature. Normally, the semiconductor arrangement is electrically connected to an electronic circuit comprising an arrangement for compensating the temperature caused deviation. Such compensating arrangement is, however, expensive and requires space, and the dimension thereof depends on the necessitated degree of compensation. In order to reduce the deviation caused by a changing temperature, it is sometimes attempted to limit the amount of free space around the semiconductor in the cavity. The limited space reduces the amount of pressure-transmitting medium necessary to fill up the cavity and thus reduces the impact of changes in the temperature. Both U.S. Pat. No. 5,436,491 and U.S. Pat. No. 4,502,335 disclose pressure sensors of this kind. These kinds of refined sensors comprise housings made from moulded or machined body casings and further comprise moulded fillers to reduce the free space in the cavity. The design and corresponding manufacturing costs of the sensors are even higher than the costs of making the aforementioned traditional sensors, and the use of fillers introduce additional manufacturing steps. SUMMARY OF THE INVENTION It is an object of the present invention to solve problems associated with the manufacturing of pressure sensors. Accordingly, the invention in a first aspect provides a pressure sensor of the kind mentioned in the introduction, characterised in that the housing comprises an intermediary member attached between the bottom part and the membrane and comprising an aperture forming at least a part of the cavity. Due to the use of an intermediary member attached between the bottom part and the membrane, the housing can be made in simple and fast production steps e.g. by stamping or punching the bottom part, the intermediary member and/or the membrane out of plate shaped bodies, and subsequently assembling the parts, e.g. by welding. The aperture in the intermediary member may e.g. form part of the sidewall of the cavity. The intermediary member may be formed by any number of parts. It may have a laminated structure made from a plurality of discs or it may be formed from sectors of semicircular disc segments joint by welding. If it is desired to limit the amount of the pressure-transmitting medium, e.g. to reduce the need for compensation of the signal from the sensor, the spacing around the pressure sensing arrangement in the cavity can easily be reduced. In this case, the intermediate member can be made with an aperture having a cross sectional profile matching the profile of the pressure sensing arrangement in a corresponding cross-sectional view. When the intermediate member is attached between the bottom part and the membrane, the aperture forms a sidewall of the cavity, and due to the matching cross-sectional profiles of the aperture and the pressure sensing arrangement, the amount of pressure-transmitting medium necessary to fill up the cavity is reduced. The possibly somewhat tortuous profile of the aperture can be made in the intermediary member using any convenient process known in the art, e.g. a stamping process, and it is thus possible to make the profile at a high speed even within narrow dimensional tolerances. If additional space is required for electrical connections between the pressure sensing arrangement and external equipment, the aperture could be punched in any shape and thus provide the necessary space for such additional components. As an example, it may be desired to arrange connecting pins through the bottom part and into the cavity for establishing electrical connections through the housing. The openings in the bottom part may be punched or stamped in one and the same operation in which the general shape of the bottom part is made and the intermediary member may have an aperture, e.g. with a cross sectional shape as a star, leaving space in the middle for a pressure sensing arrangement and space in the projecting points or fingers of the star for the connecting pins. In a specifically simple and easily manufactured embodiment, the intermediary member and the bottom part are joined in matching plane surfaces. The bottom part and/or the intermediary member could be made from a plate shaped material, e.g. of a non-corrosive material such as stainless steel, a ceramic material or Kovar. Similarly, the membrane could be made from a disc of stainless steel. The bottom part and the intermediary member could be joined by laser welding, Electron Beam Welding (EBW), Wolfram Inert gas welding (WIG), resistance welding or by soldering or gluing. The membrane could be fastened to the intermediary member by any similar process, e.g. by use of a ring extending circumferentially around the outer peripheral edge of the membrane and preferably overlapping this edge. Preferably, the pressure sensing arrangement is a semiconductor arrangement having a base, e.g. made of glass. A conduit for filling the cavity with the pressure-transmitting medium, e.g. silicone oil, may be made as a penetration through one of the bottom part and the intermediary member. The hole could be sealed with a closure having the shape of a spherical ball and being fastened to the hole via welding, e.g. resistance welding. Such welding may be conducted with the housing submersed into silicon oil. In one embodiment, the conduit is formed between the bottom part and the intermediary member, e.g. by making a groove in the surface wherein the intermediary member and the bottom part are joined. Electrically conductive pins entering into the cavity e.g. through holes in the bottom part or in the intermediary member for electrically connecting the semiconductor arrangement with outside equipment may preferably be electrically isolated from the bottom part or intermediary member, in particular if the bottom part or intermediary member is made from an electrically conductive material. The membrane could be attached to a first contact flange of an upper surface of the intermediary member, i.e. opposite the surface where the intermediate member is attached to the base part, e.g. by welding, gluing or by similar assembling processes. In order to ensure a more solid fixation of the membrane to the intermediary member, a supporting ring could be fastened on top of the membrane, e.g. in a welding operation wherein the supporting ring is welded to the membrane, and to the intermediary member. In order to reduce contact between the membrane and the intermediary member, the first contact flange may form a circumferentially extending elevation of the upper surface allowing the membrane to rest on the contact flange and to remain unsupported by the remaining part of the intermediary member. In a similar manner, the supporting ring may have a second contact flange of a lower surface thereof, i.e. on a surface opposite to an upper and outer surface of the supporting ring when attached to the membrane and to the intermediary member. The second contact flange is attached to an outer surface of the membrane above the first contact flange, and in order to reduce contact between the membrane and the supporting ring, the second contact flange may form a circumferentially extending elevation of the lower surface. According to a second aspect, the present invention relates to a method of making a pressure sensor comprising a housing with a cavity having an opening in an upper surface of the housing, a pressure sensing arrangement placed in the cavity for sensing pressure, and a membrane covering the opening and attached to the housing to provide a substantially closed space in the cavity, wherein a bottom part and an intermediary member is assembled to form the housing, characterized in that the membrane is attached to a contact face of the intermediary member. In particular, one of the bottom part and the intermediary member may be formed in a stamping process. The method may be combined with any step necessary for making any of the aforementioned embodiments of a pressure sensor. BRIEF DESCRIPTION OF THE DRAWINGS In the following, the invention will be described in further details with reference to the drawing in which: FIG. 1 shows an exploded view of a first preferred embodiment of a pressure sensor according to the present invention, FIG. 2 shows an isometric view of the pressure sensor of FIG. 1, when it is assembled, FIG. 3 shows a cross-sectional view of the pressure sensor of FIG. 1, FIG. 4 shows a cross-sectional view of an alternative embodiment of a pressure sensor, FIG. 5 shows a cross-sectional view of the pressure sensor along 5-5 in FIG. 4, and FIGS. 6 and 7 show sectional views of alternative embodiments of the pressure sensor. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows an exploded view of an electronic silicon-based pressure sensor 1 comprising a housing made from a plate shaped bottom part 2 fastened on a first surface 3 to a plate shaped intermediary member 4. The intermediary member is penetrated by an aperture 5 forming, in combination with the bottom part 2 and a flexible membrane 6, a closed cavity (numeral 28 in FIG. 2) for housing a semiconductor arrangement 7. The bottom part comprises a base for fastening the semiconductor arrangement to the bottom part. The pressure sensor further comprises a supporting ring 9. The bottom part 2 has the shape of a circular disc made with four holes 10-13 penetrating the bottom part to form apertures into the cavity. Electrically conductive pins 14-17 are arranged and fixed to the apertures via an electrically isolating glass material (shown in FIG. 2). Each pin is held in a position wherein a smaller part of the pin projects out from the upper surface 18 of the bottom part 2 whereas a larger part extends from the opposite lower surface 19 of the bottom part. Each pin is, moreover, positioned so that they do not touch the inner surfaces of the apertures. In addition to the four holes, an oil-channel 20 for filling the cavity with a pressure-transmitting medium such as silicon oil is made in the bottom part. The oil-channel is formed by a hole penetrating the bottom part, and which has a circular cross-sectional shape. The pressure channel 30 is described in further details later. The contact flange 21 forms a circumferentially extending elevation of the upper surface of the intermediary member. In a corresponding manner, the contact flange 22 of the supporting ring also forms a circumferentially extending elevation of the lower surface of the supporting ring. The elevated flanges 21, 22 provide free space between the membrane and the intermediary member and supporting ring, respectively. The free space is better seen in FIG. 2. The elevated flanges are introduced in order to reduce contact between the membrane and the intermediary member and the supporting ring to a minimum, i.e. so that contact merely exists along an outer peripheral edge of the parts whereby the movement of the membrane is less influenced by the housing. The semiconductor arrangement is fastened to the base by glue 37. The semiconductor arrangement comprises a chip 23 and a glass base 24 joined via an electrostatic process. In one area, the chip 23 forms a semiconductor membrane 25, i.e. the thickness of the chip is relatively low. The membrane may be circular, quadrangular or it may have other shapes. The area of the semiconductor membrane deflects upon impact of a force and the size of the defection is determined by extensometers in a manner known per se. The semiconductor arrangement is connected to the pins via electrically conductive wires (not shown). Via the wires and the electrically conductive pins, it is possible to transmit a signal representing the deflection of the membrane out of the housing of the pressure sensor. In the disclosed embodiment, the semiconductor arrangement has a rectangular cross sectional profile but semiconductors with alternative profiles exist. Corresponding to the bottom part, the intermediary member has the shape of a circular disc. The intermediary member is made with a hole 5 forming an aperture in the housing, which aperture is sealed by the flexible membrane. As it appears from FIG. 4, the inner cross-sectional shape of the aperture is fitted to the outer cross sectional shape of the semiconductor arrangement and the pins. The pins are arranged to form corner points of a rectangle around the semiconductor arrangement, which semiconductor arrangement thereby forms the centre of the rectangle. The thickness of the intermediary member corresponds substantially to the distance from the upper surface 26 of the semiconductor arrangement to the upper surface 18 of the bottom part. The membrane 6 is a thin circular plate with concentric corrugations 27 which enhance the stiffness of the membrane and which gives the membrane substantially linear pressure/displacement characteristics. The supporting ring 9 has the shape of a circular ring. The supporting ring 9, the intermediary member 4, the bottom part 2 and the membrane 6 are made from an anti corrosive material, e.g. stainless steel. Stainless steel is preferred since it facilitates assembling of the parts by welding but other materials which are suitable for the applied pressures of a specific application could be considered. The shape of the bottom part, the intermediary member and the membrane is chosen to facilitate an easy manufacturing, e.g. in a stamping or punching process. FIG. 2 shows an isometric, cross-sectional view of the assembled pressure sensor. The semiconductor arrangement is arranged in the rectangle formed by the pins. The intermediary member is attached to the bottom part e.g. by welding, e.g. laser welding so that it encircles the semiconductor arrangement and the parts of the pins which project out of the upper surface 18 of the bottom part. The membrane 6 is arranged concentrically on top of the intermediary member, and by means of the supporting ring 9, it is welded onto the intermediary member. The elevated flanges of the intermediary member and of the supporting ring which have been introduced to reduce contact between the membrane and the intermediary member and the supporting ring to a minimum, are clearly seen in FIG. 2. The cavity 28 created by the housing and the membrane is filled with a pressure-transmitting medium, e.g. silicone oil which is injected through the oil channel 20, and subsequently, the channel is sealed with a closure ball 29. The closure ball could be made in a dimension so that it must be pressed into the opening whereby a tight sealing is provided, or the ball could be attached in the opening e.g. by welding, e.g. by resistance welding thereby forming a sealed cavity in the housing. The measuring of the pressure is carried out when the membrane 6 is subjected to a pressure, e.g. when the pressure sensor is mounted in a pressure pipe, e.g. in a chemical process plant. The pressure deflects the membrane 6 and propagates via the silicon oil to the semiconductor arrangement. In the semiconductor arrangement, the deflection of the semiconductor membrane area is sensed by the extensometer, and a signal representing the pressure is transmitted out of the pressure sensor via the pins. FIG. 3 shows a cross-sectional view of the pressure sensor of FIG. 2. As shown the sensor includes a pressure channel 30 establishing fluid communication between a reference pressure chamber 31 of the semiconductor arrangement 7 and a reference pressure medium, e.g. the surrounding atmosphere. Due to channel 30, the semiconductor membrane 25 deflects according to a pressure difference between the pressure in the reference pressure chamber (atmospheric pressure) and the pressure of the medium acting on the membrane 6. The pressure channel 30 is optional, but if present it provides atmospheric pressure in the reference pressure chamber 31. If the pressure channel is omitted the reference pressure chamber is typically evacuated and sealed, thereby providing a substantially fixed reference pressure corresponding to substantially zero pressure. FIGS. 4 and 5 show an alternative embodiment wherein the closure ball 29 is larger than the corresponding ball of the previous embodiments. The ball is fastened in the opening by welding along the joint 38 to completely seal the oil channel 20. Also the intermediary member 4, and the supporting ring 9 are different from those of FIGS. 1-3. In this case the upper surface of the intermediary member as well as the lower surface of the supporting ring are plane. I.e. the contact flanges are not elevated from the upper surface of the intermediary member and the lower surface of the supporting ring. In order to reduce contact between the membrane and the other parts, i.e. the intermediary member and supporting ring, respectively, the membrane comprises a fold 32 raising the middle portion of the membrane from the intermediary member. In FIG. 4, it is clearly seen that the pressure sensor of this embodiment is made for measuring absolute pressure, i.e. the sensor is made without the pressure channel. In FIG. 5, it is clearly seen that the through hole in the intermediary member has a shape corresponding to the shape of the semiconductor arrangement, i.e. a quadrangular shape. For each connecting pin, projecting points or fingers 33 extend radially outwardly to incorporate these pins into the cavity. The reduced volume resulting from the matching shapes of the through hole and the objects within the cavity improves the sensor since it reduces the amount of pressure-transmitting oil necessary for filling up the cavity and thus reduces the need for compensation of temperature caused deviation. FIG. 6 shows an alternative embodiment of the pressure sensor wherein the bottom part 34 is made with a recessed flange forming an apron ring 35 circumferentially around the outer surface of the flange. The apron ring could be welded to the inner surface e.g. of a pressure pipe (not shown). In the shown embodiment, the bottom part is formed with an axially displaced flange whereby the welding surface in a similar manner is displaced axially in relation to the embodiment of FIGS. 1-5. By the axial displacement, the distance between the silicone filled cavity and the outer surface is increased. Since only a fraction of the heat propagates to the cavity, the increased distance facilitates welding with an increased effect without thermally overloading the silicone oil. In accordance with the invention, the geometry of the bottom part is still simple and can be made in a stamping or punching process. FIG. 7 shows a third embodiment of the pressure sensor. The bottom part is similarly made with a recessed flange but the outer surface of the flange is provided with an increased area of the surface 36 when compared to the embodiments of FIGS. 1-5. The increased area provides a larger welding surface enabling a stronger welding, e.g. necessitated by large pressures to be measured. To avoid thermal overloading of the silicone oil, it may be necessary to cool down the pressure sensor during the welding process. Also this geometry of the bottom part may be produced in a cost efficient way by stamping or punching. The pressure sensor housings disclosed in any of the figures are made by at least 3 parts. The bottom part and the intermediary member are made as two separate pieces joined by welding. This facilitates a simple manufacturing in a punching or stamping process and thus makes it possible to lower the manufacturing costs. While the present invention has been illustrated and described with respect to a particular embodiment thereof, it should be appreciated by those of ordinary skill in the art that various modifications to this invention may be made without departing from the spirit and scope of the present invention.
<SOH> BACKGROUND OF THE INVENTION <EOH>Pressure sensors of the above described kind are used in numerous applications, e.g. in connection with operation of combustion engines, chemical process plants and refrigeration systems. In semiconductor based electronic pressure sensors, a silicon chip with a semiconductor membrane area constitutes the pressure-sensing element. An extensometer is mounted to the membrane area for registering deflection in the membrane area when it is exposed to the pressure of a medium. In the heretofore known pressure sensors, the silicon chip is typically mounted on a base made of glass. The chip arrangement, constituted by the silicon chip and the glass base, is mounted in a housing comprising a membrane for separation of the silicon chip from the medium. The separating membrane and housing form a sealed space surrounding the chip arrangement. This space is normally filled completely with a pressure-transmitting medium, e.g. silicon oil through which pressure can propagate. In order to transmit the pressure substantially without pressure-loss, the pressure-transmitting medium inside the housing must have a low compressibility. When the separating membrane is exposed to a pressure, the pressure will be transmitted to the silicon chip and cause a deflection of the semiconductor membrane, which deflection is detected by the extensometer. The required tolerances of the housing are narrow and, accordingly, expensive and time-consuming manufacturing processes have traditionally been used in making pressure sensors of the above-mentioned kind. Typically, the housing, and in particular the cavity therein, is made in a time consuming milling process wherein material is removed from a solid piece of a steel block, or the housing is made by sintering with subsequent machining. Inevitably, this occupies expensive production facilities for a relatively long time. Since the pressure-transmitting medium normally changes volume differently from the housing when exposed to a change in temperature, the pressure signal deriving from the semiconductor arrangement depends on the temperature. I.e. in response to a specific change in temperature, the volume of the chamber, and the volume of the pressure-transmitting medium changes differently. Since the chamber is completely filled with an incompressible medium, and since the chamber is sealed, the volumetric differences must be compensated by deflection of the flexible membrane thereby introducing a deviation in the pressure signal which deviation depends on the flexibility of the membrane and the temperature. Normally, the semiconductor arrangement is electrically connected to an electronic circuit comprising an arrangement for compensating the temperature caused deviation. Such compensating arrangement is, however, expensive and requires space, and the dimension thereof depends on the necessitated degree of compensation. In order to reduce the deviation caused by a changing temperature, it is sometimes attempted to limit the amount of free space around the semiconductor in the cavity. The limited space reduces the amount of pressure-transmitting medium necessary to fill up the cavity and thus reduces the impact of changes in the temperature. Both U.S. Pat. No. 5,436,491 and U.S. Pat. No. 4,502,335 disclose pressure sensors of this kind. These kinds of refined sensors comprise housings made from moulded or machined body casings and further comprise moulded fillers to reduce the free space in the cavity. The design and corresponding manufacturing costs of the sensors are even higher than the costs of making the aforementioned traditional sensors, and the use of fillers introduce additional manufacturing steps.
<SOH> SUMMARY OF THE INVENTION <EOH>It is an object of the present invention to solve problems associated with the manufacturing of pressure sensors. Accordingly, the invention in a first aspect provides a pressure sensor of the kind mentioned in the introduction, characterised in that the housing comprises an intermediary member attached between the bottom part and the membrane and comprising an aperture forming at least a part of the cavity. Due to the use of an intermediary member attached between the bottom part and the membrane, the housing can be made in simple and fast production steps e.g. by stamping or punching the bottom part, the intermediary member and/or the membrane out of plate shaped bodies, and subsequently assembling the parts, e.g. by welding. The aperture in the intermediary member may e.g. form part of the sidewall of the cavity. The intermediary member may be formed by any number of parts. It may have a laminated structure made from a plurality of discs or it may be formed from sectors of semicircular disc segments joint by welding. If it is desired to limit the amount of the pressure-transmitting medium, e.g. to reduce the need for compensation of the signal from the sensor, the spacing around the pressure sensing arrangement in the cavity can easily be reduced. In this case, the intermediate member can be made with an aperture having a cross sectional profile matching the profile of the pressure sensing arrangement in a corresponding cross-sectional view. When the intermediate member is attached between the bottom part and the membrane, the aperture forms a sidewall of the cavity, and due to the matching cross-sectional profiles of the aperture and the pressure sensing arrangement, the amount of pressure-transmitting medium necessary to fill up the cavity is reduced. The possibly somewhat tortuous profile of the aperture can be made in the intermediary member using any convenient process known in the art, e.g. a stamping process, and it is thus possible to make the profile at a high speed even within narrow dimensional tolerances. If additional space is required for electrical connections between the pressure sensing arrangement and external equipment, the aperture could be punched in any shape and thus provide the necessary space for such additional components. As an example, it may be desired to arrange connecting pins through the bottom part and into the cavity for establishing electrical connections through the housing. The openings in the bottom part may be punched or stamped in one and the same operation in which the general shape of the bottom part is made and the intermediary member may have an aperture, e.g. with a cross sectional shape as a star, leaving space in the middle for a pressure sensing arrangement and space in the projecting points or fingers of the star for the connecting pins. In a specifically simple and easily manufactured embodiment, the intermediary member and the bottom part are joined in matching plane surfaces. The bottom part and/or the intermediary member could be made from a plate shaped material, e.g. of a non-corrosive material such as stainless steel, a ceramic material or Kovar. Similarly, the membrane could be made from a disc of stainless steel. The bottom part and the intermediary member could be joined by laser welding, Electron Beam Welding (EBW), Wolfram Inert gas welding (WIG), resistance welding or by soldering or gluing. The membrane could be fastened to the intermediary member by any similar process, e.g. by use of a ring extending circumferentially around the outer peripheral edge of the membrane and preferably overlapping this edge. Preferably, the pressure sensing arrangement is a semiconductor arrangement having a base, e.g. made of glass. A conduit for filling the cavity with the pressure-transmitting medium, e.g. silicone oil, may be made as a penetration through one of the bottom part and the intermediary member. The hole could be sealed with a closure having the shape of a spherical ball and being fastened to the hole via welding, e.g. resistance welding. Such welding may be conducted with the housing submersed into silicon oil. In one embodiment, the conduit is formed between the bottom part and the intermediary member, e.g. by making a groove in the surface wherein the intermediary member and the bottom part are joined. Electrically conductive pins entering into the cavity e.g. through holes in the bottom part or in the intermediary member for electrically connecting the semiconductor arrangement with outside equipment may preferably be electrically isolated from the bottom part or intermediary member, in particular if the bottom part or intermediary member is made from an electrically conductive material. The membrane could be attached to a first contact flange of an upper surface of the intermediary member, i.e. opposite the surface where the intermediate member is attached to the base part, e.g. by welding, gluing or by similar assembling processes. In order to ensure a more solid fixation of the membrane to the intermediary member, a supporting ring could be fastened on top of the membrane, e.g. in a welding operation wherein the supporting ring is welded to the membrane, and to the intermediary member. In order to reduce contact between the membrane and the intermediary member, the first contact flange may form a circumferentially extending elevation of the upper surface allowing the membrane to rest on the contact flange and to remain unsupported by the remaining part of the intermediary member. In a similar manner, the supporting ring may have a second contact flange of a lower surface thereof, i.e. on a surface opposite to an upper and outer surface of the supporting ring when attached to the membrane and to the intermediary member. The second contact flange is attached to an outer surface of the membrane above the first contact flange, and in order to reduce contact between the membrane and the supporting ring, the second contact flange may form a circumferentially extending elevation of the lower surface. According to a second aspect, the present invention relates to a method of making a pressure sensor comprising a housing with a cavity having an opening in an upper surface of the housing, a pressure sensing arrangement placed in the cavity for sensing pressure, and a membrane covering the opening and attached to the housing to provide a substantially closed space in the cavity, wherein a bottom part and an intermediary member is assembled to form the housing, characterized in that the membrane is attached to a contact face of the intermediary member. In particular, one of the bottom part and the intermediary member may be formed in a stamping process. The method may be combined with any step necessary for making any of the aforementioned embodiments of a pressure sensor.
20050609
20071225
20060309
72051.0
G01L700
0
ALLEN, ANDRE J
PRESSURE SENSOR
UNDISCOUNTED
0
ACCEPTED
G01L
2,005
10,538,294
ACCEPTED
Washer fluid squirt device for motor vehicle windscreen washer jets
The device is comprised of a jet body (2) and a body for a fan shaped squirt (3) which can be mutually coupled. The squirt body (3) has a squirting orifice (9) which comprises four consecutively connected portions, of which, in the washer fluid flow direction, the first portion (10) is conical and in decreasing section; the second section portion (11) forms a spherical cap in decreasing section; the third portion (12) is in rectangular cross-section and in increasing section; and the fourth portion (15) is in rectangular cross-section in decreasing section in said flow direction and configures a convex outlet edge (16), which is surrounded by an outer lateral squirting groove.
1. Washer fluid squirt device for motor vehicle windscreen washer jets object of the invention, comprised of a jet body (2) and a body (3) for a fan-shaped squirt of washer fluid equipped with a squirting orifice (9) and coupled to the jet body (2), in such a way that it can be rotated around its longitudinal axis, characterised in that the squirting orifice (9) comprises four conduit portions which are consecutively connected without interruption, thus defining a conduit axis and in such a way that its longitudinal section is symmetrical with regard to a theoretical main transverse plane, of which the first portion (10), which is the innermost one, is conical and in progressively decreasing section in the flow direction of the washer fluid; the second portion (11) forms a spherical cap in decreasing section in the flow direction of the washer fluid; the third portion (12) is in rectangular cross-section and in progressively increasing section in the flow direction of the washer fluid and when connecting with the second portion (11) configures a rectangular window (13) whose end sides (14) are situated inwardly with regard to the tangency determined by the connection of the first portion (10) with the second portion (11); and the fourth portion (15) is in rectangular cross-section in decreasing section in the flow direction of the washer fluid, which configures without interruption a convex exit edge (16) of the washer fluid and in that the squirt body (3) is provided with a lateral squirting groove (18) perpendicularly arranged as regards the conduit axis of the squirting orifice (9), which surrounds the exit edge (16) of the squirting orifice (9) and the bottom part of which is below the level corresponding to the connection of the third portion (12) with the fourth portion (15) of the squirting orifice (9). 2. Squirt device according to claim 1, characterised in that the lateral squirting groove (18) has a cross-section whose outline comprises a first concave portion (19) that connects tangentially with the convex exit edge (16) of the squirting orifice (9) and a second straight portion (20) that connects tangentially with the first concave portion (19), forming an outwardly orientated angularity.
TECHNICAL SECTOR OF THE INVENTION The present invention relates to a washer fluid squirt device for motor vehicle windscreen washer jets. BACKGROUND TO THE INVENTION Many embodiments of washer fluid squirt devices for motor vehicle windscreens are known. Essentially, said devices are comprised of a jet body and a squirt body, capable of being mutually coupled, wherein the jet body is equipped with means for its mounting onto the vehicle bodywork and means for the connection of a washer fluid pipe from a tank, and the squirt body is equipped with means for squirting washer fluid onto the windscreen and means for allowing said squirt to be directed in order to optimise the action of the wiper blades. The patent ES P 200100234, by the same applicant, discloses a washer fluid squirt device which, in essence, comprises a jet body and a unit for a fan-shaped squirt of washer fluid, consisting of a first squirt body and a second squirt body, capable of being mutually coupled and configuring two equal conduits of washer fluid which originate in an inlet chamber and converge in an outlet chamber. The patent FR 2 803 542 discloses a water jet for motor vehicle windscreen washer fluid, essentially comprised of a jet body and a body for a fan-shaped squirt of washer fluid, equipped with a rectangular section conduit, wherein there is a longitudinal centred rib, said conduit originating in a transversally cylindrical inlet chamber. The Pat. No. 2,726,204 discloses a jet for cleaning motor vehicle windscreens which is essentially comprised of a jet body and a body for a fan-shaped squirt of washer fluid, equipped with a circular section conduit, the outer end of which has a transversally arranged V-shaped outlet aperture. EXPLANATION OF THE INVENTION The washer fluid squirt device for motor vehicle windscreen washer jets object of the invention, Is comprised of a jet body and a body for a fan-shaped squirt of washer fluid provided with a squirting orifice and coupled to the jet body, in such a way that it can be rotated around its longitudinal axis. The device of the invention Is characterised in that the squirting orifice comprises four conduit portions which are consecutively connected without interruption, thus defining a conduit axis and in such a way that its longitudinal section is symmetrical with regard to a theoretical main transverse plane, of which the first portion, which is the innermost one, is conical and in progressively decreasing section in the flow direction of the washer fluid; the second portion forms a spherical cap of decreasing section in the flow direction of the washer fluid; the third portion is in rectangular cross-section and in progressively increasing section in the flow direction of the washer fluid and when connecting with the second portion configures a rectangular window whose end sides are situated inwardly with regard to the tangency determined by the connection of the first portion with the second portion; and the fourth portion is in rectangular cross-section in decreasing section in the flow direction of the washer fluid, which configures without interruption, a convex outlet edge for the washer fluid and wherein the squirt body is equipped with a lateral squirting groove, perpendicularly arranged as regards the conduit axis of the squirting orifice, which surrounds the exit edge of the squirting orifice and the bottom part thereof is below the level corresponding to the connection of the third portion with the fourth portion of the squirting orifice. It is also characteristic of the device of the invention that the lateral squirting groove has a cross-section whose outline comprises a first concave portion that connects tangentially with the convex exit edge of the squirting orifice and a second straight portion that connects tangentially with the first concave portion, forming an outwardly directed angularity. The previously described features of the device of the invention provide solutions to problems which the known embodiments of squirt devices, such as the aforementioned create, most prominent among said problems being the uniform distribution of washer fluid in the arc shaped by the fan-shaped squirt; the plugging of the sides of the squirt aperture, caused by low temperatures, resulting in the washer fluid being squirted onto one place on the windscreen as a single jet; and high production costs. The characteristics of the device of the invention provide the advantages which are set out in detail below. The fan-shaped squirting of washer fluid is done by concentrating a greater amount of washer fluid in the outer areas of the fan, thus enhancing the driver's vision during the spraying of the windscreen, unlike the known embodiments wherein the fluid distribution Is uniform throughout the entire fan-shaped squirt; the washer fluid is squirted by means of an outlet aperture which is large enough to ensure a fan-shaped squirt at low temperatures, unlike the known embodiments, wherein the outlet aperture leads to the plugging of its lateral areas, and thus results in the loss of the fan-shaped squirt of liquid; and, the fact that the squirt body is made up of a single part reduces production costs in relation to those embodiments requiring two or more parts in order to attain the fan-shaped squirting of washer fluid. BRIEF DESCRIPTION OF THE DRAWINGS Illustrated in the attached drawings, by way of non-limiting example, is a form of embodiment of the washer fluid squirt device for motor vehicle windscreen washer jets object of the invention. In said drawings: FIG. 1 is a diagrammatic view of the squirt device of the invention; FIGS. 2, 3 and 4 are respective side views of the squirt body of the squirt device of the invention; FIG. 5 is the view corresponding to section V-V of FIG. 2; and FIG. 6 is the view corresponding to section VI-VI of FIG. 2. DETAILED DESCRIPTION OF THE DRAWINGS In FIG. 1, the washer fluid squirt device 1 for motor vehicle windscreen washer jets object of the invention is represented and which, as an embodiment example, is described below. The squirt device 1 essentially comprises a jet body 2, which is basically parallelepiped and adapted to each specific application and an essentially cylindrical-shaped body 3 for a fan-shaped squirting of washer fluid, both being mutually coupled. The jet body 2 is provided with a slot 4, adapted to snugly receive the squirt body 3 and In such a way that the latter may be rotated around its longitudinal axis, with means for fixing to the vehicle bodywork, not shown, and with means for connecting a washer fluid pipe, which are also not shown, as well as a conduit 5, represented by dashes, which connects said washer fluid pipe hydraulically with the slot 4. In FIGS. 2, 3 and 4, it can be appreciated that the squirt body 3 is provided with positioning means with regard to the jet body 2, which comprise a protuberance 6 at one of its ends and a groove 7 at the other end, the protuberance 6 being adapted for housing in a corresponding cavity, not shown, of the slot 4 of the jet body 2, intended to limit the rotation of the squirt body 3 around its longitudinal axis, whereas the groove 7 is adapted for receiving a tool, such as the blade end of a screwdriver, enabling the user to rotate the squirt body 3, thus determining the area in which the washer fluid squirted in a fan-shape 8 reaches the vehicle windscreen. With reference to FIGS. 5 and 6, it can be appreciated that the squirt body 3 is equipped with a squirting orifice 9, arranged transversally and in such a way that, as FIG. 1 shows, it remains facing the conduit 5 that connects hydraulically with said washer fluid pipe. FIG. 5 shows in detail that the squirting orifice 9 comprises four well-defined conduit portions, which are connected consecutively and whose longitudinal section is symmetrical with regard to a theoretical main transverse plane of the squirt body 3. The first portion 10, that which is facing the conduit 5 of the jet body 2, is conical and has a progressively decreasing section in the flow direction of the washer fluid; the second portion 11 forms a spherical cap with decreasing section in the flow direction of the washer fluid; the third portion 12 has a rectangular cross-section and progressively increasing section in the flow direction of the washer fluid, configuring, in its connection with the second portion 11, a rectangular window 13, represented in FIGS. 2 and 4, whose end sides 14, represented in FIG. 6, are situated inwardly with regard to the tangency determined by the connection of the first portion 10 with the second portion 11, indicated in FIG. 6 by means of a dashed line; and the fourth portion 15 has a rectangular cross-section in decreasing section in the flow direction of the washer fluid, this fourth portion 15 determining a large outwardly convex outlet edge 16 which, in this embodiment example of the device of the invention, confines itself to a circumferential edge over a spherical cap 17 which configures the lateral surface of the squirt body 3, represented in FIGS. 3 and 4. The squirt body 3 has a lateral squirting groove 18, shown in section in FIG. 5, perpendicularly arranged with regard to the longitudinal axis of the squirting orifice 9 and which surrounds the outlet edge 16, the squirt groove 18 having a cross-section whose outline comprises a first concave portion 19 which connects tangentially at one end with the convex edge 16 of the squirting orifice 9, and by one end connects with a second straight portion 20 that forms an outwardly directed angularity, all adapted so that the bottom part of the lateral squirt groove 18 is situated below the level corresponding to the connection of the third portion 12 with the fourth portion 15 of the squirting orifice 9. The fan-shaped squirting of the washer fluid by the squirting device of the invention is represented in FIG. 1, wherein it can firstly be appreciated that the squirting of washer fluid onto the vehicle windscreen is symmetrical with regard to a vertical plane Y-Y, and secondly, that it results in a greater concentration of washer fluid at the ends of the fan-shaped squirt, and this, as has been pointed out earlier, enhances the driver's vision during the spraying of the windscreen.
<SOH> BACKGROUND TO THE INVENTION <EOH>Many embodiments of washer fluid squirt devices for motor vehicle windscreens are known. Essentially, said devices are comprised of a jet body and a squirt body, capable of being mutually coupled, wherein the jet body is equipped with means for its mounting onto the vehicle bodywork and means for the connection of a washer fluid pipe from a tank, and the squirt body is equipped with means for squirting washer fluid onto the windscreen and means for allowing said squirt to be directed in order to optimise the action of the wiper blades. The patent ES P 200100234, by the same applicant, discloses a washer fluid squirt device which, in essence, comprises a jet body and a unit for a fan-shaped squirt of washer fluid, consisting of a first squirt body and a second squirt body, capable of being mutually coupled and configuring two equal conduits of washer fluid which originate in an inlet chamber and converge in an outlet chamber. The patent FR 2 803 542 discloses a water jet for motor vehicle windscreen washer fluid, essentially comprised of a jet body and a body for a fan-shaped squirt of washer fluid, equipped with a rectangular section conduit, wherein there is a longitudinal centred rib, said conduit originating in a transversally cylindrical inlet chamber. The Pat. No. 2,726,204 discloses a jet for cleaning motor vehicle windscreens which is essentially comprised of a jet body and a body for a fan-shaped squirt of washer fluid, equipped with a circular section conduit, the outer end of which has a transversally arranged V-shaped outlet aperture.
<SOH> BRIEF DESCRIPTION OF THE DRAWINGS <EOH>Illustrated in the attached drawings, by way of non-limiting example, is a form of embodiment of the washer fluid squirt device for motor vehicle windscreen washer jets object of the invention. In said drawings: FIG. 1 is a diagrammatic view of the squirt device of the invention; FIGS. 2, 3 and 4 are respective side views of the squirt body of the squirt device of the invention; FIG. 5 is the view corresponding to section V-V of FIG. 2 ; and FIG. 6 is the view corresponding to section VI-VI of FIG. 2 . detailed-description description="Detailed Description" end="lead"?
20050610
20071016
20060223
63604.0
B05B110
0
HWU, DAVIS D
WASHER FLUID SQUIRT DEVICE FOR MOTOR VEHICLE WINDSCREEN WASHER JETS
UNDISCOUNTED
0
ACCEPTED
B05B
2,005
10,538,376
ACCEPTED
Novel semisynthetic macrolide antibiotics of the azalide series
The invention relates to N″-substituted 9a-N-(N′-carbamoyl-γ-aminopropyl), 9a-N-(N′-thiocarbamoyl-γ-amino-propyl), 9a-N-[N′-((β-cyanoethyl)-N′-carbamoyl-γ-aminopropyl] and 9a-N-[N′-((β-cyanoethyl)-N′-thiocarbamoyl-γ-aminopropyl] derivatives of 9-deoxo-9-dihydro-9a-aza-9a-homoerithromycin A and 5-0-desosaminyl-9-deoxo-9-dihydro-9a-aza-9a-homoerithronolide A, novel semisynthetic macrolide antibiotics of the azalide series, of the general formula 1, wherein R represents H or cladinosyl moiety, R1 represents H or (β-cyanoethyl moiety, R2 represents isopropyl, 1-naphtyl, 2-naphtyl, benzyl, 2-(trifluommethyl)phenyl, 3-phenylpropyl, β-phenylethyl, ethoxycarbonylmethyl, 1-(1-naphtyl)ethyl, 3,4,5-trimethoxyphenyl and 2,4-dichlorophenyl group, and X represents 0 and S, and their acceptable addition salts thereof with inorganic or organic acids, to the process for preparation of their pharmaceutical compositions as well as the use their compositions in the treatment of bacterial infections.
1. N″-Substituted 9a-N-(N′-carbamoyl-γ-aminopropyl), 9a-N-(N′-thiocarbamoyl-γ-aminopropyl), 9a-N-[N′-(β-cyanoethyl)-N′-carbamoyl-γ-aminoprolpyl] and- 9a-N-[N′-((β-cyanoethyl)-N′-thiocarbamoyl-γ-aminopropyl] derivatives of 9-deoxo-9-dihydro-9a-aza-9a-homoerithromycin A and 5-O-desosaminyl-9-deoxo-9-dihydro-9a-aza-9a-homoerithronolide A, novel semisynthetic macrolide antibiotics of the azalide series of the general formula 1, wherein R represents H or cladinosyl moiety, R1 represents H or β-cyanoethyl moiety, R2 represents isopropyl, 1-naphtyl, 2-naphtyl, benzyl, 2-(trifluoromethyl)phenyl, 3-phenylpropyl, β-phenylethyl, ethoxycarbonyl-methyl, 1-(1-naphtyl)ethyl, 3,4,5-trimethoxyphenyl or a 2,4-dichlorophenyl group, and X represents O or S, and their acceptable addition salts thereof with inorganic or organic acids. 2. Substance according to claim 1, characterized in that R1 represents H, R2 represents isopropyl group and X is O. 3. Substance according to claim 1, characterized in that, R1 represents H, and R2 represents 1-naphthyl group and X is O. 4. Substance according to claim 1, characterized in that R1 represents H and R2 represents 2-naphtyl group and X is O. 5. Substance according to claim 1, characterized in that R1 represents H and R2 represents benzyl group and X is O. 6. Substance according to claim 1, characterized in that R1 represents H and R2 represents 2-(trifluoromethyl) phenyl group and X represents O. 7. Substance according to claim 1, characterized in that R1 represents H and R2 represents 3-phenylpropyl group and X is S. 8. Substance according to claim 1, characterized in that R1 represents H and R2 represents β-phenylethyl group and X is S. 9. Substance according to claim 1, characterized in that R1 represents H and R2 represents ethoxycarbonylmethyl group and X is O. 10. Substance according to claim 1, characterized in that R1 represents H and R2 represents 1-(1-naphtyl) ethyl group and X is O. 11. Substance according to claim 1, characterized in that R1 represents H and R2 represents 3,4,5-trimethoxyphenyl group and X is O. 12. Substance according to claim 1, characterized in that R1 represents H and R2 represents 2,4-dichlorophenyl group and X is O. 13. Substance according to claim 1, characterized in that R1 represents H and R2 represents benzyl group or 1-naphtyl group and X is S. 14-19. (canceled) 20. Substance according to claim 1, characterized in that, R1 represents β-cyanoethyl group, R2 represents 3-phenylpropyl group and X is S. 21. Substance according to claim 1, characterized in that R1 represents β-cyanoethyl group, R2 represents β-phenylethyl group and X is S. 22-24. (canceled) 25. Substance according to claim 1, characterized in that R1 represents β-cyanoethyl group, R2 represents 2,4-dichlorophenyl group and X is O. 26-53. (canceled) 54. Process for the preparation of N″-substituted 9a-N-(N′-carbamoyl-γ-aminopropyl), 9a-N-(N′-thiocarbamoyl-γ-aminopropyl), 9a-N-[N′-(β-cyanoethyl)-N′-carbamoyl-γ-aminopropyl] and 9a-N-[N′-(β-cyanoethyl)-N′-thiocarbamoyl-γ-aminopropyl] derivatives of 9-deoxo-9-dihydro-9a-aza-9a-homoerithromycin A and 5-O-desosaminyl-9-deoxo-9-dihydro-9a-aza-9a-homoerithronolide A, of the general formula 1, wherein R represents H or cladinosyl moiety, R1 represents H or β-cyanoethyl moiety, R2 represents isopropyl, 1-naphtyl, 2-naphtyl, benzyl, 2-(trifluoromethyl) phenyl, 3-phenylpropyl, β-phenylethyl, ethoxycarbonylmethyl, 1-(1-naphtyl)ethyl, 3,4,5-trimethoxyphenyl and 2,4-dichlorophenyl group, and X represents O or S, characterized in that 9a-N-(γ-aminopropyl) and 9a-N-[N′-(β-cyanoethyl)-γ-aminopropyl] derivatives of 9-deoxo-9-dihydro-9a-aza-9a-homoerithromycin A and 5-O-desosaminyl-9-deoxo-9-dihydro-9a-aza-9a-homoerithronolide A general formula 2, wherein R represents H or a cladinosyl group and R1 represents H or a β-cyanoethyl group is reacted with isocyanates or isothiocyanates general formula 3 R2—N═C═X3 wherein R2 represents isopropyl, 1-naphtyl, 2-naphtyl, benzyl, 2-(trifluoromethyl) phenyl, 3-phenylpropyl, (3-phenylethyl, ethoxycarbonyl-methyl, 1-(1-naphtyl) ethyl, 3,4,5-trimethoxyphenyl and 2,4-dichlorophenyl group, and X represents O or S, in toluene, xylene or some others aprotic solvents at a temperature 0°-110° C. and then, if appropriate, to a reaction with inorganic or organic acids. 55. Pharmaceutical compositions comprising a pharmaceutically acceptable carrier and an antibacterially effective amount of the substance according to claim 1. 56. (canceled) 57. A method of treating bacterial infections comprising administering the substance according to claim 1. 58. The method according to claim 57, wherein R1 represents H. 59. The method according to claim 57, wherein R2 represents a 1-naphthyl, 2-naphthyl, 1-(1-naphtyl)ethyl, or 2,4-dichlorophenyl group.
TECHNICAL FIELD The present invention relates to N″-substituted 9a-N-(N′-carbamoyl-γ-aminopropyl), 9a-N-(N′-thiocarbamoyl-γ-aminopropyl), 9a-N-[N′-(β-cyanoethyl)-N′-carbamoyl-γ-aminopropyl] and 9a-N-[N′-(β-cyanoethyl)-N′-thiocarbamoyl-γ-aminopropyl] derivatives of 9-deoxo-9-dihydro-9a-aza-9a-homoerithromycin A and 5-O-desosaminyl-9-deoxo-9-dihydro-9a-aza-9a-homoerithronolide A, novel semisynthetic macrolide antibiotics of the azalide series having antibacterial activity, of the general formula 1, wherein R represents H or cladinosyl moiety, and R1 represents H or β-cyanoethyl group, R2 represents isopropyl, 1-naphtyl, 2-naphtyl, benzyl, 2-(trifluoromethyl)phenyl, 3-phenylpropyl, β-phenylethyl, ethoxycarbonylmethyl, 1-(1-naphtyl)ethyl, 3,4,5-trimethoxyphenyl and 2,4-dichlorophenyl group, and X represents O or S, to pharmaceutically acceptable addition salts thereof with inorganic or organic acids, to a process for the preparation of the pharmaceutical compositions as well as to the use of the pharmaceutical compositions obtained in the treatment of bacterial infections. PRIOR ART Erithromycin A is a macrolide antibiotic , whose structure is characterized by 14-membered macrolactone ring having carbonyl group in C-9 position. It was found by McGuire in 1952 [Antibiot. Chemother., 2 (1952) 281] and for over 40 years it has been considered as a reliable and effective antimicrobial agent in the treatment of diseases caused by Gram-positive and some Gram-negative microorganisms. However, in an acidic medium it is easily converted into anhydroerythromycin A, an inactiv C-6/C-12 metabolite of a spiroketal structure [P. Kurath et al., Experientia 27 (1971) 362]. It is well-known that spirocyclisation of aglycone ring of erythromycin A is successfully inhibited by a chemical transformation of C-9 ketones or hydroxy groups in C-6 and/or C-12 position. By the oximation of C-9 ketones [S. okić et al., Tetrahedron Lett. 1967: 1945] and by subsequently modifying the obtained 9(E)-oxime into 9-[O-(2-methoxy-ethoxy)methyloxime]erithromycin A (ROXITHROMYCIN) [G. S. Ambrieres, Fr. pat. 2,473,525, 1981] or 9(S)-erithromycylamine [R. S. Egan et al., J. Org. Chen. 39 (1974) 2492] or a more complex oxazine derivative thereof, 9-deoxo-11-deoxy-9,11-{imino[2-(2-methoxyethoxyethylidene]oxy}-9(S)-erythromycin A (DIRITHROMYCIN) [P. Lugar et al., J. Crist. Mol. Struct. 9 (1979) 329], novel semisynthetic macrolides were synthetized, whose basic characteristic, in addition to a greater stability in an acidic medium, is a better pharmacokinetics and a long half-time with regard to the parent antibiotic erythromycin A. In a third way for modifying C-9 ketones use is made of Beckmann rearrangement of 9(E)-oxime and of a reduction of the obtained imino ether (G. Kobrehel et al., U.S. Pat. No. 4,328,334, 1982.) into 11-aza-10-deoxo-10-dihydroerythromycin A (9-deoxo-9a-aza-9a-homoerythromycin A) under broadening the 14-member ketolactone ring into a 15-member azalactone ring. By reductive N-methylation of 9a-amino group according to Eschweiler-Clark process (G. Kobrehel et al., BE Pat. 892,397, 1982.) or by a preliminary protection of amino group by means of conversion into the coresponding N-oxides and then by alkylation and reduction [G. M. Bright, U.S. Pat. No. 4,474,768, 1984.] N-methyl-11-aza-10-deoxo-10-dihydroerythromycin A (9-deoxo-9a-methyl-9a-aza-9a-homoerithromycin A, AZITHROMYCIN) was syntetized, a prototype of azalide antibiotics, which, in addition to a broad antimicrobial spectrum including Gram-negative bacteria and intrcellular microorganisms, are characterized by a specific mechanism of transport to the application site, a long biological half-time and a short therapy period. In EP A 0316128 (Bright G. M. et al.) novel 9a-allyl and 9a-propargyl derivatives of 9-deoxo-9a-aza-9a-homoerythromycin A are disclosed and in U.S. Pat. No. 4,492,688, from 1985 (Bright G. M.) the synthesis and the antibactertial activity of the corresponding cyclic ethers are disclosed. In the there are further disclosed the syntesis and the activity spectrum of novel 9-deoxo-9a-aza-11-deoxy-9a-homoerythromycin A 9a,11-cyclic carbamates and O-methyl derivatives thereof (G. Kobrehel et al., J. Antibiot. 46 (1993) 1239-1245). By reaction of 9-deoxo-9-dihydro-9a-aza-9a-homoerithromycin A with isocyanates or isothiocyanates respectively [N. Kujundzić et al. Croat. Pat. 931480, 1993.], 9a-N-(N′-carbamoyl) and 9a-N-(N′-thiocarbamoyl) derivatives of 9-deoxo-9-dihydro-9a-aza-9a-homoerithromycin A with a certian antibacterial activity are obtained. According to the known and established Prior Art, N″-substituted 9a-N-(N′-carbamoyl-γ-aminopropyl), 9a-N-(N′-thiocarbamoyl-γ-aminopropyl), 9a-N-[N′-(β-cyanoethyl)-N′-carbamoyl-γ-aminopropyl] and 9a-N-[N′-(β-cyanoethyl)-N′-thiocarbamoyl-γ-aminopropyl] derivatives of 9-deoxo-9-dihydro-9a-aza-9a-homoerithromycin A and 5-O-desosaminyl-9-deoxo-9-dihydro-9a-aza-9a-homoerithronolide A and pharmaceutically acceptable addition salts thereof with inorganic or organic acids, a process for the preparation thereof as well as the preparation methods and use an pharmaceutical preparations have not been disclosed as yet. It has been found and it is object of the present invention, that N″-substituted 9a-N-(N′-carbamoyl-γ-aminopropyl), 9a-N-(N′-thiocarbamoyl-γ-aminopropyl), 9a-N-[N′-(β-cyanoethyl)-N′-carbamoyl-γ-aminopropyl] and 9a-N-[N′-(β-cyanoethyl)-N′-thiocarbamoyl-γ-aminopropyl] derivatives of 9-deoxo-9-dihydro-9a-aza-9a-homoerithromycin A and 5-O-desosaminyl-9-deoxo-9-dihydro-9a-aza-9a-homoerithronolide A, novel semisinthetic macrolide antibiotic of the azalide series and pharmaceutically acceptable addition salts thereof with inorganic or organic acids, may be prepared by reacting 9a-N-(γ-aminopropyl) and 9a-N-[N′-(β-cyanoethyl)-γ-aminopropyl] derivatives of 9-deoxo-9-dihydro-9a-aza-9a-homoerithromycin A and 5-O-desosaminyl-9-deoxo-9-dihydro-9a-aza-9a-homoerithronolide A with isocyanates or isothiocyanates and optionally by reacting the obtained N″-substituted 9a-N-(N′-carbamoyl-γ-aminopropyl), 9a-N-(N′-thiocarbamoyl-γ-aminopropyl), 9a-N-[N′-(β-cyanoethyl)-N′-carbamoyl-γ-aminopropyl] and 9a-N-[N′-(β-cyanoethyl)-N′-thiocarbamoyl-γ-aminopropyl] derivatives of 9-deoxo-9-dihydro-9a-aza-9a-homoerithromycin A and 5-O-desosaminyl-9-deoxo-9-dihydro-9a-aza-9a-homoerithronolide A with organic and inorganic acids. TECHNICAL SOLUTION It has been found that novel N″-substituted 9a-N-(N′-carbamoyl-γ-aminopropyl), 9a-N-(N′-thiocarbamoyl-γ-aminopropyl), 9a-N-[N′-(β-cyanoethyl)-N′-carbamoyl-γ-aminopropyl] and 9a-N-[N′-(β-cyanoethyl)-N-thiocarbamoyl-γ-aminopropyl] derivatives of 9-deoxo-9-dihydro-9a-aza-9a-homoerithromycin A and 5-O-desosaminyl-9-deoxo-9-dihydro-9a-aza-9a-homoerithronolide A of the general formula 1, wherein R represents H or cladinosyl group, R1 represents H or β-cyanoethyl moiety, R2 represents isopropyl, 1-naphtyl, 2-naphtyl, benzyl, 2-(trifluoromethyl)phenyl, 3-phenylpropyl, β-phenylethyl, ethoxycarbonylmethyl, 1-(1-naphtyl)ethyl, 3,4,5-trimethoxyphenyl and 2,4-dichlorophenyl group, and X represents O or S, and their acceptable addition salts there of with inorganic or organic acids, may be prepared by reacting 9a-N-(β-aminopropyl) and 9a-N-[N′-(β-cyanoethyl)-γ-aminopropyl] derivatives of 9-deoxo-9-dihydro-9a-aza-9a-homoerithromycin A and 5-O-desosaminyl-9-deoxo-9-dihydro-9a-aza-9a-homoerithronolide A general formula 2, wherein R represents H or cladinosyl group and R1 represents H or β-cyanoethyl moiety, with isocyanates or thioisocyanates general formula 3, R2—N═C═X 3 wherein R2 and X have above meanings, in toluene, xylene or some other aprotic solvent, at a temperature 0° to 110° C. Pharmaceutically acceptable acid addition salts, which also represent an object of present invention, were obtained by reaction N″-substituted 9a-N-(N′-carbamoyl-γ-aminopropyl), 9a-N-(N′-thiocarbamoyl-γ-aminopropyl), 9a-N-[N′(β-cyanoethyl)-N′-carbamoyl-γ-aminopropyl] and 9a-N-[N′-(β-cyanoethyl)-N′-thiocarbamoyl-γ-aminopropyl] derivatives of 9-deoxo-9-dihydro-9a-aza-9a-homoerithromycin A and 5-O-desosaminyl-9-deoxo-9-dihydro-9a-aza-9a-homoerithronolide A with an at least equimolar amount of the corresponding inorganic or organic acid such as hydrochloric acid, hydroiodic acid, sulfuric acid, phosphoric acid, acetic acid, trifluoroacetic acid, propionic acid, benzoic acid, benzenesulfonic acid, methane sulfonic acid, laurylsulfonic acid, stearic acid, palmitic acid, succinic acid, ethylsuccinic acid, lactobionic acid, oxalic acid, salicylic acid and similar acid, in a solvent inert to the reaction. Addition salts are isolated by evaporating the solvent or, alternatively, by filtration after a spontaneous precipitation or a precipitation by the addition of a non-polar cosolvent. N″-Substituted 9a-N-(N′-carbamoyl-γ-aminopropyl), 9a-N-(N′-thiocarbamoyl-γ-aminopropyl), 9a-N-[N′-(β-cyanoethyl)-N′-carbamoyl-γ-aminopropyl] and 9a-N-[N′-(β-cyanoethyl)-N′-thiocarbamoyl-γ-aminopropyl] derivatives of 9-deoxo-9-dihydro-9a-aza-9a-homoerithromycin A and 5-O-desosaminyl-9-deoxo-9-dihydro-9a-aza-9a-homoerithronolide A of the general formula 1 and pharmaceutically acceptable addition salts with inorganic or organic acids thereof possess an antibacterial activity in vitro. Minimal inhibitory concentration (MC) is defined as the concentration which shows 90% growth inhibition, and was determinated by broth dilution methods National Committe for Clinical Laboratory Standards (NCCLS, M7-A2 protocols). Final concentration of test substances were in range from 64 to 0.125 mg/l. MIC levels for all compound were determinated on panel of susceptible, and resistant Gram positive bacterial strains (S. aureus, S. pneumoniae and S. pyogenes) and on Gram negative strains (E. coli, H. influenzae, E. faecalis, M. catarrhalis). It is evident from Table 1 and Table 2 that standard strains are susceptible to newly synthetized compounds of general formula 1. Thus they may be used as therapeutic agents in the treatment of invective diseases in animals, especially mammals and humans, caused by a broad spectrum of Gram-positive and Gram-negative bacteria, mycoplasmas and generally patogenic microorganisms that are susceptible to the compounds of the formula 1. To this purpose the above compounds and pharmaceutically acceptable acid addition salts thereof may be administered orally in usual doses from 0.2 mg/kg body weight daily to about 250 mg/kg/day, most preferably from 0.5-50 mg/kg/day, or parenterally in the form of subcutaneous and intramuscular injections. Process for the preparation of N″-substituted 9a-N-(N′-carbamoyl-γ-aminopropyl), 9a-N-(N′-thiocarbamoyl-γ-aminopropyl), 9a-N-[N′-(β-cyanoethyl)-N′-carbamoyl-γ-aminopropyl] and 9a-N-[N′-(β-cyanoethyl)-N′-thiocarbamoyl-γ-aminopropyl] derivatives of 9-deoxo-9-dihydro-9a-aza-9a-homoerithromycin A and 5-O-desosaminyl-9-deoxo-9-dihydro-9a-aza-9a-homoerithronolide A of this invention is illustrated by the following Examples which should in no way be construed as a limitation of the scope thereof. TABLE 1 Antibacerial in vitro activity of novel N″-substituted 9a-N-(N′--carbamoyl-γ-aminopropyl) and 9a-N-(N′-thiocarbamoyl-γ-aminopropyl) derivatives of 9-deoxo-9-dihydro-9a-aza-9a-homoerithromycin A presented as MIC values in comperison with erythromycin A (Er). MIK μg/ml Compound from example Test organisms 1 2 3 4 5 6 7 8 9 10 11 12* Er S. aureus 2 0.5 0.5 2 2 2 1 1 8 16 4 8 ≦0.125 ATCC 13709 S. pneumoniae ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 8 ≦0.125 16 ≦0.125 S. pyogenes ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 0.25 S. pyogenes 8 2 4 2 4 8 4 4 16 8 32 2 >64 iMLS S. pyogenes M 32 4 8 4 4 32 8 8 64 16 64 8 8 M. catarrhalis 0.5 0.25 1 1 2 8 1 1 4 4 16 0.5 — ATCC 23246 H. influenzae 32 1 2 2 2 16 2 2 32 2 16 2 2 ATCC 49247 E. faecalis 32 4 16 8 4 64 16 16 >64 16 >64 8 1 ATCC 29212 E. coli 16 8 16 16 8 32 16 32 >64 64 >64 32 32 ATCC 25922 TABLE 2 Antibacerial in vitro activity of novel N″-substituted 9a-N-[N′-(β--cyanoethyl)-N′-carbamoyl-γ-aminopropyl] and 9a-N-[N′-(β-cyanoethyl)-N′--thiocarbamoyl-γ-aminopropyl] derivatives of 9-deoxo-9-dihydro-9a-aza-9a--homoerithromycin A presented as MIC values in comperison with erythromycin A (Er). MIK μg/ml Test Compound from example organisms 27 28 29 30 31 32 33 34 36 37 38 39* Er S. aureu 4 1 2 1 4 4 1 1 2 4 1 1 ≦0.125 ATCC 13709 S. pneumoniae ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ATCC S. pyogenes ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 ≦0.125 0.25 ATCC S. pyogenes 8 2 16 2 4 8 4 4 8 47 2 32 >64 iMLS S. pyogenes M 32 4 64 4 4 32 8 8 16 8 8 64 8 M. catarrhalis 0.5 0.25 4 1 2 8 1 1 4 1 0.5 16 - ATCC 23246 H. influenzae 32 1 32 2 2 16 2 2 2 2 2 16 2 ATCC 49247 E. faecalis 32 4 >64 8 4 64 16 16 16 16 8 >64 1 ATCC 29212 E. coli 16 8 >64 16 8 32 16 32 64 16 32 >64 32 ATCC 25922 EXAMPLE 1 9-Deoxo-9-dihydro-9a-N-(N′-isopropylcarbainoyl-γ-aminopropyl)-9a-aza-9a-homoerithromycin A A mixture of 1.0 g (1.26 mmol) 9-deoxo-9-dihydro-9a-aza-9a-(γ-aminopropyl)-9a-homoerithromycin A and 0.1 g (1.3 mmol) of isopropylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:amnmonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-(N′-isopropylcarbamoyl-γ-aminopropyl)-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=877. EXAMPLE 2 9-Deoxo-9-dihydro-9a-N-[N′-(1-naphtyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 1.0 g (1.26 mmol) 9-deoxo-9-dihydro-9a-aza-9a-(γ-aminopropyl)-9a-homoerithromycin A and 0.22 g (1.26 mmol) of 1-naphtylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(1-naphtyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=961. EXAMPLE 3 9-Deoxo-9-dihydro-9a-N-(N′-benzylcarbamoyl-γ-aminopropyl)-9a-aza-9a-homoerithromycin A A mixture of 1.0 g (1.26 mmol) 9-deoxo-9-dihydro-9a-aza-9a-(γ-aminopropyl)-9a-homoerithromycin A and 0.17 g (1.3 mmol) of benzylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-(N′-benzylcarbamoyl-γ-aminopropyl)-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=925. EXAMPLE 4 9-Deoxo-9-dihydro-9a-N-(N′-benzylthiocarbamoyl-γ-aminopropyl)-9a-aza-9a-homoerithromycin A A mixture of 1.0 g (1.26 mmol) 9-deoxo-9-dihydro-9a-aza-9a-(γ-aminopropyl)-9a-homoerithromycin A and 0.17 g (1.3 mmol) of benzylisothiocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-(N′-benzyltiocarbamoyl-γ-aminopropyl)-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=941. EXAMPLE 5 9-Deoxo-9-dihydro-9a-N-[N′-(1-naphtyl)thiocarbarmoyl-γ-aminopropyl-9a-aza-9a-homoerithromycin A A mixture of 1.0 g (1.26 mmol) 9-deoxo-9-dihydro-9a-aza-9a-(γ-aminopropyl)-9a-homoerithromycin A and 0.17 g (1.3 mmol) of 1-naphtylisothiocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(1-naphtyl)thiocarbamoyl-γ-aminopropyl-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=977. EXAMPLE 6 9-Deoxo-9-dihydro-9a-N-[N′-(2-trifluoromethyl)phenylcarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 1.0 g (1.26 mmol) 9-deoxo-9-dihydro-9a-aza-9a-(γ-aminopropyl)-9a-homoerithromycin A and 0.24 g (1.3 mmol) of 2-(trifluoromethyl)phenylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(2-trifluoromethylphenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=979. EXAMPLE 7 9-Deoxo-9-dihydro-9a-N-[N′-(3-phenylpropyl)thiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 1.0 g (1.26 mmol) 9-deoxo-9-dihydro-9a-aza-9a-(γ-aminopropyl)-9a-homoerithromycin A and 0.22 g (1.3 mmol) of 3-phenylpropylisothiocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(3-phenylpropyl)thiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=969. EXAMPLE 8 9-Deoxo-9-dihydro-9a-N-[N′-(β-phenylethyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 1.0 g (1.26 mmol) 9-deoxo-9dihydro-9a-aza-9a-(γ-aminopropyl)-9a-homoerithromycin A and 0.21 g (1.3 mmol) of β-phenylethylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(β-phenylethyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=979. EXAMPLE 9 9-Deoxo-9-dihydro-9a-N-(N′-ethoxycarbonylmethylcarbamoyl-γ-aminopropyl)-9a-aza-9a-homoerithromycin A A mixture of 1.0 g (1.26 mmol) 9-deoxo-9-dihydro-9a-aza-9a-(γ-aminopropyl)-9a-homoerithromycin A and 0.16 g (1.3 mmol) of ethoxycarbonylmethylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-(N′-ethoxy-carbonylmethylcarbamoyl-γ-aminopropyl)-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=921. EXAMPLE 10 9-Deoxo-9-dihydro-9a-N-{N′-[1-(1-naphtyl)ethylcarbamoyl-γ-aminopropyl}-9a-aza-9a-homoerithromycin A A mixture of 1.0 g (1.26 mmol) 9-deoxo-9-dihydro-9a-aza-9a-(γ-aminopropyl)-9a-homoerithromycin A and 0.25 g (1.3 mmol) of 1-(1-naphtyl)ethylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-{N′-[1-(1-naphtyl)ethylcarbamoyl-γ-aminopropyl}-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=989. EXAMPLE 11 9-Deoxo-9-dihydro-9a-N-[N′-(3,4,5-trimethoxyphenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 1.0 g (1.26 mmol) 9-deoxo-9-dihydro-9a-aza-9a-(γ-aminopropyl)-9a-homoerithromycin A and 0.26 g (1.3 mmol) of 3,4,5-trimethoxyphenylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(3,4,5-trimethoxyphenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=1001. EXAMPLE 12 9-Deoxo-9-dihydro-9a-N-[N′-(2-naphtyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 1.0 g (1.26 mmol) 9-deoxo-9-dihydro-9a-aza-9a-(γ-aminopropyl)-9a-homoerithromycin A and 0.23 g (1.3 mmol) of 2-naphtylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(2-naphtyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=961. EXAMPLE 13 9-Deoxo-9-dihydro-9a-N-[N′-(2,4-dichlorophenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 1.0 g (1.26 mmol) 9-deoxo-9-dihydro-9a-aza-9a-(γ-aminopropyl)-9a-homoerithromycin A and 0.23 g (1.3 mmol) of 2,4-dichlorophenylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(2,4-dichlorophenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=979. EXAMPLE 14 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-(N′-isopropylcarbamoyl-γ-aminopropyl)-9a-aza-9a-homoerithronolide A A mixture of 1.0 g (1.57 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.13 g (1.57 mmol) of isopropylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(N′-isopropylcarbamoyl-γ-aminopropyl)-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=719. EXAMPLE 15 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(1-naphtyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 1.0 g (1.57 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.13 g (1.57 mmol) of 1-naphtylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(1-naphtyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=803. EXAMPLE 16 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-(N′-benzylcarbamoyl-γ-aminopropyl)-9a-aza-9a-homoerithronolide A A mixture of 1.0 g (1.57 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.21 g (1.57 mmol) of benzylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(N′-benzylcarbamoyl-γ-aminopropyl)-9a-aza-9a-homoerithronolide A was obtained. MS (ES+)m/z=767. EXAMPLE 17 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-(N′-benzylthiocarbamoyl-γ-aminopropyl)-9a-aza-9a-homoerithronolide A A mixture of 1.0 g (1.57 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.24 g (1.57 mmol) of benzylisothiocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(N′-benzylthiocarbamoyl-γ-aminopropyl)-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=783. EXAMPLE 18 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(1-naphtyl)thiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronofide A A mixture of 1.0 g (1.57 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.29 g (1.57 mmol) of 1-naphtylisothiocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(1-naphtyl)thiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=819. EXAMPLE 19 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(2-(trifluoromethyl)phenylcarbamoyl)-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 1.0 g (1.57 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.30 g (1.57 mmol) of 2-(trifluoromethyl)phenylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(2-(trifluoromethyl)phenylcarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=821. EXAMPLE 20 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(3-phenylpropyl)thiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 1.0 g (1.57 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.28 g (1.57 mmol) of 3-phenylpropylisothiocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(3-phenylpropyl)thiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=811. EXAMPLE 21 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-phenylethyl)thiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 1.0 g (1.57 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.26 g (1.57 mmol) of β-phenylethylisothiocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-phenylethyl)thiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=797. EXAMPLE 22 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-(N′-ethoxykarbonylmethyl-carbamoyl-γ-aminopropyl)-9a-aza-9a-homoerithronolide A A mixture of 1.0 g (1.57 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.20 g (1.57 mmol) of ethoxykarbonylmethylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(N′-ethoxykarbonylmethylcarbamoyl-γ-aminopropyl)-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=763. EXAMPLE 23 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(2-naphtyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 1.0 g (1.57 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.27 g (1.57 mmol) of 2-naphtylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(2-naphtyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=803. EXAMPLE 24 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-{N′-[1-(1-naphtyl)ethyl]carbamoyl-γ-aminopropyl}-9a-aza-9a-homoerithronolide A A mixture of 1.0 g (1.57 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.31 g (1.57 mmol) of 1-(1-naphtyl)ethylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-{N′-[1-(1-naphtyl)ethyl]carbamoyl-γ-aminopropyl}-9a-aza-9a-homoerithronolide A was obtained. MS (ES+)m/z=831. EXAMPLE 25 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(3,4,5-trimethoxyphenyl)-carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 1.0 g (1.57 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.31 g (1.57 mmol) of 3,4,5-trimethoxyphenylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(3,4,5-trimethoxyphenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=843. EXAMPLE 26 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(2,4-dichlorophenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 1.0 g (1.57 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.31 g (1.57 mmol) of 2,4-dichlorophenylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(3,4,5-trimethoxyphenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=821. EXAMPLE 27 9-Deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-isopropylcarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 0.5 g (0.591 mmol) 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-γ-aminopropyl]-9a-aza-9a-homoerithromycin A and 0.06 g (0.591 mmol) of isopropylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-isopropylcarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=931. EXAMPLE 28 9-Deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(1-naphtyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 0.5 g (0.591 mmol) 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-γ-aminopropyl]-9a-aza-9a-homoerithromycin A and 0.11 g (0.591 mmol) of 1-naphtylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(1-naphtyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=. EXAMPLE 29 9-Deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-benzylcarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 0.5 g (0.591 mmol) 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-γ-aminopropyl]-9a-aza-9a-homoerithromycin A and 0.08 g (0.591 mmol) of benzylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-benzylcarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=931. EXAMPLE 30 9-Deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-benzylthiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 0.5 g (0.591 mmol) 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-γ-aminopropyl]-9a-aza-9a-homoerithromycin A and 0.09 g (0.591 mmol) of benzylisothiocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-benzylthiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=995. EXAMPLE 31 9-Deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(1-naphtyl)thiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 0.5 g (0.591 mmol) 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-γ-aminopropyl]-9a-aza-9a-homoerithromycin A and 0.12 g (0.591 mmol) of 1-naphtylisothiocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(1-naphtyl)thiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=1029. EXAMPLE 32 9-Deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(2-(trifluoromethyl)phenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 0.5 g (0.591 mmol) 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-γ-aminopropyl]-9a-aza-9a-homoerithromycin A and 0.08 g (0.591 mmol) of 2-(trifluoromethyl)phenylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(2-(trifluoromethyl)phenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=1033. EXAMPLE 33 9-Deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(3-phenylpropyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 0.5 g (0.591 mmol) 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-γ-aminopropyl]-9a-aza-9a-homoerithromycin A and 0.10 g (0.591 mmol) of 3-phenylpropylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(3-phenylpropyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=1022. EXAMPLE 34 9-Deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(β-phenylethyl)thiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 0.5 g (0.591 mmol) 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-γ-aminopropyl]-9a-aza-9a-homoerithromycin A and 0.10 g (0.591 mmol) of β-phenylethylisothiocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(β-phenylethyl)thiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=1008. EXAMPLE 35 9-Deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-ethoxycarbonylmethyl-carbamoyl]-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 0.5 g (0.591 mmol) 9-deoxo-9-dihydro-9a-N-[N-(β-cyanoethyl)-γ-aminopropyl]-9a-aza-9a-homoerithromycin A and 0.10 g (0.591 mmol) of ethoxycarbonylmethylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-ethoxycarbonylmethylcarbamoyl]-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=974. EXAMPLE 36 9-Deoxo-9-dihydro-9a-N-{N′-(β-cyanoethyl)-N′-[1-(1-naphtyl)ethyl]carbamoyl-γ-aminopropyl}-9a-aza-9a-homoerithromycin A A mixture of 0.5 g (0.591 mmol) 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-γ-aminopropyl]-9a-aza-9a-homoerithromycin A and 0.11 g (0.591 mmol) of 1-(1-naphtyl)ethylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-{N′-(β-cyanoethyl)-N′-[1-(1-naphtyl)ethyl]carbamoyl-γ-aminopropyl}-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=1042. EXAMPLE 37 9-Deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(3,4,5-trimethoxyphenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 0.5 g (0.591 mmol) 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-γ-aminopropyl]-9a-aza-9a-homoerithromycin A and 0.12 g (0.591 mmol) of 3,4,5-trimethoxyphenylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(3,4,5-trimethoxyphenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=1053. EXAMPLE 38 9-Deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(2-naphtyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 0.5 g (0.591 mmol) 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-γ-aminopropyl]-9a-aza-9a-homoerithromycin A and 0.11 g (0.591 mmol) of 2-naphtylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(2-naphtyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=1014. EXAMPLE 39 9-Deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(2,4-dichlorophenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A A mixture of 0.5 g (0.591 mmol) 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-γ-aminopropyl]-9a-aza-9a-homoerithromycin A and 0.11 g (0.591 mmol) of 2-naphtylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:9:1.5, pure 9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(2,4-dichlorophenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithromycin A was obtained. MS(ES+)m/z=1033. EXAMPLE 40 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-isopropylcarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 0.5 g (0.728 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.06 g (0.728 mmol) of isopropylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-isopropylcarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=771. EXAMPLE 41 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(1-naphtyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 0.5 g (0.728 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.12 g (0.728 mmol) of 1-naphtylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(1-naphtyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=855. EXAMPLE 42 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-benzylcarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 0.5 g (0.728 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.10 g (0.728 mmol) of benzylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-benzylcarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=819. EXAMPLE 43 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-benzylthiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 0.5 g (0.728 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.11 g (0.728 mmol) of benzylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on silica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-benzylthiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=835. EXAMPLE 44 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(1-naphtyl)thiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 0.5 g (0.728 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.14 g (0.728 mmol) of 1-naphtylisothiocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(1-naphtyl)thiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=855. EXAMPLE 45 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(2-(trifluoromethyl)phenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 0.5 g (0.728 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.14 g (0.728 mmol) of 2-(trifluoromethyl)phenylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(2-(trifluoromethyl)-phenylcarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=873. EXAMPLE 46 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(3-phenylpropyl)thiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 0.5 g (0.728 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.13 g (0.728 mmol) of 3-phenylpropylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(3-cyanoethyl)-N′-(3-phenylpropyl)thiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=863. EXAMPLE 47 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(β-phenylethyl)thiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 0.5 g (0.728 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.12 g (0.728 mmol) of β-phenylethylisothiocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(β-phenylethyl)thiocarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=. EXAMPLE 48 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-ethoxy-carbonylmethylcarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 0.5 g (0.728 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.09 g (0.728 mmol) of β-phenylethylisothiocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-ethoxycarbonylmethylcarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=815. EXAMPLE 49 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(2-naphtyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 0.5 g (0.728 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.12 g (0.728 mmol) of 2-naphtylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(2-naphtyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=855. EXAMPLE 50 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-[1-(1-naphtyl)ethylcarbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 0.5 g (0.728 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.15 g (0.728 mmol) of 1-(1-naphtyl)ethylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-[1-(1-naphtyl)ethyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=883. EXAMPLE 51 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(3,4,5-trimethoxyphenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 0.5 g (0.728 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.14 g (0.728 mmol) of 3,4,5-trimethoxyphenylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(3,4,5-trimethoxyphenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=895. EXAMPLE 52 5-O-Desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(2,4-dichlorophenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A A mixture of 0.5 g (0.728 mmol) 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-(γ-aminopropyl)-9a-aza-homoerithronolide A and 0.14 g (0.728 mmol) of 2,4-dichlorophenylisocyanate in 10 ml dry toluene was stirred for 30 minutes at room temperature to complete the reaction. The crystalls of the crude product were filtered, wherefrom by chromatography on sillica gel column using the solvent system methylene-chloride:methanol:ammonia=90:20:1.5, pure 5-O-desosaminyl-9-deoxo-9-dihydro-9a-N-[N′-(β-cyanoethyl)-N′-(2,4-dichlorophenyl)carbamoyl-γ-aminopropyl]-9a-aza-9a-homoerithronolide A was obtained. MS(ES+)m/z=874.
<SOH> TECHNICAL FIELD <EOH>The present invention relates to N″-substituted 9a-N-(N′-carbamoyl-γ-aminopropyl), 9a-N-(N′-thiocarbamoyl-γ-aminopropyl), 9a-N-[N′-(β-cyanoethyl)-N′-carbamoyl-γ-aminopropyl] and 9a-N-[N′-(β-cyanoethyl)-N′-thiocarbamoyl-γ-aminopropyl] derivatives of 9-deoxo-9-dihydro-9a-aza-9a-homoerithromycin A and 5-O-desosaminyl-9-deoxo-9-dihydro-9a-aza-9a-homoerithronolide A, novel semisynthetic macrolide antibiotics of the azalide series having antibacterial activity, of the general formula 1, wherein R represents H or cladinosyl moiety, and R 1 represents H or β-cyanoethyl group, R 2 represents isopropyl, 1-naphtyl, 2-naphtyl, benzyl, 2-(trifluoromethyl)phenyl, 3-phenylpropyl, β-phenylethyl, ethoxycarbonylmethyl, 1-(1-naphtyl)ethyl, 3,4,5-trimethoxyphenyl and 2,4-dichlorophenyl group, and X represents O or S, to pharmaceutically acceptable addition salts thereof with inorganic or organic acids, to a process for the preparation of the pharmaceutical compositions as well as to the use of the pharmaceutical compositions obtained in the treatment of bacterial infections.
20060414
20080311
20061109
68582.0
A61K317052
0
PESELEV, ELLI
NOVEL SEMISYNTHETIC MACROLIDE ANTIBIOTICS OF THE AZALIDE SERIES
UNDISCOUNTED
0
ACCEPTED
A61K
2,006
10,538,426
ACCEPTED
Lubricating oil additive and lubricating oil composition
A lubricating oil additive and a lubricating oil composition wherein no precipitation is generated to exhibit a good storage stability even if a combination of a salicylate detergent and another metal detergent is used is provided by rendering the additive and composition an additive and a composition obtained by incorporating, into a lubricant base oil, (A) an alkali metal or alkaline earth metal salicylate having at its 3 and 5-positions hydrocarbon groups having 1 to 40 carbon atoms and a (per)basic salt, and (B) a metal detergent other than any salicylate detergent.
1. A lubricating oil additive obtained by incorporating, into a lubricant base oil, (A) a salicylate detergent and (B) a metal detergent other than any salicylate detergent, wherein the salicylate detergent (A) is an alkali metal or alkaline earth metal salicylate represented by the general formula (1) and/or a (per)basic salt thereof: wherein R1 and R2 may be the same or different and each represent a hydrocarbon group having 1 to 40 carbon atoms, the hydrocarbon group may contain oxygen or nitrogen, m represents an alkali metal or alkaline earth metal, and n is 1 or 2 in accordance with the valence of the metal. 2. The lubricating oil additive according to claim 1, wherein one of R1 and R2 in the general formula (1) is a hydrocarbon which has 10 to 40 carbon atoms, and the other is a hydrocarbon which has less than 10 carbon atoms (and may have oxygen or nitrogen). 3. The lubricating oil additive according to claim 1, wherein R1 and R2 in the general formula (1) are each a hydrocarbon group having 10 to 40 carbon atoms. 4. The lubricating oil additive according to any one of claims 1 to 3, wherein the component (A), has a metal ratio of 1.1 or more. 5. The lubricating oil additive according to any one of claims 1 to 4, wherein the metal detergent (B) other than any salicylate detergent is at least one selected from alkali metal or alkaline earth metal sulfonates and (per)basic salts thereof. 6. The lubricating oil additive according to any one of claims 1 to 5, which further comprises at least one selected from (C) an anti-wear agent, (D) an ashless dispersing agent, and (E) an antioxidant. 7. A lubricating oil composition, into which the lubricating oil additive according to any one of claims 1 to 6 is incorporated. 8. A method for improving the storage stability of a lubricating oil composition comprising a salicylate detergent and another metal detergent, wherein the lubricating oil additive according to any one of claims 1 to 6 is used.
TECHNICAL FIELD The present invention relates to a lubricating oil additive and a lubricating oil composition, specifically, a lubricating oil additive and a lubricating oil composition into which two or more metal detergents are incorporated to exhibit good storage stability. BACKGROUND ART Lubricating oils are required to have various performances in accordance with their use purposes. In particular, engine oils are required to have high thermal stability, high-temperature detergency, oxidization stability, wear prevention and others, and are produced by incorporating lubricating oil additives such as an anti-wear agent, an ashless dispersing agent, a metal detergent, and an antioxidant thereinto. Examples of the metal detergent include such as salicylates, phenates and sulfonates. These are used alone or in combination in order to improve the high-temperature detergency and other properties of lubricating oils. About such a technical field, for example, patent document 1 (Japanese Patent Application Laid-Open (JP-A) No. 8-176583) and patent document 2 (JP-A No. 10-53784) disclose diesel engine oil compositions into which a combination of metal detergents having different base numbers is incorporated. However, the following have been coming to light: in the case of using a combination of a monoalkyl salicylate and a metal detergent (such as a sulfonate) other than any salicylate both of which have been in general commercially available and used hitherto, calcium carbonate and others, which are dispersed in the metal detergent, precipitate when the composition is stored, so as to cause the following problems: the clogging of a producing line filter, a shipping line filter, an engine filter and so on for the lubricating oil additives and the lubricating oil; a drop in qualities required as products of the lubricating oil additives or the lubricating oil, such as a drop in the base number thereof; the generation of abnormal abrasion when the composition is actually used; and others. In particular, in the case of using a monoalkyl salicylate made into a (per)base by use of calcium carbonate, calcium borate or the like together with a neutral or (per)basic sulfonate detergent, in particular, a neutral sulfonate, precipitation is generated at an early stage. Thus, this combination cannot be virtually used in any lubricating oil additive or lubricating oil product under the present circumstances. Thus, the circumstances have been desired to be improved. DISCLOSURE OF THE INVENTION In light of situations as described above, it is an object of the present invention to provide a lubricating oil additive and a lubricating oil composition which comprise a combination of a salicylate detergent and a metal detergent other than it wherein no precipitation is generated to exhibit a good storage stability. Patent document 2, paragraph (0010) specifically describes SAP 001, SAP 005, and SAP 007 manufactured by Shell Chemicals Japan and OSCA 435B and OSCA 463 manufactured by Osca Chemical as examples of a “highly basic calcium salicylate/magnesium salicylate”, and patent document 2, paragraph (0012) specifically describes SAP 002 manufactured by Shell Chemicals Japan and OSCA 431B manufactured by Osca Chemical as “low basic calcium salicylates”. However, all of these commercially available products are products made mainly of a monoalkyl type salicylate (the constituent ratio of the monoalkyl salicylate in the salicylate structure thereof is over 90% by mole). Furthermore, patent documents 1 and 2 are not even aware of problems as described above. The inventors have paid attention to the structure of a salicylate as a metal detergent, and made eager investigations to find out that in the case of using a combination of a salicylate having a specific structure and a metal detergent other than any salicylate, no precipitation is generated in the form of a lubricating oil additive or a lubricating oil composition so that a very good storage stability is exhibited. Thus, the present invention has been made. Accordingly, the present invention is a lubricating oil additive and a lubricating oil composition obtained by incorporating, into a lubricant base oil, (A) a salicylate detergent and (B) a metal detergent other than any salicylate detergent, wherein the salicylate detergent (A) is an alkali metal or alkaline earth metal salicylate represented by the general formula (1) and/or a (per)basic salt thereof: wherein R1 and R2 may be the same or different and each represent a hydrocarbon group having 1 to 40 carbon atoms, the hydrocarbon group may contain oxygen or nitrogen, M represents an alkali metal or alkaline earth metal, and n is 1 or 2 in accordance with the valence of the metal. It is preferred that one of R1 and R2 in the general formula (1) is a hydrocarbon which has 10 to 40 carbon atoms, and the other is a hydrocarbon which has less than 10 carbon atoms (and may have oxygen or nitrogen) or R1 and R2 are each a hydrocarbon group having 10 to 40 carbon atoms. The lubricating oil additive and the lubricating oil composition of the present invention are particularly useful in the case where the metal ratio of the component (A) is 1.1 or more. It is preferred that the metal detergent (B) other than any salicylate detergent is at least one selected from alkali metal or alkaline earth metal sulfonates, alkali metal or alkaline earth metal phenates, and (per)basic salts thereof. It is preferred that the lubricating oil additive and the lubricating oil composition of the present invention further comprise at least one lubricating oil additive selected from (C) an anti-wear agent, (D) an ashless dispersing agent, and (E) an antioxidant. BEST MODES FOR CARRYING OUT THE INVENTION The present invention will be described in detail hereinafter. As the lubricant base oil in the lubricating oil additive and the lubricating oil composition of the present invention, a mineral type base oil or synthetic type base oil that is used in ordinary lubricating oil can be used without any especial limit. Specific examples of the mineral oil type base oil include oils obtained by purifying a lubricating oil fraction yielded by distilling an atmospheric residue oil, which is obtained by distilling crude oil under normal pressure, under reduced pressure by at least one selected from solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, hydrorefining and other treatments; wax-isomerized mineral oils; and base oils produced by isomerizing GTL wax (gas-to-liquid wax). Specific examples of the synthetic type base oil include polybutene or hydrogenated products thereof; poly-α-olefins, such as 1-octene oligomer and 1-decene oligomer, or hydrogenated products thereof; diesters such as ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate and di-2-ethylhexyl cebacate; polyol esters such as trimethylolpropane caprilate, trimethylolpropane pelargonate, pentaerythritol-2-ethyl hexanoate, and pentaerythritol pelargonate; and aromatic synthesis oils such as alkylnaphthalene, alkylbenzene, and aromatic esters; and mixtures thereof. In the invention, the above-mentioned mineral oil type base oils, the above-mentioned synthetic type base oils, or any mixture composed of two or more lubricating oils selected therefrom can be used. Examples thereof include one or more out of the mineral oil type base oils, one or more out of the synthetic type base oils, and a mixture of one or more out of the mineral oil type base oils and one or more out of the synthetic type base oils. The aromatic fraction content in the lubricant base oil is not particularly limited, and the content as % CA is preferably 10 or less, more preferably 3 or less, in particular preferably 2 or less by mass. When the aromatic fraction content in the base oil is set as described above, a composition better in oxidation stability can be obtained. The “% CA” represents the percentage of the number of the aromatic carbon atoms to the number of all the carbon atoms, the percentage being obtained by ring analysis prescribed in ASTM D 3238. The kinematic viscosity of the lubricant base oil is not particularly limited, and the kinematic viscosity at 100° C. is preferably 20 mm2/s or less, more preferably 10 mm2/S or less in order to keep the low-temperature viscosity property good. On the other hand, the kinematic viscosity is preferably 1 mm2/s or more, more preferably 2 mm2/S or more in order to form a sufficient oil film at lubrication places, thereby keeping lubricity and further control the evaporation loss of the lubricant base oil into a low value. The evaporation loss quantity of the lubricant base oil is 20% or less by mass, more preferably 16% or less by mass, and in particular preferably 10% or less by mass as NOACK evaporation quantity. When the NOACK evaporation quantity of the lubricant base oil is kept at a value of 20% or less by mass, the evaporation loss of the lubricating oil can be controlled into a low value and further in the case of using the lubricating oil composition as a lubricating oil for internal combustion engine, it is possible to prevent sulfur compounds, phosphorus compounds or metals in the composition from being deposited together with the lubricant base oil on an exhaust gas purifying device so as to prevent a bad effect on the exhaust gas purifying performance in advance. The NOACK evaporation quantity referred to herein is measured in accordance with CEC L-40-T-87. The viscosity index of the lubricant base oil is not particularly limited, and the value thereof is preferably 80 or more, more preferably 100 or more, and even more preferably 120 or more to obtain a good viscometric property at temperatures from low temperature and high temperature. The component (A) in the invention is an alkali metal or alkaline earth metal salicylate represented by the general formula (1) and/or a (per)basic salt thereof: wherein R1 and R2 may be the same or different and each represent a hydrocarbon group having 1 to 40 carbon atoms, the hydrocarbon group may contain oxygen or nitrogen, M represents an alkali metal or alkaline earth metal such as sodium, potassium, calcium and magnesium, and is preferably calcium or magnesium, more desirably calcium, and n is 1 or 2 in accordance with the valence of the metal. Examples of the hydrocarbon group having 1 to 40 carbon atoms include alkyl, cycloalkyl, alkenyl, alkyl-substituted cycloalkyl, aryl, alkyl-substituted aryl and arylalkyl groups. Specific examples thereof include alkyl groups which have 1 to 40 carbon atoms (and may be linear or branched) such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl groups; cycloalkyl groups having 5 to 7 carbon atoms such as cyclopentyl, cyclohexyl and cycloheptyl; alkylcycloalkyl groups having 6 to 10 carbon atoms (the position(s) where the alkyl group(s) is/are substituted on the cycloalkyl group being arbitrary) such as methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, diethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, and dimethylcycloheptyl, methylethylcycloheptyl; alkenyl groups (which may be linear or branched, the position of the double bond therein being arbitrary) such as butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl and nonadecenyl groups; aryl groups such as phenyl and naphthyl groups; alkylaryl groups having 7 to 10 carbon atoms (wherein the alkyl group(s) may be linear or branched, the position(s) where the alkyl group(s) is/are substituted on the aryl group being arbitrary) such as tolyl, xylyl, ethylphenyl, propylphenyl, and butylphenyl groups; and arylalkyl groups which have 7 to 10 carbon atoms (the alkyl group being allowable to be linear or branched) such as benzyl, phenylethyl, phenylpropyl, and phenylbutyl groups. R1 can be combined with R2 without any especial limitation. Preferred examples of the combination thereof are the following combination (1) or (2): (1) One of R1 and R2 is a hydrocarbon group having 10 to 40 carbon atoms, preferably 10 to less than 20 carbon atoms, or 20 to 30 carbon atoms, and the other is a hydrocarbon having less than 10 carbon atoms, preferably less than 5 carbon atoms, in particular preferably 1 carbon atom; or (2) R1 and R2 are each a hydrocarbon group having 10 to 40 carbon atoms, preferably 10 to less than 20 carbon atoms, or 20 to 30 carbon atoms, and these are preferably the same as each other. The hydrocarbon group having 10 to 40 carbon atoms is preferably a secondary alkyl group derived from a polymer or copolymer made from ethylene, propylene, butylene or the like and represented by the following general formula (2): wherein x and y are each an integer from 0 to 37 and x+y is from 7 to 37; preferably, x and y are each an integer from 0 to 27 and x+y is from 7 to 27; more preferably, x and y are each an integer from 0 to 16 and x+y is from 7 to 16 or x and y are each an integer from 0 to 23 and x+y is from 17 to 23; and in particular preferably, x and y are each an integer from 0 to 15 and x+y is from 11 to 15. The hydrocarbon having less than 10 carbon atoms may be an alkyl group having 1 to less than 10 carbon atoms such as a methyl, ethyl, butyl, or t-butyl group, and may contain oxygen or nitrogen. An example thereof is a —COOH group. Of these, t-butyl and methyl groups are preferable and a methyl group is most preferable. The process for producing the component (A) is not particularly limited, and a known process disclosed in JP-B-48-35325, JP-B-50-3082 or the like can be used. For example, in the case where one of R1 and R2 is an alkyl group having 10 to less than 20 carbon atoms or 20 to 30 carbon atoms and the other is a methyl group, the component (A) can be obtained by using an o-cresol or p-cresol as a starting material to alkylate the p-position or o-position thereof with an olefin having 10 to less than 20 carbon atoms or 20 to 30 carbon atoms, carboxylating the resultant, and further causing the resultant to react with a metal base such as an oxide or hydroxide of an alkali metal or alkaline earth metal or converting the resultant once into an alkali metal salt such as a sodium or potassium salt and then substituting the salt with an alkaline earth metal salt. In the case where phenol is used as a starting material, it is advisable to produce the component (A) through steps of using an olefin having 10 to less than 20 carbon atoms or 20 to 30 carbon atoms in an amount of 1.5 to 4 moles, preferably 2 to 3 moles per mole of phenol to conduct alkylation followed by carboxylation (or steps reverse thereto). About the component (A) in the invention, salicylates other than the salicylate represented by the general formula (1), that is, monoalkyl salicylates having 1 to 40 carbon atoms such as 3-alkyl salicylate, 4-alkyl salicylate and 5-alkyl salicylate may be contained as components resulting from impurities in the process of producing the salicylate represented by the general formula (1) or as optional components. The constituent ratio thereof is preferably 50% or less by mole, more preferably 30% or less by mole, even more preferably 10% or less by mole, most preferably approximately 0% by mole. In the case where the content of the monoalkyl salicylate(s) is restricted as described above, a composition wherein the generation of a precipitation is suppressed can be obtained when the component (A) is used together with a sulfonate or the like. In the case of, for example, 3-alkyl-5-methyl salicylate, 3-methyl-5-alkyl salicylate or the like, which is obtained by use of o-cresol or p-cresol as a starting material as described above, monoalkyl salicylates are not substantially contained. In the case of a dialkyl salicylate, which is obtained by use of the above-mentioned phenol as a starting material, the content of monoalkyl salicylate(s) can be decreased by using an olefin in an amount of 2 moles or more per the phenol to conduct alkylation or by separating and removing monoalkyl salicylate(s) from the resultant mono- and di-alkyl salicylate mixture. The component (B) in the lubricating oil additive and the lubricating oil composition of the invention is a metal detergent other than any salicylate detergent. That is, examples thereof include alkali metal or alkaline earth metal detergents made of sulfonates, phenates, carboxylates and naphthenates of alkali metal or alkaline earth metals. In the invention, one or more alkali metal or alkaline earth metal detergents can be used which are selected from the group consisting of the above. Alkaline earth metal sulfonate detergents and alkaline earth metal phenate detergents, in particular, alkaline earth metal sulfonate detergents are preferably used. The alkaline earth metals are each an alkaline earth metal salt, in particular, a magnesium salt and/or a calcium salt of an alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound having a molecular weight of 300 to 1500, preferably 400 to 700, and the calcium salt is preferably used. Specific examples of the alkyl aromatic sulfonic acid include petroleum sulfonic acid and synthetic sulfonic acid. As the petroleum sulfonic acid, there is generally used a sulfonated alkyl aromatic compound of a lubricant fraction of mineral oil or the so-called mahogany acid, which is produced as a byproduct when white oil is produced. As the synthetic sulfonic acid, there is used, for example, a sulfonated alkylbenzene having a linear or branched alkyl group, which is obtained by alkylating benzene with an oligomer of an olefin having 2 to 12 carbon atoms (such as ethylene or propylene), or a product obtained by sulfonating an alkylnaphthalene such as dinonylnaphthalene. The sulfonating agent used when these alkyl aromatic compounds are sulfonated is not limited to any especial kind. Usually, fuming sulfuric acid or sulfuric anhydride is used. Examples of the alkaline earth metal phenates include alkaline earth metal salts, in particular, magnesium and calcium salts of Mannich reactants of alkyl phenol, alkylphenol sulfide or alkylphenol. Specific examples thereof include substances represented by the following formulae (3), (4) and (5): wherein R21, R22, R23, R24, R25 and R26 may be the same or different and each represent a linear or branched alkyl group having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms, and M1, M2 and M3 each represent an alkaline earth metal, preferably calcium or magnesium, and x represents 1 or 2. Specific examples of R21, R22, R23, R24, R25 and R26, which are each independent, include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl groups. These may be linear or branched. These may also be primaryl alkyl, secondary alkyl or tertiary alkyl groups. Examples of the component (A) and component (B) of the invention include not only neutral salts as described above but also basic salts obtained by heating these neutral salts together with an excessive amount of an alkali metal or alkaline earth metal salt or an alkali metal or alkaline earth metal base (a hydroxide or oxide of an alkali metal or alkaline earth metal) in the presence of water; and perbasic salts obtained by causing the neutral salts to react with a base such as a hydroxide of an alkali metal or alkaline earth metal in the presence of carbon dioxide gas, boric acid or a borate. These reactions are usually conducted in a solvent (an aliphatic hydrocarbon solvent such as hexane, an aromatic hydrocarbon solvent such as xylene, a light lubricant base oil, or the like), so as to yield salts having a metal content of 1.0 to 20% by mass, preferably 2.0 to 16% by mass. In the invention, the metal ratio of the component (A) or component (B) is not particularly limited, and the component (A) and component (B) having a metal ratio of 1 to 40, preferably 1 to 20 can be used. The metal ratio of the component (A) is 1.1 or more, preferably 1.5 or more, in particular preferably 2.3 or more, and is preferably 10 or less, more preferably 6 or less since the salicylate which may generate a precipitation is a monoalkyl salicylate made into a (per)base with calcium carbonate or the like. The component (A) having a metal ratio within such a range is very useful. In the case of using the above-mentioned monoalkyl salicylate, which has a metal ratio of 1.1 or more, for example, a monoalkyl salicylate having a metal ratio of 2.7 together with a sulfonate detergent as the component (B), a precipitation is generated whether the metal ratio of the sulfonate detergent is 1 or 10. However, as the metal ratio of the sulfonate detergent is smaller (in the case where the ratio is, for example, 5 or less, or 2 or less, in particular 1), a precipitation is generated at an earlier stage. It is therefore very useful to use the component (B) having such a small metal ratio together with the component (A) having a metal ratio as described above. In the case where the metal ratios of the components (A) and (B) are each 1, a precipitation resulting from calcium carbonates or the like is not generated. Thus, this case is also preferred. The metal ratio referred to herein is represented by (the valence of the metal element in an alkali metal or alkaline earth metal salicylate, an alkali metal or alkaline earth metal sulfonate, or the like)×(content (% by mole) of the metal element therein/(content (% by mole) of the soap group therein). The metal element means calcium, magnesium or the like, and the soap group means the alkylsalicylic acid group, the alkylsulfonic acid group, or the like. In the lubricating oil additive and the lubricating oil composition of the invention, the contents of the component (A) and the component (B) are not particularly limited, and are decided as the needs arise for a lubricating oil additive or a lubricating oil product. The lower limit of each of the contents is 0.01% by mass, preferably 0.1% by mass of the whole of the composition. The upper limit thereof is 40% by mass, preferably 20% by mass, in particular preferably 10% or less by mass. When the composition of the invention is used as a lubricating oil composition for internal combustion engine, preferred examples of the contents of the component (A) and the component (B) are as follows: the amount of the component (A) is 5% or less by mass, preferably 1% or less by mass, more preferably 0.5% or less by mass, even more preferably 0.3% or less by mass of the whole of the lubricating oil composition, and the amount of the component (B) is 5% or less by mass, preferably 1% or less by mass, more preferably 0.5% or less by mass, even more preferably 0.3% or less by mass, most preferably 0.15% or less by mass of the whole of the lubricating oil composition, these amounts being in terms of the amounts of the alkali metal or alkaline earth metal element. In the case of the component (B) (in particular, a sulfonate) having a metal ratio of 2 or less, it is desired that the component is incorporated preferably in an amount of 0.08% or less by mass, in particular preferably in an amount of 0.05% or less by mass since the content of the soap group (such as sulfonic acid) becomes relatively high. The lubricating oil additive and the lubricating oil composition of the invention are a lubricating oil additive and a lubricating oil composition wherein the component (A) and the component (B) are incorporated into a lubricant base oil, and are good in not only storage stability but also high-temperature detergency, base number maintainability, oxidization stability and others. In order to make the performances better and make other required performances better, one or more additives may be arbitrarily incorporated thereinto, the additives being selected from (C) an anti-wear agent, (D) an ashless dispersing agent, and (E) an antioxidant, or from known additives such as a friction modifier, a viscosity index improver, a corrosion inhibitor, a rust inhibitor, an anti-emulsifier, a metal inactivator, an antifoaming agent, and a colorant. The resultant composition can be supplied as an additive package or lubricating oil product into which these are incorporated. Examples of the anti-wear agent (C) include sulfur-containing compounds such as zinc dithiophosphate, zinc dithiocarbamate, thiophosphoric acid esters, disulfides, olefin sulfides, and oil and fat sulfides; monoesters or diesters of phosphorous acid or phosphoric acid, metal (such as zinc) salts thereof, and amine salts thereof; and triesters of phosphorous acid or phosphoric acid. These may be incorporated usually at a ratio of 0.1 to 20% by mass, preferably at a ratio of 0.2 to 10% by mass. The component (A) in the invention less easily hinders the effect of the anti-wear agent (C) than any monoalkyl type salicylate; therefore, when the component (C) is used in the lubricating oil composition of the invention, the content thereof can be decreased. In the case of, for example, an anti-wear agent containing sulfur, the amount of the agent (C) can be 0.2% or less by mass, preferably 0.15% or less by mass of the whole of the lubricating oil composition, the amount being in terms of the amount of the sulfur element therein. In the case of, for example, an anti-wear agent containing phosphorus, the amount of the agent (C) can be 0.08% or less by mass, more restrictedly 0.05% or less by mass of the whole of the lubricating oil composition, the amount being in terms of the amount of the phosphorus element therein. Such a case is useful when the composition of the invention is used as a lubricating oil composition for internal combustion engine. This is because a bad effect thereof onto an exhaust gas purifying catalyst can be decreased. Examples of the ashless dispersing agent (D) include succinimide ashless dispersing agents, benzylamine ashless dispersing agents, polybutenylamine ashless dispersing agents, and compounds obtained by modifying these compounds with a boron compound, a oxygen-containing organic compound, a phosphorus compound, a sulfur compound or the like. These may be incorporated usually at a ratio of 0.1 to 20% by mass, preferably at a ratio of 0.5 to 10% by mass. As the antioxidant (E), any antioxidant that is ordinarily used in lubricating oil can be used, examples thereof including phenol type antioxidants such as 2,6-di-tert-butyl-4-methylphenol, 4,4′-methylenebis(2,6-di-tert-butylphenol), octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and octyl-3-(3-methyl-5-tert-butyl-4-hydroxyphenyl)propionate, amine type antioxidants such as phenyl-α-naphthylamine, alkylphenyl-α-naphthylamine, and dialkyldiphenylamine, and metal type antioxidants such as molybdenum and copper antioxidants. These may be incorporated usually at a ratio of 0.1 to 10% by mass, preferably at a ratio of 0.1 to 5% by mass. Examples of the friction modifier include molybdenum dithiophosphate, molybdenum dithiocarbamate, aliphatic acid esters, aliphatic amines, aliphatic amides, and aliphatic ethers. Specific examples of the viscosity index improver include the so-called non-dispersion type viscosity index improvers, which are polymers or copolymers made from one or more monomers selected from various methacrylic acid esters, or hydrogenated products thereof; the so-called dispersion type viscosity index improvers, which are obtained by copolymerizing them further with various methacrylic acid esters containing a nitrogen compound; non-dispersion type or dispersion type ethylene/α-olefin copolymers (examples of the α-olefin including propylene, 1-butene and 1-pentene), or hydrogenated products thereof; polyisobutylene, or hydrogenated products thereof; hydrogenated products of styrene/diene copolymer; styrene/anhydrous maleic acid ester copolymer; and polyalkylstyrene. It is necessary that the molecular weight of these viscosity index improvers is selected, considering shear stability. Specifically, the number-average molecular weight of the viscosity index improvers is usually from 5,000 to 1,000,000, preferably from 100,000 to 900,000 in the case of, for example, the dispersion type and the non-dispersion type polymethacrylates; is usually from 800 to 5,000, preferably from 1,000 to 4,000 in the case of the polyisobutylene or the hydrogenated products thereof; and is usually from 800 to 500,000, preferably from 3,000 to 200,000 in the case of the ethylene/α-olefin copolymers or the hydrogenated products thereof. In the case where the ethylene/α-olefin copolymers or the hydrogenated products thereof are used out of these viscosity index improvers, a lubricating oil additive and a lubricating oil composition particularly good in shear stability can be obtained. One or more compounds selected at will from the above-mentioned viscosity index improvers can be contained in an arbitrary amount. Examples of the corrosion inhibitor include benztriazole type, tolyltriazole type, thiadiazole type, and imidazole type compounds. Examples of the rust inhibitor include petroleum sulfonate, alkylbenzenesulfonate, dinonylnaphthalenesulfonate, alkenylsuccinic acid esters, and polyhydric alcohol esters. Examples of the anti-emulsifier include polyalkylene glycol type nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether and polyoxyethylene alkyl naphthyl ether. Examples of the metal inactivator include imidazolin, pyrimidine derivatives, alkylthiadiazole, mercaptobenzothiazole, benzotriazole or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiazolyl-2,5-bisdialkyldithiocarbamate, 2-(alkyldithio)benzimidazole, and β-(o-carboxybenzylthio)propionitrile. Examples of the antifoamer include silicone, fluorosilicone, and fluoroalkyl ether. In the case where these additives are incorporated into the lubricating oil additive of the invention, these additives can be appropriately added in accordance with the use purpose of a lubricating oil composition wherein the lubricating oil additive is to be used, so as to construct the so-called additive package. When one of these additives is incorporated into the lubricating oil composition of the invention, the content thereof is usually selected from the range of 0.1 to 5% by mass of the whole of the lubricating oil composition in the case of the friction modifier, from the range of 0.1 to 20% by mass thereof in the case of the viscosity index improver, from the range of 0.005 to 5% by mass thereof in the case of the corrosion inhibitor, the rust inhibitor or the anti-emulsifier, form the range of 0.005 to 1% by mass thereof in the case of the metal inactivator, and from the range of 0.0005 to 1% by mass thereof in the case of the antifoamer. EXAMPLES The content of the present invention will be more specifically described by way of the following examples and comparative examples. However, the invention is not limited by these examples. Examples 1 to 8, and Comparative Examples 1 to 8 As shown in Tables 1 and 2, lubricating oil compositions of the invention (Examples 1 to 8) and lubricating oil compositions for comparison (Comparative Examples 1 to 8) were each prepared. TABLE 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Hydro-refined mineral oil 1) % by mass Balance Balance Balance Balance Solvent refined mineral oil 2) % by mass Balance Balance Balance Balance Perbasic Ca monoalkylsalicylate 1 3) % by mass — — — — — — — — Amount in terms of the alkaline earth % by mass — — — — — — — — metal element Perbasic Ca monoalkylsalicylate 2 4) % by mass — — — — — — — — Amount in terms of the alkaline earth % by mass — — — — — — — — metal element (A) Perbasic Ca 3-alkyl-5-methylsalicylate % by mass 4 4 2.5 2.5 — — — — 5) Amount in terms of the alkaline earth % by mass (0.24) (0.24) (0.18) (0.18) — — — — metal element (A) Perbasic Ca dialkylsalicylate 6) % by mass — — — — 4 4 2.5 2.5 Amount in terms of the alkaline earth % by mass — — — — (0.24) (0.24) (0.18) (0.18) metal element (B) Neutral Ca sulfonate 7) % by mass 1 1 — — 1 1 — — Amount in terms of the alkaline earth % by mass (0.02) (0.02) — — (0.02) (0.02) — — metal element (B) Perbasic ca sulfonate 8) % by mass — — 1 1 — — 1 1 Amount in terms of the alkaline earth % by mass — — (0.1) (0.1) — — (0.1) (0.1) metal element (C)ZDTP 9) % by mass 1 1 1 1 1 1 1 1 Amount in terms of the phosphorus % by mass (0.07) (0.07) (0.07) (0.07) (0.07) (0.07) (0.07) (0.07) element (D) Ashless dispersing agent 10) % by mass 5 5 5 5 5 5 5 5 (E) Antioxidant 11) % by mass 2 2 2 2 2 2 2 2 Viscosity index improver 12) % by mass 4 4 4 4 4 4 4 4 Anti-emulsifier 13) % by mass 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Storage stability test (vol %) 1 WEEK Not Not Not Not Not Not Not Not generated generated generated generated generated generated generated generated 2 WEEK Not Not Not Not Not Not Not Not generated generated generated generated generated generated generated generated 3 WEEK Not Not Not Not Not Not Not Not generated generated generated generated generated generated generated generated 4 WEEK Not Not Not Not Not Not Not Not generated generated generated generated generated generated generated generated 1) % CA: 0, Sulfur content: 0 ppm by mass, 100° C. kinematic viscosity: 6.5 mm2/s, viscosity index: 125 2) % CA: 6.5, Sulfur content: 1700 ppm by mass, 100° C. kinematic viscosity: 6.9 mm2/s, viscosity index: 100 3) Infineum C9371(SAP001) Total base value: 170 mgKOH/g, Ca content: 6.1% by mass, Metal ratio: 2.7, Alkyl groups: C14, C16, C18, Constituent ratio of monoalkyl compounds: 96 mol % 4) OSCA463 Total base value: 170 mgKOH/g, Ca content: 6.1% by mass, Metal ratio: 2.7, Alkyl groups: C14, C16, C18, Constituent ratio of monoalkyl compounds: 95 mol % 5) Total base value: 170 mgKOH/g, Ca content: 6.1% by mass, Metal ratio: 2.7, Alkyl groups: C14, C16, C18 6) Total base value: 170 mgKOH/g, Ca content: 6.1% by mass, Metal ratio: 2.7, Alkyl groups: C14, C16, C18 7) Total base value: 20 mgKOH/g, Ca content: 2.35% by mass, Metal ratio: 1.0 8) Total base value: 300 mgKOH/g, Ca content: 10.4% by mass, Metal ratio: 10.0 9) Alkyl group: 1,3-dimethylbutyl group, Phosphorus content: 7.2% by mass, Sulfur content: 14.4% by mass 10) Polybutenylsuccnimide, Number-average molecular weight of the polybutenyl groups: 1300 11) Phenol type and amine type antioxidants (1:1) 12) OCP Average molecular weight: 150000 13) Anti-emulsifier: polyoxyethylene alkyl ether TABLE 2 Compar- Compar- Compar- Compar- Compar- Compar- Compar- Compar- ative ative ative ative ative ative ative ative example 1 example 2 example 3 example 4 example 5 example 6 example 7 example 8 Hydro-refined mineral oil 1) % by mass Balance Balance Balance Balance Solvent refined mineral oil 2) % by mass Balance Balance Balance Balance Perbasic Ca monoalkylsalicylate 1 3) % by mass 4 4 2.5 2.5 — — — — Amount in terms of the alkaline earth % by mass (0.24) (0.24) (0.18) (0.18) — — — — metal element Perbasic Ca monoalkylsalicylate 2 4) % by mass — — — — 4 4 2.5 2.5 Amount in terms of the alkaline earth % by mass — — — — (0.24) (0.24) (0.18) (0.18) metal element (A) Perbasic Ca 3-alkyl-5-methylsalicylate % by mass — — — — — — — — 5) Amount in terms of the alkaline earth % by mass — — — — — — — — metal element (A) Perbasic Ca dialkylsalicylate 6) % by mass — — — — — — — — Amount in terms of the alkaline earth % by mass — — — — — — — — metal element (B) Neutral Ca sulfonate 7) % by mass 1 1 — — 1 1 — — Amount in terms of the alkaline earth % by mass (0.02) (0.02) — — (0.02) (0.02) — — metal element (B) Perbasic ca sulfonate 8) % by mass — — 1 1 — — 1 1 Amount in terms of the alkaline earth % by mass — — (0.1) (0.1) — — (0.1) (0.1) metal element (C)ZDTP 9) % by mass 1 1 1 1 1 1 1 1 Amount in terms of the phosphorus % by mass (0.07) (0.07) (0.07) (0.07) (0.07) (0.07) (0.07) (0.07) element (D) Ashless dispersing agent 10) % by mass 5 5 5 5 5 5 5 5 (E) Antioxidant 11) % by mass 2 2 2 2 2 2 2 2 Viscosity index improver 12) % by mass 4 4 4 4 4 4 4 4 Anti-emulsifier 13) % by mass 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Storage stability test (vol %) 1 WEEK Generated Generated Not Not Generated Generated Not Not (0.3) (0.3) Generated Generated (0.3) (0.3) Generated Generated 2 WEEK Generated Generated Generated Generated Generated Generated Generated Generated (0.3) (0.3) (0.02) (0.02) (0.3) (0.3) (0.02) (0.02) 3 WEEK Generated Generated Generated Generated Generated Generated Generated Generated (0.3) (0.3) (0.02) (0.02) (0.3) (0.3) (0.02) (0.02) 4 WEEK Generated Generated Generated Generated Generated Generated Generated Generated (0.3) (0.3) (0.02) (0.02) (0.3) (0.3) (0.02) (0.02) 1) % CA: 0, Sulfur content: 0 ppm by mass, 100° C. kinematic viscosity: 6.5 mm2/s, viscosity index: 125 2) % CA: 6.5, Sulfur content: 1700 ppm by mass, 100° C. kinematic viscosity: 6.9 mm2/s, viscosity index: 100 3) Infineum C9371(SAP001) Total base value: 170 mgKOH/g, Ca content: 6.1% by mass, Metal ratio: 2.7, Alkyl groups: C14, C16, C18, Constituent ratio of monoalkyl compounds: 96 mol % 4) OSCA463 Total base value: 170 mgKOH/g, Ca content: 6.1% by mass, Metal ratio: 2.7, Alkyl groups: C14, C16, C18, Constituent ratio of monoalkyl compounds: 95 mol % 5) Total base value: 170 mgKOH/g, Ca content: 6.1% by mass, Metal ratio: 2.7, Alkyl groups: C14, C16, C18 6) Total base value: 170 mgKOH/g, Ca content: 6.1% by mass, Metal ratio: 2.7, Alkyl groups: C14, C16, C18 7) Total base value: 20 mgKOH/g, Ca content: 2.35% by mass, Metal ratio: 1.0 8) Total base value: 300 mgKOH/g, Ca content: 10.4% by mass, Metal ratio: 10.0 9) Alkyl group: 1,3-dimethylbutyl group, Phosphorus content: 7.2% by mass, Sulfur content: 14.4% by mass 10) Polybutenylsuccnimide, Number-average molecular weight of the polybutenyl groups: 1300 11) Phenol type and amine type antioxidants (1:1) 12) OCP Average molecular weight: 150000 13) Anti-emulsifier: polyoxyethylene alkyl ether About the resultants compositions, the following storage stability test was made. (1) Storage Stability Test A volume of 100 mL of each of the resultants lubricating oil compositions was put into a graduated test tube for centrifugation (see, for example, JIS K 2601), and the following cycle test was made: 0° C. for one week→60° C. for 1 week→0° C. for 1 week→60° C. for 1 week. It was checked with the naked eye whether or not a precipitation was generated. Examples 1 to 8 Lubricating oil compositions of Examples 1 to 8 according to the invention were each a composition obtained by incorporating, into a lubricant base oil, calcium-carbonate-perbasic calcium (3-alkyl-5-methyl)salicylate or calcium (3,5-dialkyl)salicylate having a metal ratio of 2.7 as a component (A), calcium-carbonate-perbasic calcium sulfonate having a metal ratio of 1 or 10 as a component (B), (C) zinc dithiophosphate, (D) succinimide, (E) phenol type and amine type antioxidants, a viscosity index improver, and an anti-emulsifier. No precipitation was generated even after 4 weeks passed in the above-mentioned cycle test, so as to exhibit good storage stability. Calcium phenate having a metal ratio of 1 was used as the component (B). As a result, no precipitation was generated in the same manner, so as to exhibit good storage stability. Comparative Examples 1 to 8 In the case of using, as the component (A) in Examples 1 to 8, calcium-carbonate-perbasic calcium (monoalkyl)salicylates having a metal ratio of 2.7 (about the constituent ratios of monoalkylsalicylates in the salicylate structure thereof, the ratio of C9371 manufactured by Infineum Co. (corresponding to SAP 001 manufactured by previous Shell Chemicals Japan) was 96% by mole and that of OSCA 463 manufactured by Osca Chemical Co. was 95% by mole) and calcium sulfonate having a metal ratio of 1 (Comparative Examples 1, 2, 5 and 6), a white precipitation which appeared to be calcium carbonate was evidently generated within one week. In the case of using calcium (monoalkyl) salicylate having a metal ratio of 2.7 together with perbasic calcium sulfonate having a metal ratio of 10 (Comparative Examples 3, 4, 7 and 8), the same precipitation was evidently generated within 2 weeks. Thus, it is understood that they were poor in storage stability. INDUSTRIAL APPLICABILITY The lubricating oil additive and the lubricating oil composition of the present invention generate no precipitation and have good storage stability. It has been become possible to supply a lubricating oil additive product or a lubricating oil composition product made of a combination of a (per)basic salicylate and a metal detergent such as (neutral) sulfonate, which has generated a precipitation so as not to be circulated as a product so far or so as to cause a trouble even if it has been circulated. It has been become possible to prevent the generation of troubles even under a situation that a salicylate-containing lubricating oil is mixed with another metal-detergent-containing lubricating oil or a situation that these are mixed with each other when the kind of oil is exchanged in a storage tank. It has been verified that the lubricating oil additive and the lubricating oil composition of the invention are good in high-temperature detergency and oxidation stability and can be made high in long drain property. It is also possible to give a desired performance to the additive or composition by incorporating various additives thereinto. Accordingly, the lubricating oil additive and the lubricating oil composition of the invention are useful as a lubricating oil additive or a lubricating oil composition, and can be preferably used as a lubricating oil additive and a lubricating oil composition for internal combustion engines such as gasoline engines, diesel engines and gas engines for two-wheeled vehicles, four-wheeled vehicles, power generation, ships or the like, in particular, a lubricating oil additive and a lubricating oil composition for internal combustion engines using low-sulfur fuels (for example, gasoline, light oil, natural gas and LPG which have a sulfur content of 50 ppm or less by mass, preferably 10 ppm or less by mass, or hydrogen, dimethyl ether (DME), gas-to-liquid (GTL) fuels (light oil fractions and gasoline fractions) and alcohol fuel which do not substantially contain sulfur) since long-drain performance can be made higher. Moreover, the lubricating oil additive and the lubricating oil composition of the invention can be preferably used as a lubricating oil about which storage stability, high-temperature detergency and oxidation stability as described above are required, for example, a lubricating oil for a driving system such as an automatic or manual transmission, or a lubricating oil such as grease, wet brake oil, hydraulic oil, turbine oil, compressor oil, shaft bearing oil or refrigerator oil, and as an additive used therein.
<SOH> BACKGROUND ART <EOH>Lubricating oils are required to have various performances in accordance with their use purposes. In particular, engine oils are required to have high thermal stability, high-temperature detergency, oxidization stability, wear prevention and others, and are produced by incorporating lubricating oil additives such as an anti-wear agent, an ashless dispersing agent, a metal detergent, and an antioxidant thereinto. Examples of the metal detergent include such as salicylates, phenates and sulfonates. These are used alone or in combination in order to improve the high-temperature detergency and other properties of lubricating oils. About such a technical field, for example, patent document 1 (Japanese Patent Application Laid-Open (JP-A) No. 8-176583) and patent document 2 (JP-A No. 10-53784) disclose diesel engine oil compositions into which a combination of metal detergents having different base numbers is incorporated. However, the following have been coming to light: in the case of using a combination of a monoalkyl salicylate and a metal detergent (such as a sulfonate) other than any salicylate both of which have been in general commercially available and used hitherto, calcium carbonate and others, which are dispersed in the metal detergent, precipitate when the composition is stored, so as to cause the following problems: the clogging of a producing line filter, a shipping line filter, an engine filter and so on for the lubricating oil additives and the lubricating oil; a drop in qualities required as products of the lubricating oil additives or the lubricating oil, such as a drop in the base number thereof; the generation of abnormal abrasion when the composition is actually used; and others. In particular, in the case of using a monoalkyl salicylate made into a (per)base by use of calcium carbonate, calcium borate or the like together with a neutral or (per)basic sulfonate detergent, in particular, a neutral sulfonate, precipitation is generated at an early stage. Thus, this combination cannot be virtually used in any lubricating oil additive or lubricating oil product under the present circumstances. Thus, the circumstances have been desired to be improved.
20050610
20091208
20060323
81610.0
C10M12950
0
GOLOBOY, JAMES C
LUBRICATING OIL ADDITIVE AND LUBRICATING OIL COMPOSITION
UNDISCOUNTED
0
ACCEPTED
C10M
2,005
10,538,467
ACCEPTED
Exposure apparatus and device manufacturing method
An exposure apparatus includes a projection optical system (3) for projecting a pattern of a mask (2) onto a substrate (5), and a fluid supply unit (6) for supplying a fluid between said projection optical system and the substrate, said fluid supply unit (6) including an injection unit (19) for injecting carbon dioxide into the fluid.
1. An exposure apparatus comprising: a projection optical system for projecting a pattern of a mask onto a substrate; and a fluid supply unit for supplying a fluid between said projection optical system and the substrate, said fluid supply unit including an injection unit for injecting carbon dioxide into the fluid. 2. An exposure apparatus according to claim 1, wherein said fluid supply unit includes a degassing unit for degassing the fluid, said degassing unit being located at an upstream side of the injection unit. 3. An exposure apparatus according to claim 1, wherein said injection apparatus includes a membrane module for injecting the carbon dioxide. 4. An exposure apparatus according to claim 1, wherein the injection unit injects the carbon dioxide at a concentration of the carbon dioxide in the fluid between 0.02 ppm and 750 ppm. 5. An exposure apparatus according to claim 4, wherein the injection unit injects the carbon dioxide at the concentration of the carbon dioxide in the fluid between 0.06 ppm and 300 ppm. 6. An exposure apparatus according to claim 1, wherein the fluid supply unit includes a resistivity meter for measuring a resistivity value of the fluid, and the injection unit injects the carbon dioxide based on a measurement result of the resistivity meter. 7. An exposure apparatus according to claim 1, wherein the injection unit injects the carbon dioxide so that a resistivity value of the fluid is between 0.02 MΩ·cm and 10 MΩ·cm. 8. An exposure apparatus according to claim 7, wherein the injection unit injects the carbon dioxide so that the resistivity value of the fluid is between 0.04 MΩ·cm and 5 MΩ·cm. 9. An exposure apparatus comprising: an illumination optical system for illuminating a mask using light from a light source; and a projection optical system for projecting a pattern of the mask onto a substrate, wherein a fluid supplied to a space between said projection optical system and the substrate has a concentration of carbon dioxide between 0.02 ppm and 750 ppm. 10. An exposure apparatus according to claim 9, wherein the injection unit injects the carbon dioxide at the concentration of the carbon dioxide in the fluid between 0.06 ppm and 300 ppm. 11. An exposure apparatus comprising: an illumination optical system for illuminating a mask using light from a light source; and a projection optical system for projecting a pattern of the mask onto a substrate, wherein a fluid supplied to a space between said projection optical system and the substrate has a resistivity value between 0.02 MΩ·cm and 10 MΩ·cm. 12. An exposure apparatus according to claim 11, wherein the injection unit injects the carbon dioxide so that the resistivity value between 0.04 MΩ·cm and 5 MΩ·cm. 13. A device manufacturing method comprising the steps of: exposing an object using an exposure apparatus according to claim 1 and developing the exposed object. 14. An exposure apparatus according to claim 2, wherein said injection apparatus includes a membrane module for injecting the carbon dioxide. 15. An exposure apparatus according to claim 2, wherein the injection unit injects the carbon dioxide at a concentration of the carbon dioxide in the fluid between 0.02 ppm and 750 ppm. 16. An exposure apparatus according to claim 3, wherein the injection unit injects the carbon dioxide at a concentration of the carbon dioxide in the fluid between 0.02 ppm and 750 ppm. 17. An exposure apparatus according to claim 2, wherein the fluid supply unit includes a resistivity meter for measuring a resistivity value of the fluid, and the injection unit injects the carbon dioxide based on a measurement result of the resistivity meter. 18. An exposure apparatus according to claim 3, wherein the fluid supply unit includes a resistivity meter for measuring a resistivity value of the fluid, and the injection unit injects the carbon dioxide based on a measurement result of the resistivity meter. 19. An exposure apparatus according to claim 2, wherein the injection unit injects the carbon dioxide so that a resistivity value of the fluid is between 0.02 MΩ·cm and 10 MΩ·cm. 20. An exposure apparatus according to claim 3, wherein the injection unit injects the carbon dioxide so that a resistivity value of the fluid is between 0.02 MΩ·cm and 10 MΩ·cm. 21. An exposure apparatus according to claim 6, wherein the injection unit injects the carbon dioxide so that a resistivity value of the fluid is between 0.02 MΩ·cm and 10 MΩ·cm.
TECHNICAL FIELD This invention relates generally to an exposure apparatus that utilizes an immersion method, and is suitable, for example, for the lithography process for manufacturing highly integrated devices, such as semiconductor devices, e.g., ICs and LSIs, image pick-up devices, e.g., CCDs, display devices, e.g., a liquid crystal panels, communication devices, e.g., optical waveguides, and magnetic heads by transferring a pattern of a mask (or a reticle) onto a photosensitive agent applied substrate. BACKGROUND ART An exposure apparatus for exposing a mask pattern onto a photosensitive-agent applied substrate have conventionally been used to manufacture semiconductor devices and liquid crystal panels. Since finer processing of a pattern is demanded for improved integrations of devices, exposure apparatuses are improved so as to resolve fine patterns. The following Rayleigh equation (1) defines resolution R of a projection optical system in an exposure apparatus, which is an index of a size of a resolvable pattern: R=k1(λ/NA) (1) where λ is an exposure wavelength, NA is a numerical aperture of the projection optical system at its image side, and k1 is a constant determined by a development process and others, which usually is approximately 0.5. As understood from Equation (1), the resolving power of the optical system in the exposure apparatus becomes higher as the exposure wavelength is shorter and the image-side NA of the projection optical system is greater. Therefore, following the mercury lamp i-line (with approximately 365 nm in wavelength), a KrF excimer laser (with approximately 248 nm in wavelength) and an ArF excimer laser (with approximately 193 nm in wavelength) have been developed, and more recently an F2 excimer laser (with approximately 157 nm in wavelength) is reduced to practice. However, a selection of the exposure light having a shorter wavelength makes it difficult to meet material requirements with respect to transmittance, uniformity and durability, etc., causing an increasing cost of the apparatus. An exposure apparatus having a projection optical system with a NA of 0.85 is commercially available, and a projection optical system with a NA of 0.9 or greater is researched and developed. Such a high-NA exposure apparatus has difficulties in maintaining good imaging performance with little aberration over a large area, and thus utilizes a scanning exposure system that synchronizes the mask with a substrate during exposure. However, a conventional design cannot make the NA greater than 1 in principle due to a gas layer having a refractive index of about 1 between the projection optical system and the substrate. On the other hand, an immersion method is proposed as means for improving the resolving power by equivalently shortening the exposure wavelength. It is a method used for the projection exposure, which fills liquid in a space between the final surface of the projection optical system and the substrate, instead of filling this space with air as in the prior art. The projection exposure apparatus uses, as the immersion method, a method for immersing the final surface of the projection optical system and the entire substrate in the liquid tank (see, for example, Japanese Patent Application, Publication No. 6-124873), and a local fill method that flows the fluid only in the space between the projection optical system and the substrate (see, for example, International Publication No. WO99/49504 pamphlet). The immersion method has an advantage in that the equivalent exposure wavelength has a wavelength of a light source times 1/n, where n is a refractive index of the used liquid. This means that the resolving power enhances by 1/n times the conventional resolving power, even when the light source having the same wavelength is used. For example, when the light source has a wavelength of 193 nm and the fluid is the water, the refractive index is about 1.44. Therefore, use of the immersion method can improve the resolving power by 1/1.44 times the conventional method. The most common fluid used for the immersion method is water. The water has a good transmittance relative to the ultraviolet light down to about 190 nm. In addition, advantageously, a large amount of water is used in the semiconductor manufacturing process, and the water gets along with the wafer and photosensitive agent. It is important to reduce the influence of the air gas bubbles to the exposure in the immersion exposure apparatus. These gas bubbles that enter the exposure area between the final surface of the projection optical system and the substrate scatter the exposure light. Therefore, the transferred pattern's critical dimension varies beyond the permissible range, causing insulations and short circuits contrary to the design intent in the worst case. Degassing of the fluid is the most effective, known method to prevent the influence of the gas bubbles to the exposure. Since the gas bubbles are unlikely to occur or the generated gas bubbles extinguish in a short time period in the degassed fluid, the influence of the gas bubbles to the exposure is prevented. However, the water widely used for the immersion method increases the resistivity, when degassed, and is likely to generate static electricity disadvantageously. For example, the pure water (i.e., the water containing few impurities) used for the semiconductor manufacturing process reaches the resistivity of 18 MQ-cm after degas. The substrate surface is electrically insulated since the photosensitive agent is applied on it. Therefore, as the stage moves the substrate, the static electricity is generated on the substrate surface and makes the device on the substrate defective. DISCLOSURE OF INVENTION With the foregoing in mind, the present invention has an exemplary object to provide an exposure apparatus that uses an immersion method while reducing the static electricity on the substrate. An exposure apparatus according to one aspect of the present invention includes a projection optical system for projecting a pattern of a mask onto a substrate, and a fluid supply unit for supplying a fluid between the projection optical system and the substrate, the fluid supply unit including an injection unit for injecting carbon dioxide into the fluid. An exposure apparatus according to another aspect of the present invention includes an illumination optical system for illuminating a mask using light from a light source, and a projection optical system for projecting a pattern of the mask onto a substrate, wherein a fluid supplied to a space between the projection optical system and the substrate has a concentration of carbon dioxide between 0.02 ppm and 750 ppm. An exposure apparatus according to still another aspect of the present invention includes an illumination optical system for illuminating a mask using light from a light source, and a projection optical system for projecting a pattern of the mask onto a substrate, wherein a fluid supplied to a space between the projection optical system and the substrate has a resistivity value between 0.02 MΩ·cm and 10 MΩ·cm. A device manufacturing method according to another aspect of the present invention includes the steps of exposing an object using the above exposure apparatus, and developing the exposed object. Other objects and further features of the present invention will become readily apparent from the following description of the embodiments with reference to accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention. FIG. 1 is a schematic view of a principal part in an exposure apparatus of a first embodiment. FIG. 2 is a schematic view showing a structural example of an injection unit of carbon dioxide. FIG. 3 is an explanatory view showing a relationship between a potential on a wafer and a pure water's resistivity in a wafer's cleansing step. FIG. 4 is an explanatory view showing a relationship between the pure water's resistivity and the concentration of carbon dioxide. FIG. 5 is an explanatory view showing a relationship between a normalized life of a gas bubble and a normalized concentration of a dissolved gas. FIG. 6 is an explanatory view showing a relationship between a water's PH value and a concentration of the carbon dioxide. FIG. 7 is a schematic view showing a principal part of an exposure apparatus as a variation of the first embodiment. FIG. 8 is a manufacture flow of a device. FIG. 9 is a wafer process shown in FIG. 8. BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will now be described in detail in accordance with the accompanying drawings. First Embodiment FIG. 1 is a schematic view of a principal part of an exposure according to a first embodiment. This embodiment applies the present invention to a scanning exposure apparatus. In FIG. 1, 1 denotes an illumination optical system for illuminating a reticle (or a mask) with light from a light source. The light source is an ArF excimer laser (with a wavelength of 193 nm), a KrF excimer laser (with a wavelength of 248 nm), and F2 laser, and the illumination optical system 1 includes a known optical system etc. (not shown). 3 denotes a refracting or catadioptric or another projection optical system for projecting a circuit pattern of a reticle 2 illuminated by the illumination optical system 1, onto a wafer 5 (substrate) as a second object. 15 denotes a distance measuring laser interferometer for measuring a two-dimensional position on a horizontal plane of each of a reticle stage 12 and a wafer stage 13 via a reference mirror 14. A stage controller 17 controls positioning and synchronizations of the reticle 2 and the wafer 5 based on this measurement value. The wafer stage 13 serves to adjust a position in a longitudinal direction, a rotational angle, and an inclination of a wafer so that the surface of the wafer 5 matches the image surface of the projection optical system 3. This embodiment uses the immersion method to shorten the equivalent exposure wavelength, and improve the exposure resolution. Therefore, this embodiment arranges a supply port 10 and a recovery port 11 around the final surface of the projection optical system 3, supply the water between the final surface of the projection optical system 3 and the wafer 5, and form a liquid film 4 there. An interval between the final surface of the projection optical system 3 and the wafer 5 is preferably small enough to stably form the liquid film 4, such as 0.5 mm. The supply port 10 is connected via a supply tube 8 to a fluid supply unit 6 that supplies the water. The recovery port 11 is connected via a recovery tube 9 to a fluid recovery unit 7 that recovers the water. The fluid supply unit 6 includes a degassing unit 18 and a carbon dioxide injection unit 19 provided at the downstream of the degassing unit 18. The degassing unit 18 can have, for example, a well-known membrane module (not shown) and a vacuum pump (not shown). An immersion controller 16 sends a control signal to the fluid supply unit 6 and the fluid recovery unit 7, and transmits and receives data with a stage controller 17. Thereby, the immersion controller 16 adjusts the liquid supply amount and recovery amount according to the wafer's moving direction and speed. This embodiment injects a predetermined concentration of carbon dioxide into the degassed water, prevents influence of gas bubbles to the exposure, and restrains the static electricity on the substrate. Carbon dioxide advantageously is inexpensive and does not contaminate the substrate. Referring to FIG. 2, a description will be given of one exemplary structure of the carbon dioxide injection unit 19. A membrane module 22 is provided between an inflow port 20 of the water and an outflow port 21. The membrane module 22 is connected to a supply source 24, such as a CO2 cylinder, via a valve 23. The valve 23 is electrically controlled by a carbon dioxide controller 25. This configuration restrains a concentration of the carbon dioxide in the water by changing the flow of the carbon dioxide to the membrane module 22 via the valve 23. A resistivity meter 26 is provided at a downstream side of the carbon dioxide injection unit. It is more preferable to control the concentration of the carbon dioxide within a predetermined range by electrically feeding back an output of the resistivity meter 26 to the carbon dioxide controller 25. Carbon dioxide gas may be injected into the water from a nozzle instead of using a membrane module. In this case, it is preferable to eliminate fine particles in the carbon dioxide gas using a filter in advance. A description will now be given of an optimal concentration of carbon dioxide. The lower limit of the carbon-dioxide concentration is determined from the necessity to restrain the static electricity on the wafer. FIG. 3 shows a relationship between the potential on the wafer and the water's resistivity when the wafer is cleansed with pure water from the nozzle (as detailed in Asano, “Spray, Contact, Flow Charges of Pure Water and Ultra-pure Water”, The Institute of Electrical Engineering of Japan, Vol. 108 (1988), pp. 362-366). It is understood from FIG. 3 that when the water's resistivity exceeds 10 MΩ·cm, the large potential is likely to generate on the wafer. On the other hand, when the water's resistivity is equal to or smaller than 5 MΩ·cm, the static electricity does not pose a problem. FIG. 4 shows a relationship between the carbon-dioxide concentration and the resistivity in the pure water. As the carbon-dioxide concentration increases, the resistivity decreases. The carbon-dioxide concentrations of 0.02 ppm and 0.06 ppm correspond to the resistivity of 10 MΩ·cm and 5 MΩ·cm. This means that the carbon-dioxide concentration in the water is preferably 0.02 ppm or greater, more preferably 0.06 ppm or greater, in order to restrain the static electricity on the wafer. The upper limit of the carbon-dioxide concentration can be determined from a problem of the gas bubbles. The gas-bubble generation is caused by a pressure variance in the water and inclusions of fine gas bubbles in the carbon-dioxide injection unit. In either case, as the carbon-dioxide concentration in the water increases, the gas bubble is likely to generate and its life (or a time period during which a generated gas bubble extinguishes due to diffusion) becomes long. In other words, the gas bubble is unlikely to extinguish and a danger of the influence of the gas bubbles to the exposure increases. FIG. 5 shows the normalized life τ/τ0 of a gas bubble as a function of Cs/C∞ as a normalized concentration of dissolved gas (as detailed in C. E. Brennen, “Cavitation and Bubble Dynamics,” Oxford University Press (1995), Chapter 2). Here, τ0 is the life when C∞=0.0 and Cs is a saturated concentration. When normalized concentration Cs/C∞ is 0.2 or smaller, the life of a gas bubble is close to C∞=0.0 and the gas bubble is likely to extinguish relatively immediately. On the other hand, when normalized concentration Cs/C∞ becomes 0.5 or greater, the life of a gas bubble drastically increases and gas bubble is unlikely to extinguish. As a result of this, in order to prevent the influence of the gas bubble to the exposure, the concentration of gas dissolved in the water is preferably 50% or smaller of the saturated concentration, and more preferably 20% or smaller of the saturated concentration. The saturated concentration of carbon dioxide in the water is about 1500 ppm in one air pressure. Therefore, in order to prevent the influence of the gas bubbles to the exposure, the carbon-dioxide concentration may be preferably 750 ppm or smaller, more preferably 300 ppm. These values are much greater than the lower limit of the carbon-dioxide concentration necessary to restrain the static electricity, and it is possible to reconcile the prevention of the gas bubble's influence with the restraint of the static electricity. In summary, the carbon-dioxide concentration in the water supplied to the liquid film 4 ranges preferably from 0.02 ppm to 750 ppm, and more preferably from 0.06 ppm to 300 ppm. The equivalent condition is that the resistivity ranges preferably from 0.02 MΩ·cm to 10 MΩ·cm, and more preferably from 0.04 MΩ·cm to 5 MΩ·cm. This configuration prevents the influence of the gas bubbles to the exposure and restrains the static electricity on the substrate. This embodiment can implement an acid environment suitable for a chemical amplification type of resist. The chemical amplification type of resist is widely used as the highly sensitive resist optimal to the lithography that uses a KrF laser and an ArF laser for a light source. On the other hand, when alkali contaminations in the water, such as ammonia, enter the resist surface in the chemical amplification type of resist, a chemical reaction is restricted and a problem on the pattern, such as T-top, occurs. This embodiment decreases the PH value by dissolving carbon dioxide in the water, and restrains the influence of alkali contaminations. FIG. 6 shows a relationship between the water's PH value and the carbon-dioxide concentration. Usually, the semiconductor factory has the pure water facility, and many of the pure water facilities have a degassing function. Where the degassed water is supplied from the pure water facility outside the exposure apparatus to the projection exposure apparatus, the projection exposure apparatus can omit the degassing unit 18. The omission of the degassing unit 18 would reduce the cost. FIG. 7 shows a variation of the exposure apparatus according to the instant embodiment that implements the above concept. The exposure apparatus as a variation differs from that shown in FIG. 1 in that the fluid supply unit 6 has no degassing unit. A structure of the carbon-dioxide injection unit, the optimal carbon-dioxide concentration in the water and resistivity in the exposure apparatus in this variation are the same as those in the exposure apparatus shown in FIG. 1. Thus, the immersion exposure apparatus of this embodiment prevents the influence of the gas bubbles to the exposure and restrains the static electricity on the substrate. Second Embodiment A description will now be given of an embodiment of a device manufacturing method using the exposure apparatus of the first embodiment. FIG. 8 is a flowchart for explaining a fabrication of devices (i.e., semiconductor chips such as IC and LSI, liquid crystal panels, and CCDs). Step 1 (circuit design) designs a device circuit. Step 2 (mask fabrication) forms a reticle having the designed circuit pattern. Step 3 (wafer making) manufactures a wafer using materials such as silicon. Step 4 (wafer process), which is referred to as a preprocess, forms actual circuitry on the wafer through photolithography using the mask and wafer. Step 5 (assembly), which is also referred to as a postprocess, forms into a semiconductor chip the wafer formed in Step 4 and includes an assembly step (e.g., dicing, bonding), a packaging step (chip sealing), and the like. Step 6 (inspection) performs various tests for the semiconductor device made in Step 5, such as a validity test and a durability test. Through these steps, a semiconductor device is finished and shipped (Step 7). FIG. 9 is a detailed flow of the wafer process. Step 11 (oxidation) oxidizes the wafer's surface. Step 12 (CVD) forms an insulating film on the wafer's surface. Step 13 (electrode formation) forms electrodes on the wafer by vapor disposition and the like. Step 14 (ion implantation) implants ions into the wafer. Step 15 (resist process) applies a photosensitive material onto the wafer. Step 16 (exposure) uses the exposure apparatus of the first embodiment to expose a circuit pattern on the mask onto the wafer. Step 17 (development) develops the exposed wafer. Step 18 (etching) etches parts other than a developed resist image. Step 19 (resist stripping) removes disused resist after etching. These steps are repeated, and multilayer circuit patterns are formed on the wafer. The device fabrication method of this embodiment may manufacture higher quality devices than the conventional one. The entire disclosure of Japanese Patent Application No. 2003-422932 filed on Dec. 19, 2003 including claims, specification, drawings, and abstract are incorporated herein by reference in its entirety. As many apparently widely different embodiments of the present invention can be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited to the specific embodiments thereof except as defined in the claims. INDUSTRIAL APPLICABLITY The inventive exposure apparatus injects carbon dioxide into the fluid used for the immersion method, and restrains the static electricity that would otherwise generate on the substrate surface. The inventive device manufacturing method can transfer an image of a device pattern on the mask onto a device substrate with high precision, and manufactures highly integrated devices, which are hard to manufacture in the prior art.
<SOH> BACKGROUND ART <EOH>An exposure apparatus for exposing a mask pattern onto a photosensitive-agent applied substrate have conventionally been used to manufacture semiconductor devices and liquid crystal panels. Since finer processing of a pattern is demanded for improved integrations of devices, exposure apparatuses are improved so as to resolve fine patterns. The following Rayleigh equation (1) defines resolution R of a projection optical system in an exposure apparatus, which is an index of a size of a resolvable pattern: in-line-formulae description="In-line Formulae" end="lead"? R=k 1 (λ/ NA )  (1) in-line-formulae description="In-line Formulae" end="tail"? where λ is an exposure wavelength, NA is a numerical aperture of the projection optical system at its image side, and k 1 is a constant determined by a development process and others, which usually is approximately 0.5. As understood from Equation (1), the resolving power of the optical system in the exposure apparatus becomes higher as the exposure wavelength is shorter and the image-side NA of the projection optical system is greater. Therefore, following the mercury lamp i-line (with approximately 365 nm in wavelength), a KrF excimer laser (with approximately 248 nm in wavelength) and an ArF excimer laser (with approximately 193 nm in wavelength) have been developed, and more recently an F 2 excimer laser (with approximately 157 nm in wavelength) is reduced to practice. However, a selection of the exposure light having a shorter wavelength makes it difficult to meet material requirements with respect to transmittance, uniformity and durability, etc., causing an increasing cost of the apparatus. An exposure apparatus having a projection optical system with a NA of 0.85 is commercially available, and a projection optical system with a NA of 0.9 or greater is researched and developed. Such a high-NA exposure apparatus has difficulties in maintaining good imaging performance with little aberration over a large area, and thus utilizes a scanning exposure system that synchronizes the mask with a substrate during exposure. However, a conventional design cannot make the NA greater than 1 in principle due to a gas layer having a refractive index of about 1 between the projection optical system and the substrate. On the other hand, an immersion method is proposed as means for improving the resolving power by equivalently shortening the exposure wavelength. It is a method used for the projection exposure, which fills liquid in a space between the final surface of the projection optical system and the substrate, instead of filling this space with air as in the prior art. The projection exposure apparatus uses, as the immersion method, a method for immersing the final surface of the projection optical system and the entire substrate in the liquid tank (see, for example, Japanese Patent Application, Publication No. 6-124873), and a local fill method that flows the fluid only in the space between the projection optical system and the substrate (see, for example, International Publication No. WO99/49504 pamphlet). The immersion method has an advantage in that the equivalent exposure wavelength has a wavelength of a light source times 1/n, where n is a refractive index of the used liquid. This means that the resolving power enhances by 1/n times the conventional resolving power, even when the light source having the same wavelength is used. For example, when the light source has a wavelength of 193 nm and the fluid is the water, the refractive index is about 1.44. Therefore, use of the immersion method can improve the resolving power by 1/1.44 times the conventional method. The most common fluid used for the immersion method is water. The water has a good transmittance relative to the ultraviolet light down to about 190 nm. In addition, advantageously, a large amount of water is used in the semiconductor manufacturing process, and the water gets along with the wafer and photosensitive agent. It is important to reduce the influence of the air gas bubbles to the exposure in the immersion exposure apparatus. These gas bubbles that enter the exposure area between the final surface of the projection optical system and the substrate scatter the exposure light. Therefore, the transferred pattern's critical dimension varies beyond the permissible range, causing insulations and short circuits contrary to the design intent in the worst case. Degassing of the fluid is the most effective, known method to prevent the influence of the gas bubbles to the exposure. Since the gas bubbles are unlikely to occur or the generated gas bubbles extinguish in a short time period in the degassed fluid, the influence of the gas bubbles to the exposure is prevented. However, the water widely used for the immersion method increases the resistivity, when degassed, and is likely to generate static electricity disadvantageously. For example, the pure water (i.e., the water containing few impurities) used for the semiconductor manufacturing process reaches the resistivity of 18 MQ-cm after degas. The substrate surface is electrically insulated since the photosensitive agent is applied on it. Therefore, as the stage moves the substrate, the static electricity is generated on the substrate surface and makes the device on the substrate defective.
<SOH> BRIEF DESCRIPTION OF DRAWINGS <EOH>The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention. FIG. 1 is a schematic view of a principal part in an exposure apparatus of a first embodiment. FIG. 2 is a schematic view showing a structural example of an injection unit of carbon dioxide. FIG. 3 is an explanatory view showing a relationship between a potential on a wafer and a pure water's resistivity in a wafer's cleansing step. FIG. 4 is an explanatory view showing a relationship between the pure water's resistivity and the concentration of carbon dioxide. FIG. 5 is an explanatory view showing a relationship between a normalized life of a gas bubble and a normalized concentration of a dissolved gas. FIG. 6 is an explanatory view showing a relationship between a water's PH value and a concentration of the carbon dioxide. FIG. 7 is a schematic view showing a principal part of an exposure apparatus as a variation of the first embodiment. FIG. 8 is a manufacture flow of a device. FIG. 9 is a wafer process shown in FIG. 8 . detailed-description description="Detailed Description" end="lead"?
20050608
20071106
20060309
96037.0
G03B2754
0
KIM, PETER B
EXPOSURE APPARATUS AND DEVICE MANUFACTURING METHOD
UNDISCOUNTED
0
ACCEPTED
G03B
2,005
10,538,605
ACCEPTED
System and method for lighting control network recovery from master failure
The present invention provides a master-slave architecture for a radio frequency RF networked lighting control system having all slave elements (ballasts) configured as backups for a network master control unit. In the system and method of the present invention a slave element can become the network master network unit without reconfiguring the network and without any human intervention. Similarly, both a master and one or more slave elements may recover from a temporary outage without necessitating reconfiguration of the network and without any human intervention.
1. A lighting control network recovery system for a wireless network of lighting elements, comprising: a plurality of ballasts each of said plurality of ballasts being configured both as a slave element and a replacement network master control unit; one of said plurality of ballasts configured as a network master control unit to control each of said plurality of ballasts as a slave element, wherein, when a network master control unit no longer functions, one of said plurality of ballasts configured as a replacement network master control unit takes its place by becoming a new network master control unit and taking control of the lighting control network. 2. The system of claim 1, further comprising: at least one remote control unit having a plurality of keys; and at least one main power line having said ballasts connected thereto such that: a. the one of said ballasts that is configured as a network master control unit is adapted to setup the network configuration of the lighting control network on power-up reset by recording the registration of each slave element and the association of each slave element with at least one key of the at least one remote control and to control said lighting control network thereafter, and b. each of said plurality of ballasts, other than said network master control unit, that is configured as a slave element is adapted to join a lighting control network on power-up reset by registering with the network master control unit and associating with at least one of said plurality of keys of said at least one remote control unit. 3. The system of claim 2, wherein said at least one remote control unit is configured as a slave element and said at least one remote control unit is connected first to the network master control unit before any of said plurality of ballasts configured both as a slave element and a replacement network master control unit. 4. The system of claim 2, further comprising: a non-volatile memory (NVM) associated with the network master control unit and each said slave element; and a pairing-link table stored in the non-volatile memory of the network master control unit and each slave element, having an initialization as empty and adapted to store c. a registration termed an “enumeration” of each said slave element that registers with the network master control unit such that the slave element is listed in the paring link table of the network master control unit, and d. a binding of each said slave element listed in said pairing-link table with at least one of said plurality of keys of said at least one remote control unit, such that the binding is recorded in the paring link table of the network master control unit, wherein, the network is established by the network master control unit once setup is accomplished and every time the pairing-link table is updated the network master control unit transmits the update to each said slave element. 5. The system of claim 4, further comprising: a periodically transmitted beacon packet by the network master control unit to each said slave element, said packet having status information of the network master control unit and being transmitted with frequency F; a periodically transmitted wakeup message by each said slave element to the network master control unit, said message being transmitted with the predetermined frequency F and at a predetermined point in time; wherein, when a slave element determines that the master is not working from at least one of the status beacon packet and the wakeup message, the slave element waits a given delay time D and then starts to convert itself to a new network master control unit such that the first said element to discover the network master control unit is not working becomes a new network master control unit and such that network recovery takes place automatically with no need to set up the network control configuration again, and wherein the new network master control unit switches to master status using a master code that has already been stored in its memory, establishes a new network using a same network ID that the previous network master control unit used and begins to act as a network master control unit for the new network using the same network ID, informs each said slave element to listen for a beacon from the new network master control unit and to send a wake up message to the new network master control unit, and updates the pairing-link table of the new network master control unit and transmits the updated pairing-link table to each said slave element for storage in its NVM. 6. The system of claim 2, wherein on power-up reset: if the network master control unit has a network ID stored in its non-volatile memory then it has been a master before and if the ID is in use the network master control unit enumerates as a slave element to the new master of the network with the ID, and if the ID is not in use then the network master control reestablishes that network using the ID and pairing-link table so that the network can be recovered after a temporary power interruption, otherwise it has not been a master before, a random ID is generated and stored in its non-volatile memory and its network is established having the randomly generated network ID; and if the slave element has a network ID stored in its non-volatile memory it has been a slave element in that network before and it rejoins that network so that the network connection is recovered after a temporary power interruption, otherwise it has not been a slave element in a network before and it tries to enumerate to a network master control unit in its radio frequency vicinity. 7. The system of claim 6, wherein the system is implemented using a low power consumption, two-way wireless communication standard having a protocol and comprising a radio, a physical layer, a data link layer, and a an application layer. 8. The system of claim 7, wherein the two-way wireless communication standard is Zigbee™ and the protocol is Protocol for Universal Radio Link (PURL). 9. A method for recovery control of a wireless lighting control network, comprising the steps of: providing a plurality of ballasts wherein each of said plurality ofballasts is configured both as a slave element and a replacement network master control unit; providing one of said provided plurality of ballasts configured as a network master control unit to control each of said plurality of ballasts as a slave element; when the network master control unit no longer functions, replacing the network master control unit with one of said plurality of provided ballasts configured as a replacement network master control unit; and communicating with each slave element to become a new network master control unit and take control of the lighting control network by the replacement network master control unit. 10. The method of claim 9, further comprising the steps of: providing at least one remote control unit having a plurality of keys; providing at least one main power line having said ballasts connected thereto; on power-up reset performing the steps of: i. setting up the network configuration of the lighting control network by the network master control unit, by performing the substeps of— registering each said slave element with the network master, and associating each registered slave element with one of said plurality of keys of said at least one remote control unit; and ii. controlling the lighting control network by the network master control unit. 11. The method of claim 10, further comprising the steps of: configuring said at least one remote control unit is as a slave element, and registering said at least one remote control unit with the network master control unit first. 12. The method of claim 10, further comprising the steps of: associating a non-volatile memory with the network master control unit and each said slave element; providing a pairing-link table in the non-volatile memory of the network master control unit; initializing each said provided pairing-link table as empty; enumerating each said slave element that registers with the network master control unit in the paring link table of the network master control unit; binding each said slave element enumerated in said pairing-link table with at least one of said plurality of keys of said at least one remote control unit; recording the bound slave element and its corresponding remote control key as updates in the paring link table of the network master control unit; informing each slave element of the recorded update made by the network master control unit to its pairing-link table; and updating by the slave element of its pairing-link table with the information of the recorded updates made by the network master control table. 13. The method of claim 12, further comprising the steps of: periodically and at a frequency F, transmitting a beacon packet by the network master control unit to each said slave element that includes status information of the network master control unit; periodically and at a frequency F and at a predetermined point in time, transmitting a wakeup message by each said slave element to the network master control unit; when a slave element determines that the master is not working from at least one of the transmitted status beacon packet and wakeup message, performing the following steps: a. waiting a given delay D by the slave element, and b. when D times out, converting itself by the slave element to a new network master control unit; when a master code is already stored in the memory of the new network master control unit, establishing a network with the same network ID that the previous network master control unit used; beginning to act as a network master control unit for the new network; informing each said slave element to listen for a beacon from the new network master control unit and to send a wake up message to the new network master control unit; updating the pairing-link table of the new network master control unit; and transmitting the updated pairing-link table to each said slave element. 14. The method of claim 10, on power-up reset further performing the steps of: enumerating as a slave element to a new network master control unit with this ID if the network master control unit has a network ID stored in its memory that is already in use; reestablishing the network by the network master control unit with its stored ID if it is not in use and with its stored pairing-link table; when there is no network ID stored in the memory of the network master control unit, performing the steps of: a. randomly generating a network ID, b. storing the ID in its non-volatile memory, and c. establishing its network using the randomly generated network ID, and if a slave element has a network ID stored in its non-volatile memory, rejoining that network by the slave element; and if a slave element does not have a network ID stored in its non-volatile memory, trying to enumerate to a network master control unit in its radio frequency vicinity by the slave element. 15. A system with a low power consumption, two-way wireless communication standard having a protocol and comprising a radio, a physical layer, a data link layer, and an application layer that performs the method of claim 14. 16. The system of claim 15, wherein the two-way wireless communication standard is Zigbee™ and the protocol is Protocol for Universal Radio Link (PURL).
BACKGROUND OF THE INVENTION 1. Field of the Invention This invention is related to recovering the ballast control in a wireless lighting control network when the main controller (master) fails. More particularly, this invention is related to a wireless lighting control network system and method in which all lighting ballasts act as backups for a network master control unit. Most particularly, this invention is related to a system and method for a master-slave architecture for a wireless lighting control network that include all lighting ballasts as backup for a network master control unit such that there is no need for reconfiguration of the network or human intervention when a master fails or functioning of the master or slave ballasts is interrupted. 2. Description of Related Art Traditional lighting has wall switches wired to the ballasts individually or in groups. If one of the switches fails, the ballasts that are controlled by other switches won't be affected. In wireless control, the on/off or light intensity is controlled by the signals transmitted from a remote table-top or handheld control unit via infra-red (IR) or radio frequency (RF) communication media. There are basically two types of system configurations in wireless control. One is a distributed system that has several remote control units, each remote unit controlling a certain number of ballasts through the wireless links. The ballasts obtain the IDs of their designated controllers during the initialization of the system. Then, during normal operation the ballasts “listen” and react to the lamp operational signals coming transmitted by these controllers. The systems described in U.S. Pat. No. 5,848,054 to Mosebrook et al. and U.S. Pat. No. 6,174,073 to Regan, fall into this category. The other type of system is a master-slave oriented networked architecture, which is the focus of this invention. There is one central device, so called “master” or “network coordinator” that manages communication among the network nodes. The ballasts and the remote controls both act as the slaves in the network. All the information about the wireless links between the keys on the remote control and the ballasts is gathered in a table stored in the master during initial configuration of the system. During the normal operation, the signal transmitted by a remote control is routed to its destination ballast by the master based on the link information in the table. The physical form of the master can be the same as a slave device, i.e. the master can reside in the remote control or the ballast. It is preferable to put the master in the ballast as it is mains-powered and at a fixed location. Connecting to the mains allows the master to transmit beacon packets that contain the master status information as a way to keep the slaves in touch every once in a while. Being at a fixed location avoids problems a missing handheld remote control since all the network information is lost in such a case. The master-slave networked system has the following advantages over the distributed system: If more than one remote-control is needed in a multi-zone office, a separate master is essential for network recovery if a remote control is lost. A master-slave architecture centralizes the control information for the local network and makes it easier to form the building-wide network. In both wireless systems, there could be several reasons for a system failure: Power Loss: In normal operation, the ballasts should not be cut off from the mains power for any reason, as they have to keep the RF communication alive all the time. Turning-off the lamps only puts the lamp-drivers in stand-by in digital ballasts, and it does not shut off the power supply to the circuits. Sometimes the controller that happens to be installed on a different mains power line from the ballasts experiences a power outage. Other times the controller could be running out of battery if battery powered. Circuit malfunction: This includes circuit failures in the master control unit (MCU) or RF transceiver, and the temporary RF signal blockage/shielding or interference such that the communications between the devices are blocked. Master Control Unit Failure: In a wireless network the master control unit represents a single point of failure. That is, once the master fails, all link information kept only by the master is lost. In a point-to-point network the network is no longer operable. This also occurs because the master routes all the packets and the master fails. There are several ways to enhance the reliability. The wireless system taught by U.S. Pat. No. 5,848,054 to Mosebrook et al., increases the reliability communications by adding repeaters between the source and destination devices. When the master and the ballasts suffer from intermittent communication in the direct path due to distance or RF interference, a repeater provides an additional communication path. However, this does not solve the problem of the master going completely dead. Another system, taught by EP0525133 to Edwards et al., solves the master power outage problem by providing a battery as a back-up power source. When AC power is available, the battery is being charged. When the AC is cut off, the power supply automatically switches to the battery. Even though this idea teaches a battery backup for conventional hardwired lighting systems, it can be applied to the wireless system too. However, it can be costly to provide an additional power supply to every control device. In a master-slave networked system, due to the important role of the master, it is critical to make sure that there is always a master working properly at all times. If the controller fails due to a power outage (dead battery) or malfunction, the problem arises of to how to regain controls of the ballasts. New replacements can be brought in, but the configuration, such as which key to control which ballasts, has to be set up again since there is no hardwiring in a wireless control system. Depending on how the wireless control network is built in the first place, sometimes this may mean starting the configuration from scratch all over again. SUMMARY OF THE INVENTION The present invention solves the problems associated with a single master, as discussed above, by providing multiple back-up masters in a master-slave orientated control network. The system and method of the present invention enhances system reliability without an extra device or costly circuitry. Each ballast in the network has the potential to be a master when needed. This means each device needs a little bit of extra memory to store the master program. In a digital ballast, the cost for additional memory is minimal. The master malfunction is automatically detected by the slaves in the network. Once a master fails, a back-up master takes control of the network following a pre-established protocol or algorithm of a preferred embodiment. The network recovery takes place automatically and is transparent to the end user. There is no need to set up the network control configuration again. The original master resides in one of the ballasts after the installation and configuration of the network, which includes the physical installation, registration of the ballasts with the network master (so called “enumeration”), and associating the ballasts with certain buttons on the remote control (so called “binding”). All the ballasts (slaves in the network) have the possibility and capability of becoming the new master if needed. It is randomly decided, when necessary, which ballast is the next back-up master. There is no priority number assigned before hand. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 illustrates a flowchart of the back-up master operation taking over control of the network. FIG. 2 illustrates the failure of a network master control unit and several slaves of the same wireless lighting network. FIG. 3 illustrates recovery of a network master control unit from a power outage. DESCRIPTION OF PREFERRED EMBODIMENTS The wireless lighting control network functions analogously to a wireless communication network. The lighting network itself is identified by a network ID, which is the essential information for communication among all the network nodes and there is a several layer communication protocol stack associated with every component of the wireless lighting network. After the network is established by the master and an enumeration of the lighting elements and pairing of enumerated lighting elements with keys are done, the master has all the pairing information stored in a pairing-link table in the protocol stack. Each pairing-link table entry specifies which ballast(s) reacts to which key and on which remote control. The master transfers this pairing-link table to all the slaves in the network. Every time the pairing-link table is changed, the master keeps all the slaves updated. Master and slaves exchange status information at pre-determined intervals to make sure that the master is working properly. The master sends out beacon packets that contains status information at these certain intervals. The slaves receive the beacon packets and determine the state of the master. As illustrated in FIG. 1, at step 11 slaves also wake up a master that is in its sleep mode at intervals t1. Each slave keeps in touch with the master with the same interval but at a different point of time (based on a randomly generated number). Once a slave finds that the master is not working, at step 13 it waits a certain delay time t2 before taking any action in case the master become operational again. Once the delay is timed out, at step 15 the first slave who discovers the master-failure will start to convert itself to the new master. While the first slave is waiting, the rest of the slaves can find out the master-failure too, but all of them have to wait for the same delay t2 before reacting, so the first to discover the master outage becomes the new master. The new master switches to the master status using the master code that has already been stored in its memory. The new master establishes the network using the same network ID that the previous master used, providing this network ID is not used by any other networks in the vicinity. Then the application layer of the master does the following, as shown in FIG. 1. 1. Informs the lower layers in the new master to act as a master (sending beacons . . . ) using the same network ID. 2. At step 15 informs the slaves that a new master is taking over the network and they should synchronize with the new master in terms of listening to the beacons and checking the master's status. 3. At step 16 updates the pairing-link table and transmits a copy of it to all the slaves. The algorithm of the present invention can be implemented in combination with a wireless communication protocol, either proprietary or open standard to ensure a reliable RF communication such as Zigbee™. Zigbee™ is a low cost, low power consumption, two-way, wireless communications standard aimed initially at automation, toys, & PC peripherals, and is a good candidate for implementing this system and method of the present invention for a recoverable RF wireless lighting control network that uses slaves as backup masters. Normal Operation The very first time the system is installed, the master and slaves all take on the physical format of a ballast. In a preferred embodiment, their roles are distinguished by certain mechanisms or algorithms. In a given single room, there must be a master and at least one slave. All the devices, including master and slaves, have nonvolatile memories (NVM) to store the enumeration status information, network ID information and pairing-link table information. When the devices are initially powered up, the master checks its NVM to see if it has been in any network as a master before. If not, it establishes its network using a randomly generated network ID. The slaves check their NVMs to see if they have been in any network as a slave before, if not, they try to enumerate to a master available in their RF vicinity. Once they are connected to a master, the lamp flashes to provide feedback to the user and the user presses a button on the remote control to confirm that it should be included in the network. The remote control is also a slave to this network and has to be connected to the master before the ballasts. Reasons for Master Failure There are two major reasons for the master to fail: 1. Power Loss: During normal operation, both master and slave must not be cut off from the main power supply for any reason, as they have to keep the RF communication alive all the time. Turning off the lamps only puts the lamp drivers in stand-by, and it does not shut off the power supply to the circuits. When the ballasts are initially powered up from the main power supply, if a ballast is supposed to be a master, it starts to establish its network. If it is supposed to be a slave, it starts to request joining a network. The ballasts store their IDs and network connection information (such as the pairing-link table, the flag indicating if it has been enumerated before, etc.) in the non-volatile memory so that the network connection can be recovered after a temporary power interruption. If the power of the whole system is consistently interrupted, then the ballasts maintain their previous roles after the power comes back. In this case, the power-up reset does not trigger the enumeration request in the ballast if it was already in a network previously. This scenario is not considered a master failure since the whole network recovers to its previous state before the power interruption without further procedures being invoked. However, sometimes the master could be installed on a different main power line from the slaves. When its power is experiencing an outage and the one for the slaves is not, a back-up master is needed to keep the rest of the slaves under control. 2. Circuit malfunction: This includes failures in the MCU or transceiver and temporary RF signal blockage/shielding around the master, etc. In this case, a back-up master is also necessary to recover the operation of all the slaves. FIG. 2 illustrates the master failure situation. If a circuit malfunction occurs and the network master control unit 22 is not functional, a new master control unit 28 takes over control of the existing lighting network by following the algorithm illustrated in FIG. 1. By way of example only, several slaves and a network master control unit 22 are shown in a non-working circuit in FIG. 2. The new network master control unit 28 takes control of the exiting lighting network 20, updates its pairing-link table to reflect these non-working units and transmits the updates to all the working slaves in the network. Disabled Master Coming Back In the case that the previous master recovers from its temporary RF blockage or power outage, it tries to join the same network again, but not as a master, instead, as a slave since there a new master has already taken over control of the network. The following describes the two different situations where the previous master recovers from a temporary power outage and RF blockage. If the previous master failure is due to circuit malfunction, it cannot recover anyway. 1. Coming Back from Temporary Power Outage Referring now to FIG. 3, when the previous master regains power 31, it goes through the power-up reset and then checks the contents of its NVM. When its NVM indicates that it was previously the master of a network 34, it tries to recover its role as master in the same network by attempting to establish its network using the same network ID 34. It starts the search at this particular network identifier, and then listens for a beacon packet to see if anyone else is already using this network ID 35. As soon as it finds out that another device has already taken its place as the master in this particular network (using the previous network ID), it withdraws itself from attempting to become the master again, and it enumerates to the network as a slave 36. Since the network ID is still the same, it does not require any user intervention during the enumeration. As can be seen in FIG. 3, some of the slaves might have been out of power, as well, if they were on the same power line as the previous master. When they regain power, they go through power-up reset and then check the contents of their NVMs. As their NVMs indicate that they were was previously slaves of a network, they try to recover this role as a the slave 36, in the same network by attempting to enumerate using the previous network ID. The new master is able to accept them without user intervention since the new master has the information that the slave has been in this network before the power was out. 2. Coming Back from Temporary RF Communication Blockage When the previous master failure is due to the temporary RF communication blockage, the protocol stack is able to report this problem to the application layer. The application layer then goes back to the beginning of the routine, which is power-up reset. Then it keeps trying to re-establish its network using the same network ID 38. If, by the time the RF channel is clear for communication for this device, the new master has already taken over the network, the old master withdraws from trying to become the master, but tries to become a slave, which is the same as the situation in coming back from temporary power outage and is discussed above and illustrated in FIG. 3. If by the time the old master regains RF accessibility, the new master has not yet taken control of the network, the old master recovers control over the same network with the same ID and this is illustrated in FIG. 3. Although the present invention has been described in relation to particular embodiments thereof, many other variations and modifications and other uses will be apparent to those skilled in the art. The present invention, therefore, should be limited not by the specific disclosure herein, but only by the appended claims.
<SOH> BACKGROUND OF THE INVENTION <EOH>1. Field of the Invention This invention is related to recovering the ballast control in a wireless lighting control network when the main controller (master) fails. More particularly, this invention is related to a wireless lighting control network system and method in which all lighting ballasts act as backups for a network master control unit. Most particularly, this invention is related to a system and method for a master-slave architecture for a wireless lighting control network that include all lighting ballasts as backup for a network master control unit such that there is no need for reconfiguration of the network or human intervention when a master fails or functioning of the master or slave ballasts is interrupted. 2. Description of Related Art Traditional lighting has wall switches wired to the ballasts individually or in groups. If one of the switches fails, the ballasts that are controlled by other switches won't be affected. In wireless control, the on/off or light intensity is controlled by the signals transmitted from a remote table-top or handheld control unit via infra-red (IR) or radio frequency (RF) communication media. There are basically two types of system configurations in wireless control. One is a distributed system that has several remote control units, each remote unit controlling a certain number of ballasts through the wireless links. The ballasts obtain the IDs of their designated controllers during the initialization of the system. Then, during normal operation the ballasts “listen” and react to the lamp operational signals coming transmitted by these controllers. The systems described in U.S. Pat. No. 5,848,054 to Mosebrook et al. and U.S. Pat. No. 6,174,073 to Regan, fall into this category. The other type of system is a master-slave oriented networked architecture, which is the focus of this invention. There is one central device, so called “master” or “network coordinator” that manages communication among the network nodes. The ballasts and the remote controls both act as the slaves in the network. All the information about the wireless links between the keys on the remote control and the ballasts is gathered in a table stored in the master during initial configuration of the system. During the normal operation, the signal transmitted by a remote control is routed to its destination ballast by the master based on the link information in the table. The physical form of the master can be the same as a slave device, i.e. the master can reside in the remote control or the ballast. It is preferable to put the master in the ballast as it is mains-powered and at a fixed location. Connecting to the mains allows the master to transmit beacon packets that contain the master status information as a way to keep the slaves in touch every once in a while. Being at a fixed location avoids problems a missing handheld remote control since all the network information is lost in such a case. The master-slave networked system has the following advantages over the distributed system: If more than one remote-control is needed in a multi-zone office, a separate master is essential for network recovery if a remote control is lost. A master-slave architecture centralizes the control information for the local network and makes it easier to form the building-wide network. In both wireless systems, there could be several reasons for a system failure: Power Loss: In normal operation, the ballasts should not be cut off from the mains power for any reason, as they have to keep the RF communication alive all the time. Turning-off the lamps only puts the lamp-drivers in stand-by in digital ballasts, and it does not shut off the power supply to the circuits. Sometimes the controller that happens to be installed on a different mains power line from the ballasts experiences a power outage. Other times the controller could be running out of battery if battery powered. Circuit malfunction: This includes circuit failures in the master control unit (MCU) or RF transceiver, and the temporary RF signal blockage/shielding or interference such that the communications between the devices are blocked. Master Control Unit Failure: In a wireless network the master control unit represents a single point of failure. That is, once the master fails, all link information kept only by the master is lost. In a point-to-point network the network is no longer operable. This also occurs because the master routes all the packets and the master fails. There are several ways to enhance the reliability. The wireless system taught by U.S. Pat. No. 5,848,054 to Mosebrook et al., increases the reliability communications by adding repeaters between the source and destination devices. When the master and the ballasts suffer from intermittent communication in the direct path due to distance or RF interference, a repeater provides an additional communication path. However, this does not solve the problem of the master going completely dead. Another system, taught by EP0525133 to Edwards et al., solves the master power outage problem by providing a battery as a back-up power source. When AC power is available, the battery is being charged. When the AC is cut off, the power supply automatically switches to the battery. Even though this idea teaches a battery backup for conventional hardwired lighting systems, it can be applied to the wireless system too. However, it can be costly to provide an additional power supply to every control device. In a master-slave networked system, due to the important role of the master, it is critical to make sure that there is always a master working properly at all times. If the controller fails due to a power outage (dead battery) or malfunction, the problem arises of to how to regain controls of the ballasts. New replacements can be brought in, but the configuration, such as which key to control which ballasts, has to be set up again since there is no hardwiring in a wireless control system. Depending on how the wireless control network is built in the first place, sometimes this may mean starting the configuration from scratch all over again.
<SOH> SUMMARY OF THE INVENTION <EOH>The present invention solves the problems associated with a single master, as discussed above, by providing multiple back-up masters in a master-slave orientated control network. The system and method of the present invention enhances system reliability without an extra device or costly circuitry. Each ballast in the network has the potential to be a master when needed. This means each device needs a little bit of extra memory to store the master program. In a digital ballast, the cost for additional memory is minimal. The master malfunction is automatically detected by the slaves in the network. Once a master fails, a back-up master takes control of the network following a pre-established protocol or algorithm of a preferred embodiment. The network recovery takes place automatically and is transparent to the end user. There is no need to set up the network control configuration again. The original master resides in one of the ballasts after the installation and configuration of the network, which includes the physical installation, registration of the ballasts with the network master (so called “enumeration”), and associating the ballasts with certain buttons on the remote control (so called “binding”). All the ballasts (slaves in the network) have the possibility and capability of becoming the new master if needed. It is randomly decided, when necessary, which ballast is the next back-up master. There is no priority number assigned before hand.
20050610
20090630
20061102
94315.0
G08B536
0
A, MINH D
SYSTEM AND METHOD FOR LIGHTING CONTROL NETWORK RECOVERY FROM MASTER FAILURE
UNDISCOUNTED
0
ACCEPTED
G08B
2,005
10,538,632
ACCEPTED
Preserving linearity of an isolator-free power amplifier by dynamically adjusting gain
An amplifier circuit (100) includes a driver stage ( ) 120 with at least an active device (140) for pre-amplification and output of a pre-amplified signal; and an output stage (160) with at least an active device (180) for further amplification of the pre-amplified signal and output of an amplified signal. A phase shifter (155) shifts the phase of the pre-amplified signal. A detector (190) measures levels of forward and reflected parts of the amplified signal, and a gain and phase control circuit (145) independently and selectively controls and adjusts the phase shifter (155) for optimal amplifier performance and minimal difference between the forward and reflected signals. The gain and phase control circuit also independently and selectively controls and modifies the gain of the active devices (140, 180) of the driver and output stages (120, 160) as a function of the levels of the forward and reflected signals to substantially maintain constant linearity of the amplifier circuit (100) with load variations.
1. An amplifier circuit comprising: a driver stage having at least a first active device which receives a signal for pre-amplification and outputs a pre-amplified signal; a phase shifter which adjusts a phase of said pre-amplified signal and outputs a phase-shifted signal; an output stage having at least a second active device which receives said phase-shifted signal for further amplification and output of an amplified signal; a detector which measures levels of forward signal and reflected signal of said amplified signal; and a control circuit which controls said phase shifter in response to said levels of forward signal and reflected signal to substantially maintain linearity of said amplifier circuit with load variations. 2. The amplifier circuit of claim 1, wherein said output stage is coupled to a load without an isolation device between said output stage and said load. 3. The amplifier circuit of claim 1, wherein said control circuit modifies a gain of at least one of said at least first active device and said at least second active device to substantially maintain said linearity of said amplifier circuit with said load variations. 4. The amplifier circuit of claim 1, wherein said control circuit independently controls said at least first active device and said at least second active device. 5. The amplifier circuit of claim 1, wherein said control circuit independently controls said phase shifter, said at least first active device and said at least second active device to substantially maintain said linearity of said amplifier circuit with said load variations. 6. The amplifier circuit of claim 1, wherein said at least first active device and said at least second active device are NPN transistors. 7. The amplifier circuit of claim 1, further comprising an input match circuit coupled between an input of said amplifier circuit and said driver stage for matching an input impedance of said amplifier circuit to an output impedance of a device coupled to said input. 8. The amplifier circuit of claim 7, further comprising at least one capacitor coupled between said input match circuit and said driver stage. 9. The amplifier circuit of claim 1, further comprising at least one capacitor coupled between an input of said amplifier circuit and said driver stage. 10. The amplifier circuit of claim 1, further comprising an inter-stage match circuit coupled between an output of said driver stage and an input of said phase shifter. 11. The amplifier circuit of claim 10, further comprising at least one capacitor coupled between said phase shifter and said output stage. 12. The amplifier circuit of claim 1, further comprising at least one capacitor coupled between said phase shifter and said output stage. 13. A wireless communication device comprising the amplifier circuit of claim 1. 14. An amplifier circuit comprising: a driver stage having at least a first active device which receives a signal for pre-amplification and outputs a pre-amplified signal; a phase shifter which adjusts a phase of said pre-amplified signal and outputs a phase-shifted signal; an output stage having at least a second active device which receives said phase-shifted signal for further amplification and output of an amplified signal; a detector which measures levels of forward signal and reflected signal of said amplified signal; and a control circuit which independently and selectively controls switching said phase shifter, said at least first active device, and said at least second active device as a function of said levels of forward signal and reflected signal to substantially maintain linearity of said amplifier circuit with load variations. 15. A method for substantially maintaining linearity of an amplifier circuit with variations of a load coupled to an output of said amplifier circuit comprising: measuring levels of forward signal and reflected signal at said output; and modifying a phase shifter to change a phase of an output signal of said amplifier circuit as a function of said levels to substantially maintain linearity of said amplifier circuit with load variations. 16. The method of claim 15, wherein said modifying act further modifies a first gain of a first active device of a driver stage, and a second gain of a second active device of an output stage of said amplifier circuit in response to said levels to substantially maintain said linearity. 17. The method of claim 16, wherein said modifying act independently and selectively modifies said phase shifter, said first gain and a second gain.
The invention relates to an isolator-free power amplifier circuit typically used in wireless communication devices which preserves linearity of the power amplifier under varying loads. More particularly, linearity is preserved by dynamically adjusting the gain by changing the input bias of active devices of the power amplifier circuit, and/or by dynamically adjusting the phase of a pre-amplified signal. Power amplifiers are used in transmitters to amplify signals, such as radio frequency (RF) signals. Such power amplifiers are included in transmitters of wireless communication devices, such as mobile telephones. The power amplifier typically provides an amplified RF signal to an antenna for transmission over the air. RF antennas as for instance applied in mobile phones, operate in strongly varying environments, resulting in a varying antenna input impedance, a VSWR (Voltage Standing Wave Ratio) of 4:1 is not uncommon. Especially at high output levels, this may result in a severe distortion of for instance a CDMA (code division multiple access), TDMA (time division multiple access), Edge or W-CDMA modulated carrier signal having a non-constant envelope. The conventional solution to protect the power amplifier of a cellular phone against antenna mismatch conditions to preserve linearity is to use an isolator, such as a circulator, placed between the power amplifier and the output load, such as the antenna, to limit the effects of load impedance variation on the performance of the power amplifier. The circulator secures proper 50 Ohm loading of the power amplifier under antenna mismatch conditions by dissipating the reflected power in the isolator or in a third circulator port termination. Directivity in the power flow is created by ferromagnetic material. The above aspects of the state of the art are described in more detail with reference to FIG. 1 which shows a basic block diagram of an arrangement 10 used for a power source 12 isolated with a circulator 14 from a mismatched antenna 16. A current source 18 and its impedance Zo represent an ideal power source (RF-transistor) 12. A matching circuit 20 is connected between the antenna 16 and power source 12, with another terminal 22 connected to ground. Part of the power Pinc—circ from the matching circuit 20 to the circulator 14 is delivered as Pinc—ant to the antenna 16 where some power is reflected back Prefl—ant to the circulator 14. Thanks to the circulator 14, the reflected power Prefl—ant from the antenna 16 is not reflected towards the source 12, but dissipated into the circulator load Pdiss. Consequently, the reflected power Prefl—circ from the circulator 14 and the reflected power Prefl—source from the matching circuit 20 towards the source 12 are zero. This avoids extremes that would occur when incident and reflected waves add up in-phase. However, since it is desired to preserve power amplifier linearity and maintain Prad constant (under control of field strength indication at the base station), then the incident power Pinc—source from the source 12 has to be increased, thus increasing power dissipation, to overcome reflection losses resulting in enhanced signal voltage and current at the source 12. Thus, the circulator 14 only partly preserves power amplifier linearity under antenna mismatch conditions. In addition, power dissipation and consumption remains high thus requiring battery charging and decreasing battery life of the mobile phone as well as decreasing efficiency. It is desirable to remove the isolator or circulator 14 connected to the antenna 16. However, removal of the isolator allows load impedance variations to detrimentally affect the performance, e.g., linearity, of the power amplifier. Accordingly, there is a need to have a power amplifier circuit where the isolator is removed yet the performance and linearity of the amplifier is preserved despite load impedance variations. According to the invention, linear power output of a power amplifier is substantially maintained constant despite load variations and having no isolator connected to the load. This is achieved by dynamically adjusting the gain of active devices and phase of signals in an isolator-less power amplifier circuit as a correction scheme for linearity under predetermined load mismatch conditions. Thus, linear output power is kept unchanged for a predetermined load delta across the dynamic range of operation, without substantially decreasing efficiency. More particularly, linearity is substantially maintained constant despite load variations by independently and selectively adjusting the gain of the active devices of driver and output stages as a function of the levels of the forward and reflected output signals. Further, the phase of a pre-amplified signal is independently and selectively adjusted as a function of the levels of the forward and reflected output signals to substantially maintain constant linearity of amplifier circuit with load variations. In one embodiment according to the present invention, an amplifier circuit for preserving linearity of an amplifier is provided. The amplifier circuit may be used in wireless communication devices, for example. The amplifier circuit includes a driver stage with at least an active device for pre-amplification and output of a pre-amplified signal; and an output stage with at least an active device an active device for further amplification of the pre-amplified signal and output of an amplified signal. A phase shifter shifts the phase of the pre-amplified signal. A detector measures levels of forward and reflected parts of the amplified signal, and a gain and phase control circuit independently and selectively controls and adjusts the phase shifter for optimal amplifier performance and maximum difference or ratio between the forward and reflected signals. The gain and phase control circuit also independently and selectively controls and modifies the gain of the active devices of the driver and output stages as a function of the levels of the forward and reflected signals to substantially maintain linearity of amplifier circuit with load variations. In another embodiment according to the present invention, a method for substantially preserving linearity of an amplifier under varying loads is provided. The method includes measuring levels of forward and reflected signals at the amplifier output; and adjusting the phase of a pre-amplified signal for optimal amplifier performance and maximum difference or ratio difference between the forward and reflected signals as a function of the measured levels, such as the difference or ratio of the measured forward and reflected signals. The method further includes independently and selectively adjusting the gain of the active devices of the driver stage and/or output stage, such as by selectively adjusting the DC bias at the input of the active devices, as a function of the levels of the forward and reflected signals to substantially maintain linearity of amplifier circuit with load variations. Further features and advantages of the invention will become more readily apparent from a consideration of the following description. The accompanying drawings specify and show preferred embodiments of the invention, wherein like elements are designated by identical references throughout the drawings; and in which: FIG. 1 shows a prior art block diagram of a power source isolated with a circulator from a mismatched antenna; FIG. 2 shows a wireless communication system according to the present invention; FIG. 3 shows an isolator-free amplifier circuit according to the present invention; FIG. 4 shows a flow chart of a method for preserving performance, e.g., linearity, of an isolator-free amplifier circuit according to the present invention; and FIG. 5 shows a summarized flow chart of the method for preserving performance, e.g., linearity, of an isolator-free amplifier circuit according to the present invention. The invention, together with attendant advantages, will be best understood by reference to the following detailed description of the preferred embodiment of the invention, taken in conjunction with the accompanying drawing. An amplifier circuit for use in wireless communication devices for example is described where, illustratively, an RF power amplifier is used in RF antenna circuits. In the following description, numerous specific details are set forth, such as specific type and number of transistors, in order to provide a thorough understanding of the present invention. However, it will be obvious to one skilled in the art that the present invention may be practiced without these specific details. In other instances, well known circuits have not been set forth in detail in order to not unnecessarily obscure the present invention. The wireless communication device may be for example a mobile cellular or cordless telephone, pager, an Internet appliance or other consumer devices, and is typically part of a communication system. FIG. 2 shows a wireless communication system, such as a mobile telephone system 40 comprising a primary or base station (BS) 50 and a plurality of secondary or mobile stations (MS) 60. The BS 50 comprises a network controller 52, such as a computer, coupled to a transceiver 54 which is in turn coupled to radio transmission means such as an antenna 56. A connection means such as a wire 58 couples the controller 52 to a public or a private network. Each MS 60 comprises a processor 62 such as a micro-controller (μC) and/or a digital signal processor (DSP). Typically, the DSP processes voice signals, while the μC manages operation of the MS 60. The processor 62 is coupled to a transceiver means 64 coupled to radio transmission means, e.g., an antenna 66. A memory 68, such as an EPROM and RAM, is coupled to the processor 62 and stores data related to operation and configuration of the MS 60. Communication from the BS 50 to MS 60 takes place on a downlink channel 72, while communication from the MS 60 to BS 50 takes place on an uplink channel 74. The MS 60 also includes a user interface such as a keyboard and a screen, as well as a microphone coupled to the transmit branch or section of the transceiver 64 and a speaker coupled to the receiver section of the transceiver 64. The transmit section of the transceiver 64 transmits signals over the uplink channel 74, which the receive branch of the transceiver 64 receives signals over the downlink channel 72. The transceiver 64 includes a selection means to selectively couple a power amplifier (PA) of the transmit section or a low noise amplifier (LNA) of the receive section to the antenna 66. Illustratively, the selection means includes a duplexer or bandpass filters tuned to the transmit and receive frequency ranges, respectively. As is well known in the art, the transceiver 64 also includes other circuits such as a down converter for converting the received radio frequency (RF) signals to intermediate frequency and/or baseband signals, and demodulator/decoder in the receive branch. By contrast, the transmit branch of the transceiver 64 includes an up converter and a modulator/encoder. Converters that convert between analog and digital formats are also typically present in the transceiver 64. FIG. 3 shows an embodiment of an amplifier circuit 100 according to the present invention which is illustratively used as a power amplifier circuit to amplify RF signals in wireless communication devices. For example, the amplifier circuit 100 is part of the transceiver 64 of the MS 60 shown in FIG. 2, and more particularly, in the transmit branch of the transceiver 64. Typically, the input of the amplifier circuit is coupled to a modulator and receives modulated RF signals for amplification. The amplifier output is coupled to a load, such as the antenna 66, where the amplified RF signals are transmitted over the air on the uplink channel 74 for example. As shown in FIG. 3, the amplifier circuit 100 comprises an input match circuit 110 for buffering the input of the amplifier circuit 100 and matching its input impedance with the output impedance of the circuit coupled thereto, such as a modulator. The output of the input match circuit 110 is coupled to a driver stage 120 through at least one direct current (DC) blocking capacitor 130. The signal to be amplified, such as a modulated signal, is provided by the input match circuit 110 to the capacitor 130, which substantially blocks DC components and provides a signal substantially without a DC offset to the driver stage 120. The driver stage 120 comprises at least one active device, such as a transistor 140, which receives the substantially DC-free signal from the capacitor 130 for pre-amplification to a first level. Illustratively, the pre-amplification transistor is a bipolar transistor, such as an NPN transistor 140 having a base 142 coupled to the capacitor 130. The base 142 is further independently coupled to a gain and phase control circuit 145 for a proper DC biasing signal. This allows the control circuit 145 to control, e.g., adjusts the DC bias at the input of the transistor 140. The emitter of the transistor 140 is coupled to ground, while the output or collector of the transistor 140 is coupled to an inter-stage match circuit 150 for buffering and impedance matching between the driver stage 120 and the input 182 of an output stage 160. The pre-amplified signal from the driver stage 120 is provided to the input 182 of the output stage 160 through the inter-stage match circuit 150, a phase shifter 155 which shifts the phase of the pre-amplified signal, and at least one DC blocking capacitor 170 for substantially blocking DC signals present in the pre-amplified and phase-shifted signal, similar to the DC blocking capacitor 130. The output stage 160 is similar to the driver stage 120 and also comprises at least one transistor 180 which receive the substantially DC-free signal from the capacitor 170 for amplification to the output level. Illustratively, the output transistor 180 is a bipolar transistor, such as an NPN transistor having a base coupled to the capacitor 170. The base 182 of the output transistor 180 is further coupled to the control circuit 145 for providing the proper DC biasing signal the output transistor 180. The emitter of transistor 180 is coupled to ground, while the output or collector of the transistor 180 is directly or indirectly coupled to the load without any isolation therebetween. Further, the emitter area of each active device 140, 180 is selected such that optimum performance is achieved for a given load, inter-stage and source conditions. In addition to being coupled to the inputs 142, 182 of the transistors 140, 180, the control circuit 145 is also coupled to a control port of the phase shifter 155. Accordingly, the control circuit 145 is configured to provide control signals for independently and selectively controlling the phase shifter 155 and transistors 140, 180. This allows the bias control circuit 1 independently and selectively adjust the amount phase shifting of the pre-amplified signal and the DC bias at the input transistors 140, 180, thus adjusting the amplification or gain of the driver and output stages 120, 160. By way of example, suppose a power amplifier is to deliver 30 dBm of output power to a 50 ohm load. If the power amplifier's final stage's output has peak voltage swing of 1.4 volts for linear operation, then a loss-less impedance matching network separating load and power amplifier must have an impedance transformation ratio of 51:1. Consider a worst case mismatch condition over all phases of a constant VSWR. The two impedance extremes are high and low loads. In the former case, large voltage swings develop across the output of the final stage causing non-linearity in the form of clipping due to the onset of high AC impedance. In the later case, the demand for output current elevates due to the onset of low AC impedance. By monitoring the incident and reverse power levels, a measurement of the impedance condition is obtained as shown in block 200 of FIG. 4. Next in block 210, the impedance level or mismatch is checked and if a normal or matched level is obtained, then normal matched operation is continued in block 220. If the impedance level or mismatch is not normal, then it is determined in block 230 whether the difference or ratio of the measured forward and reflected signals is high, indicating a relatively high forward signal, or low indicating a relatively low forward signal. Next, in block 240, the phase shifter and the input DC bias of each driver and output transistor are independently and selectively adjusted in one direction or the other, depending on whether the ratio measured in block 230 was high or low. Next, the impedance condition is re-measured by returning to block 200 and the operations are repeated until a matched level is obtained in block 210 and normal matched operation is continued in block 220. The monitoring and measurement of the impedance in block 200 are continuously or intermittently checked and adjustments are made, if needed, to arrive to the matched condition of block 220. A detector, such as a power detector 190, is also coupled to the output of transistor 180 for detecting the level, e.g., the power level, of the amplified RF signal at the output of the output stage 160. The power detector 190 is in turn coupled to the control circuit 145. The output 195 of the amplifier circuit 100 is coupled to an antenna without an isolator therebetween. The power detector 190 provides the control circuit 145 a measure of the forward and reflected output power of the amplifier circuit 100. As a function of the forward and reflected power levels, the control circuit 145 independently and selectively controls the phase shifter 155 and each of transistor 140, 180 of the driver and output stages 120, 160 to substantially maintain the optimum performance and constant linearity of the amplifier circuit 100 despite variations in the impedance of the load connected to the output 195 of the amplifier circuit 100. For example, in response to the difference between the forward and reflected power level in response to the difference between the forward and reflected power level, the control circuit 145 independently and selectively controls the phase shifter 155 and changes the DC bias on the input e.g., base 142, 182, of each driver and output transistor 140, 160. This substantially maintains linear output power despite load variations without significantly modifying the output stage of the power amplifier circuit. As is well known by one skilled in the art, the changes in the forward and reflected power levels measured by the power detector 190 are related to changes in the load impedance, e.g., the impedance of the antenna 66 shown in FIG. 2. In particular, for a load impedance substantially matched to the output impedance of the output of the amplifier circuit 100, the ratio or the difference between the forward and reflected power levels is high, while it is low for substantially mismatched impedances. U.S. Pat. No. 5,423,082, which is incorporated herein by reference in its entirety, discloses a transmitter that includes a closed loop feedback to compensate for varying antenna loads without an isolator, which is accomplished by taking the reflected output energy into account to maintain a constant overall loop gain by adjusting the gain of variable gain stages. Control circuits are also well known in the art, such as the control circuit disclosed in U.S. Pat. Nos. 5,442,322 and 5,712,593 which are incorporated herein by reference in its entirety. In U.S. Pat. No. 5,442,322, a bias control circuit compares a bias control voltage with a value indicative of the current in an active device and provides a control signal to the control terminal of the active device to control the operating point thereof. The bias point of a power amplifier is similarly controlled in U.S. Pat. No. 5,712,593 by a control circuit in response to comparing a reference value to a filtered portion of the RF output signal. Changing the amplifier bias point limits the effect of the load impedance variation on the amplifier performance. U.S. Pat. No. 6,064,266, which is incorporated herein by reference in its entirety, is also related to limiting the effect of the load impedance variation on the amplifier performance, which is achieved by modifying the RF output signal path, instead of the DC bias, by switching in a resistor in parallel with the output impedance when a threshold detector detects variations in the load impedance above a predetermined value. Phase shifters are also well known in the art, as disclosed in U.S. Pat. No. 4,312,032, which is incorporated herein by reference in its entirety. The control circuit 145 of the present amplifier circuit 100 may include a processor or a comparator for comparing the values of forward and reflected power levels measured by the power detector 190 with at least one threshold value. Based on the comparison, the control circuit 145 selectively and independently controls modifies the DC levels at the inputs 142, 182 of the transistors 140, 180, as well as controlling the phase shifter 155 to change the phase of the pre-amplified signal as necessary, namely, as a function of the levels of the forward and reflected signals, to substantially maintain constant the linearity of the amplifier circuit 100 with load variations. FIG. 5 shows a flow chart 300 of a method for preserving performance of an isolator-free amplifier circuit according to the present invention. In block 310, the power detector measures the forward and reflected power levels at the output of the amplifier circuit and provides this information to the control circuit 145. In response to the measured forward and reflected power levels, such as their difference or ratio values, in block 320, the control circuit 145 selectively and independently controls the phase shifter 155 to change the phase of the pre-amplified signal, and/or modifies the gain, e.g., by changing the base DC bias, of the input and/or output transistors 140, 180, as a function of the measured forward and reflected power levels to substantially maintain optimal performance and constant linearity of the amplifier circuit 100 with load variations. While the present invention has been described in particular detail with reference to specific exemplary embodiments thereof, it should also be appreciated that numerous modifications and changes may be made thereto without departing from the broader and intended spirit and scope of the invention as set forth in the claims that follow. The specification and drawings are accordingly to be regarded in an illustrative manner and are not intended to limit the scope of the claims which follow.
20060209
20080603
20070628
91443.0
H03G300
0
NGUYEN, HIEU P
PRESERVING LINEARITY OF AN ISOLATOR-FREE POWER AMPLIFIER BY DYNAMICALLY ADJUSTING GAIN AND PHASE
UNDISCOUNTED
0
ACCEPTED
H03G
2,006
10,538,691
ACCEPTED
Magnetic encoder
A magnetic encoder, which comprises a stainless steel sheet; and an under coat adhesive containing epoxy resin and organopolysiloxane, a top coat adhesive containing phenol resin, or phenol resin and epoxy resin, and a rubber magnet, as successively laid one upon another on the stainless steel sheet, has distinguished water resistance and saline water resistance, and thus can be effectively used particularly as a magnetic encoder in wheel speed sensors.
1. A magnetic encoder, which comprises a stainless steel sheet; and an under coat adhesive containing epoxy resin and organopolysiloxane, a top coat adhesive containing phenol resin, or phenol resin and epoxy resin, and a rubber magnetic as successively laid one upon another on the stainless steel sheet. 2. A magnetic encoder according to claim 1, wherein the under coat adhesive comprises epoxy resin, organopolysiloxane as a hydrolysis condensate of organoalkoxysilane represented by the general formula Xn—Si(OR)4-n, where X is a functional group reactive with rubber or resin, R is a lower alkyl group, and n is 1 or 2, colloidal silica, and an amide- or imide-based epoxy resin curing agent. 3. A magnetic encoder according to claim 2, wherein the under coat adhesive composition comprises 45 to 75 wt. % epoxy resin, 10 to 40 wt. % of organopolysiloxane, 3 to 10 wt. % of colloidal silica, and 0 to 5 wt. % of an amide- or imide-based epoxy resin curing agent. 4. A magnetic encoder according to claim 2, wherein the organopolysiloxane is copolymerization oligomers of amino group-containing alkoxysilane and vinyl group-containing alkoxysilane. 5. A magnetic encoder according to claim 1, wherein a base polymer of the rubber magnet is NBR or ethylene-methyl acrylate copolymerization rubber. 6. A magnetic encoder according to claim 1, for use in wheel speed sensors. 7. A magnetic encoder according to claim 3, wherein the organopolysiloxane is copolymerization oligomers of amino group-containing alkoxysilane and vinyl group-containing alkoxysilane. 8. A wheel speed sensor that comprises the magnetic encoder according to claim 1.
TECHNICAL FIELD The present invention relates to a magnetic encoder, and more particularly to a magnetic encoder with improved water resistance, saline water resistance, etc. BACKGROUND ART Magnetic encoders using a rubber magnet are excellent for detection of revolution rate at a low speed and recently have been widely used in wheel speed sensors, etc. Wheel speed sensors are used in the neighborhood position of wheel, requiring good water resistance and a saline water resistance. The magnetic encoder using a rubber magnet comprises a stainless steel sheet, a rubber magnet, and an adhesive for bonding these two. Water resistance tests show that peeling occurred at the interface between the stainless steel sheet and the adhesive of the magnetic encoder, and the water resistance of the adhesive as well as the rubber magnet itself is regarded as very important. For the adhesive layer for the water resistance purpose, epoxy resin is usually used, but owing to poor adhesion to the stainless steel sheet, the epoxy resin is not used alone in case of the stainless steel sheet. In case of a single adhesive layer, a phenol resin-based adhesive, a silane-based adhesive, an epoxy resin/silane-based adhesive, or the like is used. In case of two adhesive layers, the afore-mentioned phenol resin-based adhesive, a phenol resin/halogenated polymer-bases adhesive, a phenol resin/epoxy resin-based adhesive, or the like is used as an under coat. However, even if these under coat adhesives are used in combination with various top coat adhesives, no statisfactory water resistance can be obtained in severe circumstances such as saline water spraying. DISCLOSURE OF THE INVENTION An object of the present invention is to provide a magnetic encoder with distinguished water resistance, saline water resistance, etc., which comprises a stainless steel sheet and a rubber magnet, both being bonded to each other through an epoxy resin-based adhesive. The object of the present invention can be attained by a magnetic encoder, which comprises a stainless steel sheet; and an under coat adhesive containing epoxy resin and organopolysiloxane, a top coat adhesive containing phenol resin, or phenol resin and epoxy resin, and a rubber magnet as successively laid one upon another on the stainless steel sheet. The stainless steel sheet for use in the present invention includes those of SUS304, SUS301, SUS430, etc. For the magnetic encoder use, the sheet thickness is usually about 0.2 to about 2 mm. At first, an under coat adhesive containing epoxy resin and organopolysiloxane is applied to the stainless steel sheet. As the under coat adhesive containing epoxy resin and organopolysiloxane, an adhesive comprising epoxy resin, organopolysiloxane, which is a hydrolysis condensate of organoalkoxysilane represented by the general formula, Xn—Si(OR)4-n (where X is a functional group reactive with rubber or resin, R is a lower alkyl group and n is 1 or 2), colloidal silica, and amide- or imide-based epoxy resin curing agent, is preferably used. The epoxy resin for use in the present invention includes, preferably those obtained by reaction of bisphenol A, bisphenol F or novolak resin with epichlorohydrin. Commercially available epoxy resin can be directly used as such an epoxy resin. For example, Epikote 154 (a product of Japan Epoxy Resin Co.), Epikote 157S70 (ditto), Epikote 180S65 (ditto), etc. can be used. Aquous emulsion-type epoxy resin can be also used. For example, Epi-Rez, 5003W55 (a product of Japan Epoxy Resin Co.), Epi-Rez 6006W70 (ditto), etc. can be used. The organopolysiloxane for use in the present invention includes hydrolysis condensates of at least one of organoalkoxysilanes represented by the general formula Xn—Si(OR)4-n, where X is a functional group reactive with rubber or resin such as methyl, ethyl, 3-aminopropyl, N-(2-aminoethyl)-3-aminopropyl, N-phenyl-3-aminopropyl, vinyl, 3-methacryloxypropyl, 3-glycidoxypropyl, 3-mercaptopropyl, etc., and R is a lower alkyl group such as methyl, ethyl, etc. The organoalkoxysilane represented by such a general formula includes, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, etc. Hydrolysis condensation reaction of organoalkoxysilane is carried out by heating at about 40° to about 80° C. for about 3 to about 24 hours in the presence of an acid catalyst such as formic acid, acetic acid, etc. while keeping at least an equivalent weight of water for hydrolysis present. Such hydrolysis condensates are preferably copolymerization oligomers of amino group-containing alkoxysilane and vinyl group-containing alkoxysilane. The amino group-containing alkoxysilane as one member of the copolymerization oligomers includes, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, etc. The vinyl group-containing alkoxysilane as another counterpart member includes, for example, vinyltrimethoxysilane, vinyltriethoxysilane, etc. In the oligomerization reaction, 100 parts by weight of amino group-containing alkoxysilane, 25 to 400 parts by weight, preferably 50 to 150 parts by weight, of vinyl group-containing alkoxysilane, and 20 to 150 parts by weight of water for hydrolysis are used. When more than 400 parts by weight of vinyl group-containing alkoxysilane is used, the compatibility with the top coat adhesive or rubber will be deteriorated and consequently the adhesive-ness will be lowered, whereas in case of less than 25 parts by weight the water resistance will be lowered. The oligomerization reaction is carried out by charging these alkoxysilanes into a reactor provided with a distillation appratus and a stirrer, followed by stirring at about 60° C. for about one hour, then adding thereto about 1 to about 2 moles of an acid such as formic acid or acetic acid on the basis of one mole of the amino group-containing alkoxy-silane within one hour, while keeping the reactor temperature at about 65° C., followed by further stirring for 1 to 5 hours to proceed with the reaction and distill off alcohol formed by hydrolysis under reduced pressure at the same time, discontinuing the distillation when the distillate is turned into only water, and diluting the residue to a silane concentration of 30 to 80 wt. %, thereby obtaining the desired copolymerization oligomer. The copolymerization oligomer is soluble in an alcoholic organic solvent such as methanol, ethanol, etc. Commercially available copolymerization oligomers can be used as such. Colloidal silica for use in the present invention has particle sizes of not more than 50 nm and is selected in view of the species of a solvent to be used. For example, when the solvent is water, commercially available products Snowtex 20 (a product of Nissan Chemical Industries, Ltd.), Snowtex 30 (ditto), etc. are used. When the solvent is an organic solvent, Snowtex MEK-ST (ditto; dispersion in methyl ethyl ketone), Snowtex MIBK-ST (ditto; dispersion in methyl isobutyl ketone), etc. are used. To improve the film strength, colloidal silica is used in the following mixing proportion. As an amide- or imide-based epoxy resin curing agent, dicyandiamide, methylimidazole, etc. are used. The components of the under coat adhesive are used in such proportions as 45 to 75 wt. %, preferably 55 to 65 wt. %, of epoxy resin; 10 to 40 wt. %, preferably 25 to 35 wt. %, of hydrolysis condensate of organopolysiloxane; 3 to 10 wt. %, preferably 5 to 8 wt. %, of colloidal silica; and 0 to 5 wt. %, preferably 0.5 to 3 wt. %, of amide- or imide-based epoxy resin curing agent, upon blending. When the hydrolysis condensate of organopolysiloxane is used in a proportion of less than 10 wt. %, the adhe-siveness to stainless steel sheet will be deteriorated, whereas in a pro-portion of more than 40 wt. % no improvement effect on the water resistance and saline water resistance will be obtained. As a solvent for the under coat adhesive comprising the foregoing components such epoxy resin and organopolysiloxane, water or an organic solvent is usually used. Any organic solvent can be used, so far as it can dissolve epoxy resin, and acetone, methyl ethyl ketone, etc. are preferably used. The under coat adhesive is a solution having a concentration of about 1 to about 30 wt. %. The under coat adhesive comprising epoxy resin and organopolysiloxane is applied to a stainless steel sheet to a film thickness of about 5 to about 30 μm by dipping coating, spraying coating, brush coating, etc., followed by drying at room temperature and further drying at about 50° to about 250° C. for about 5 to about 30 minutes. A phenol resin-based top coat adhesive is applied as a vulcanization adhesive to the under coat adhesive comprising epoxy resin and organopolysiloxane laid on the stainless steel sheet. Commercially available phenol resin-based adhesives can be used as such, and include, for example, Thixon 715 (a product of Rohm & Haas Co.). Metaloc N31 (a product of Toyo Kagaku Kenkyusho K.K.), Chemlok TS1677-13 (a product of Rhodes Far East Co.) etc. An adhesive containing phenol resin and epoxy resin, for example, Metaloc XPH-27 (a product of Toyo Kagaku Kenkyusho K.K.), a composition containing novolak type epoxy resin and novolak type phenol resin derived from p-substituted phenol, disclosed in JP-A-4-13790, etc. can be used. The same application method, application temperature, and application time as in the case of the under coat adhesive are also applied to the top coat adhesive to form a top coat adhesive layer having a film thickness of about 5 to about 30 μm. An unvulcanized rubber magnet is bonded to the adhesive layer so formed, and subjected to press vulcanization molding at about 150° to about 200° C. for about 5 to about 60 minutes to form a rubber magnet layer having a thickness of about 0.5 to about 2 mm. Any rubber can be used for the rubber magnet, so far as it can be bonded to the top coat adhesive, and NBR, ethylene-methyl acrylate copolymerization rubber (AEM), etc. can be preferably used. Above all, a rubber composition for magnetic encoder, which comprises ethylene-methyl acrylate copolymerization rubber as a base polymer, magnetic powder such as ferrite magnet powder, etc. (usually used about 450 to about 1,000 parts by weight on the basis of 100 parts by weight of the base polymer) and an amine-based vulcanizing agent can give a rubber magnet with distinguished heat resistance, water resistance and saline water resistance. BEST MODES FOR CARRYING OUT THE INVENTION The present invention will be described below, referring to Examples. Reference Example 40 parts by weight of γ-aminopropyltriethoxysilane and 20 parts by weight of water were charged into a three-necked flask provided with a stirrer, a heating jacket and a dropping funnel, and pH was adjust to 4 to 5 with acetic acid, followed by stirring for several minutes. While further continuing stirring, 40 parts by weight of vinyltriethoxysilane was slowly dropwise added thereto through a dropping funnel. After the dropwise addition, heating and refluxing were carried out at about 60° C. for 5 hours, followed by cooling to room temperature to obtain copolymerization oligomer. The thus obtained amino group/vinyl group-containing oligomer (organopolysiloxane) was used as a component in the following adhesives A and B. Examples 1 to 5 and Comparative Examples 1 to 6 At first, an under coat adhesive was applied to an SUS430 stainless steel sheet, followed by air drying at room temperature and successive drying at 200° C. for 10 minutes, and then a top coat adhesive was applied thereto, followed by air drying at room temperature and successive drying at 150° C. for 10 minutes. An unvulcanized rubber magnet was bonded thereto, followed by press vulcanization at about 150° to about 200° C. for about 5 to about 60 minutes to obtain a raw material for the magnetic encoder. Parts by weight (Adhesive) Remark: Figures in parentheses shows parts by weight on solid basis A: DPP Novolak type epoxy resin 175(100) (Epi-Rez 5003W55, a product of Japan Epoxy Resin Co.; solid concentration: 57 wt. %) Amino group/vinyl group-containing 115(42) organopoly-siloxane (solid concentration: 36.5 wt. % in aqueous solution) Colloidal silica (Snowtex 20, a product 50(10) of Nissan Chemical Industries, Ltd.; solid concentration: 20 wt. % in aqueous dispersion) Dicyandiamide (epoxy resin curing agent) 4 Water 1610 B: o-Cresol novolak type epoxy resin 100(100) (Epikote 180S65, a product of Japan Epoxy Resin Co.) Amino group/vinyl group-containing 280(42) organosiloxane (Solid concentration: 15 wt. % in acetone solution) Colloidal silica (Snowtex MEK-ST; 33(10) a product of Nissan Chemical Industries, Ltd; solid concentration: 30 wt. % in methyl ethyl ketone) Dicyandiamide (epoxy resin curing agent) 4 Methyl ethyl ketone 1535 C: Phenol resin-based (Thixon 715, a product of Rhom & Haas Co.) D Phenol resin-based (Metaloc N-31, a product of Toyo Kagaku Kenkyusho K.K.) E: Phenol resin-based (Chemlok TS1677, a product of Rhodes Far East Co.) F: Phenol resin/epoxy resin-based (Metaloc PH-20, a product of Toyo Kagaku Kenkyusho K.K.) G: Phenol resin/epoxy resin-based (Metaloc XPH-27, a product of Toyo Kagaku Kenkyusho K.K.) H: Phenol resin/halogenated polymer- based (Chemlok 205, a product of Lord Far East Co.) The foregoing adhesives were all diluted to a solid concentration of 8 wt. % with methyl ethyl ketone, before use. (Unvulcanized rubber magnet) NBR (N220S, a product of JSR) 90 Liquid NBR (Nipol 1312, a product 10 of Nippon Zeon Co,. Ltd.) Strontium ferrite powder (FH-801, 800 a product of Toda Kogyo K.K.) Zinc white 3 Antioxidant (Nocrack CD, a product 2 Ouchi Shinko Kagaku K.K.) Stearic acid 2 Plasticizer (RS700, a product of 5 Asahi Denka Kogyo K.K.) Sulfur 0.8 Cross-linking aid (Nokceller TT, 2 a product of Ouchi Shinko Kagaku K.K.) Cross-linking aid (Nokceller CZ, 1 a product of Ouchi Shinko Kagaku K.K.) The raw materials for the magnetic encoder obtained in the foregoing Examples and Comparative Examples were subjected to an initial adhesiveness test, a water resistance test, and a saline water energized test. Initial adhesiveness test: To determine percent retained rubber (R) in the initial state, according to JIS K-6256 90° peeling test procedure Water resistance test: To determine percent retained rubber (R) after dipping a peeling test piece in water at 80° C. for 70 hours or 140 hours, according to JIS K-6256 90° peeling test procedure Saline water energized test: To determine percent retained rubber (R) after applying a 2A steady-state current (maximum volt: 16V) to between a JIS K-6256 90° peeling test piece at a − electrode and an aluminum plate at a + electrode in an aqueous 3 wt. % sodium chloride solution at 30° C. for 5 hours or 10 hours, according to JIS Z-2371 Results of determination in the foregoing Examples 1 to 5 and Comparative Examples 1 to 6 are shown in the following Table 1, together with the species of the under coat adhesives and the top coat adhesives, and heating-drying conditions used therein. TABLE 1 Comparative Example No. Example No. Test item 1 2 3 4 5 1 2 3 4 5 6 [Under coat adhesive] Species A A A A B A B C C F H [Top coat adhesive] Species C D E G C — — — C C C [Initial adhesiveness test] Initial (R; %) 100 100 100 100 100 100 100 100 100 100 100 [Water resistance test] After 70 hrs (R; %) 100 100 100 100 100 100 100 80 90 100 80 After 140 hrs (R; %) 100 100 100 100 100 80 80 20 50 80 20 [Saline water energized test] After 5 hrs (R; %) 100 95 100 100 95 80 80 0 30 90 20 After 10 hrs (R; %) 95 90 95 95 90 40 40 0 0 50 0 Examples 6 to 10 and Comparative Examples 7 to 12 In Examples 1 to 5 and Comparative Examples 1 to 6, an unvulcanized rubber magnet having the following composition was used: Parts by weight AEM (Vamac G, a product of DuPont-Dow 100 Elastomer Co.) Strontium ferrite powder (FH-801, a product of 700 Toda Kogyo K.K.) Stearic acid 2 Antioxidant (Nocrack CD, a product of 2 Ouchi Shinko Kagaku K.K.) Plasticizer (RS735, a product of Asahi Denka Kogyo 10 K.K.) Cross-linking aid (Nokceller DT, a product of 4 Ouchi Shinko Kagaku K.K.) Cross-linking agent (Diac No. 1 a product of 2 DuPont-Dow Elastomer Co.) Raw materials for the magnetic encoder obtained in the foregoing Examples 6 to 10 and Comparative Examples 7 to 12 were subjected to an initial adhesiveness test, a water resistance test, and a saline water energized test. Results of determination are shown in the following Table 2 together with the species of the under coat adhesives and the top coat adhesives used therein. TABLE 2 Comparative Example No. Example No. Test item 6 7 8 9 10 7 8 9 10 11 12 [Under coat adhesive] Species A A A A B A B C C F H [Top coat adhesive] Species C D E G C — — — C C C [Initial adhesiveness test] Initial (R; %) 100 100 100 100 100 100 100 100 100 100 100 [Water resistance test] After 70 hrs (R; %) 100 100 100 100 100 100 100 95 95 100 95 After 140 hrs (R; %) 100 100 100 100 100 95 95 40 60 95 40 [Saline water energized test] After 5 hrs (R; %) 100 100 100 100 100 100 100 20 30 100 30 After 10 hrs (R; %) 100 100 100 100 100 70 70 0 0 70 0 INDUSTRIAL UTILITY The present magnetic encoder has distinguished water resistance and saline water resistance, and thus can be effectively used particularly as a magnetic encoder for wheel speed sensors.
<SOH> BACKGROUND ART <EOH>Magnetic encoders using a rubber magnet are excellent for detection of revolution rate at a low speed and recently have been widely used in wheel speed sensors, etc. Wheel speed sensors are used in the neighborhood position of wheel, requiring good water resistance and a saline water resistance. The magnetic encoder using a rubber magnet comprises a stainless steel sheet, a rubber magnet, and an adhesive for bonding these two. Water resistance tests show that peeling occurred at the interface between the stainless steel sheet and the adhesive of the magnetic encoder, and the water resistance of the adhesive as well as the rubber magnet itself is regarded as very important. For the adhesive layer for the water resistance purpose, epoxy resin is usually used, but owing to poor adhesion to the stainless steel sheet, the epoxy resin is not used alone in case of the stainless steel sheet. In case of a single adhesive layer, a phenol resin-based adhesive, a silane-based adhesive, an epoxy resin/silane-based adhesive, or the like is used. In case of two adhesive layers, the afore-mentioned phenol resin-based adhesive, a phenol resin/halogenated polymer-bases adhesive, a phenol resin/epoxy resin-based adhesive, or the like is used as an under coat. However, even if these under coat adhesives are used in combination with various top coat adhesives, no statisfactory water resistance can be obtained in severe circumstances such as saline water spraying.
20050610
20070612
20061207
59399.0
B32B2738
0
MOORE, MARGARET G
MAGNETIC ENCODER
UNDISCOUNTED
0
ACCEPTED
B32B
2,005
10,538,812
ACCEPTED
Picture hanger for use with gypsum board and installtion tool therefore
A picture hanger for use with gypsum board comprises a strip of steel bent into a V to provide two legs. The first leg is arcuate and functions as an anchor upon insertion into the gypsum board. The second leg is straight, with a hook at its terminus for hanging pictures and the like. An installation tool is provided which enables the arcuate anchor leg to be driven into the gypsum board along an arcuate path corresponding to the arcuate anchor leg until the second leg is held firmly against the surface of the gypsum board.
1. A fixture for insertion into a gypsum board wall to enable pictures and the like to be hung therefrom comprising: a metal strip bent in a Vee to provide a first leg and a second leg, said first leg functioning as an anchor and said second leg functioning as a hanger; said second leg terminating in a hook; and said first leg being arcuate with a center of curvature substantially at the center of curvature of said hook. 2. A method for inserting the fixture of claim 1 into a gypsum board wall comprising the steps of: rotatably supporting the hook of said second leg so that its center of curvature is disposed at a point outwardly from the wall at about the distance of the radius of curvature of the first leg; and driving said first leg into the wall. 3. An installation tool for the fixture of claim 1 comprising a body and a driver; said driver comprising a rod terminating at its distal end with a push surface; said body having a face adapted to be urged against the surface of the wall; said body having a bore and a cavity formed therein along an axis perpendicular to said wall to receive said driver and said fixture, respectively; said cavity being formed to provide a shoulder at the base thereof in which the hook of said fixture is captured and pivotally supported when said body face is urged against said wall; said cavity being further formed to constrain said fixture therein with the distal end of said first leg pointed at said wall; said push surface being disposed to abut said fixture; and impact means for driving said driver and said push surface against said fixture to progressively drive said first leg into said wall along an arcuate path.
CROSS REFERENCE TO RELATED APPLICATIONS The present invention relates generally to a hanging fixture or hook for installation in gypsum board from which pictures, mirrors, and the like are hung. More particularly it relates to a hook for installation in gypsum board which is removable without substantial damage to the gypsum board surface. BACKGROUND OF THE INVENTION The use of gypsum board (drywall) for interior walls and ceilings of buildings is ubiquitous. Walls and ceilings may be finished in a fraction of the time required for lath and plaster finishing. Along with its many advantages, gypsum board has severe limitations with respect to its ability to support pictures, mirrors and the like. Unless a hanger is positioned directly over a stud, into which screws or nails may be driven, special fixtures are required. A common solution is to drill a hole through the board, insert an appropriately sized plastic or fiber anchor into the hole, and drive a screw into the anchor. Other devices include a self-drilling anchor which cuts its own hole and screws into the board. Yet other hangers use a nail driven downwardly into the board at an acute angle from which a hook is suspended. All of the prior art fixtures and hangers have disadvantages. Drilling a hole in gypsum board produces fine white dust, which must be cleaned up after installation is complete. Moreover, if the fixture is removed, a scar is left in the wall which requires patching with dry wall compound or plaster of paris followed by sanding and painting. In general, installing or removing the hanging fixtures of the prior art is a messy job. GENERAL DESCRIPTION OF THE INVENTION In accordance with the present invention, there is provided a steel strip bent into a Vee to provide two legs. The first leg is arcuate and functions as the anchor when inserted into gypsum board. The second leg is straight, with a hook at its terminus for hanging pictures and the like. An installation tool is provided which enables the arcuate anchor leg to be driven into the gypsum board along an arcuate path until the second leg is held firmly against the surface of the gypsum board. The hanger may be removed with a screw driver or plier, leaving a barely perceptible scar in the gypsum board. DETAILED DESCRIPTION OF THE INVENTION The construction and installation of the device of the present invention will become readily apparent from the following description and drawing, in which: FIG. 1 is an elevational view of the installation tool in accordance with the present invention with a hanger positioned therein; FIG. 2 is a side view of the installation tool of FIG. 1; FIG. 3 is an enlarged side view of the hanger; FIG. 4 is a cross-sectional view taken along lines 2-2 of FIG. 2 showing the hanger in nesting position in the installation tool before insertion into the gypsum board; FIG. 5 is a view like FIG. 4 in which the hanger has been partially driven into the gypsum board; FIG. 6 is a view like FIG. 4 showing the hanger fully inserted in the gypsum board; FIG. 7 is an elevational view of an alternative embodiment of the installation tool; and FIG. 8 is a side view of the installation tool of FIG. 7. As shown in FIG. 1 there is provided an installation tool 13 comprising a body 15 and a driver 17. The body 15 may be made of an injection molded plastic. The driver 17 preferably is a steel rod received in a bore 19 in the body 15. The bore 19 opens into a cavity 21 formed to accommodate the hanger 23 of the present invention. The driver 17 terminates in the interior of the body with a push plate 25. The push plate abuts the hanger 23. The hanger is shown more particularly in FIG. 3, and is bent into a Vee, with an anchor leg 29 and a hanger leg 31. The hanger leg terminates in a hook 33. It will be seen in FIG. 3 that the anchor leg 29 of the hanger 23 is arcuate, with the center of curvature of its arc at or near the base of the hook 33 of the hanger leg. FIG. 4 shows the installation tool 13 and the hanger 23 in the same position as illustrated in FIG. 1, before insertion of the hanger into the gypsum board. A guide line 35 (FIG. 1) on the side of the installation tool body 15 is aligned with the spot where the hook 33 is desired to be positioned on the wall. FIG. 5 shows the hanger 29 partially driven into the gypsum board. A hammer is used to strike the end of the driver 17 to drive the anchor leg 29 of the hanger progressively into the gypsum board. Throughout insertion of the hanger 23, the hook 33 of the hanger leg 31 is captured between a shoulder 37 of the cavity 21 and the surface of the wall, so that the anchor leg 29 of the hanger 23 follows an arcuate path into the wall consistent with the arc of the anchor leg 29. FIG. 6 shows the anchor leg 29 fully inserted into the gypsum board, so that the hanger leg 31 of the hanger 23 is urged snugly against the surface of the gypsum board. If it should happen that the hanger 23 is mistakenly placed in the wrong location, or if the hanger is no longer needed, the hanger 23 may be easily removed from the gypsum board using a screw driver and/or a plier to urge the anchor leg upwardly and outwardly away from the gypsum board. Upon removal, the point of entry of the hanger 23 into the wall is barely discernable. If desired, a very small amount of spackle or drywall compound of course may be used to camouflage it. FIG. 7 shows an alternative embodiment 13′ of the installation tool. It includes a driver 17′ received in a guide tube 43 affixed to the body 15′ of the installation tool. A compression spring 47 biases the driver 17′ away from the body 15′. The body 15′ encloses a magazine in which a plurality of hangers 23 are loaded. A follower 49 urges the hangers toward the end of the body underlying the driver 17′. In this respect, the body 15′ resembles the body of a stapler, in which a plurality of staples are urged toward the inserting means. In a further embodiment of the installation tool (not illustrated) the driver is electrically driven, as in an electric stapler, to insert the hangers 23 into the gypsum one at a time. The drawings and the foregoing descriptions are not intended to represent the only forms of the invention in regard to the details of its construction and manner of operation. Changes in form and in the proportion of parts, as well as the substitution of equivalents, are contemplated as circumstances may suggest or render expedient; and although specific terms have been employed, they are intended in a generic and descriptive sense only and not for the purposes of limitation, the scope of the invention being delineated by the following claims.
<SOH> BACKGROUND OF THE INVENTION <EOH>The use of gypsum board (drywall) for interior walls and ceilings of buildings is ubiquitous. Walls and ceilings may be finished in a fraction of the time required for lath and plaster finishing. Along with its many advantages, gypsum board has severe limitations with respect to its ability to support pictures, mirrors and the like. Unless a hanger is positioned directly over a stud, into which screws or nails may be driven, special fixtures are required. A common solution is to drill a hole through the board, insert an appropriately sized plastic or fiber anchor into the hole, and drive a screw into the anchor. Other devices include a self-drilling anchor which cuts its own hole and screws into the board. Yet other hangers use a nail driven downwardly into the board at an acute angle from which a hook is suspended. All of the prior art fixtures and hangers have disadvantages. Drilling a hole in gypsum board produces fine white dust, which must be cleaned up after installation is complete. Moreover, if the fixture is removed, a scar is left in the wall which requires patching with dry wall compound or plaster of paris followed by sanding and painting. In general, installing or removing the hanging fixtures of the prior art is a messy job.
20051207
20080708
20060622
94902.0
B32B306
1
THOMAS, ALEXANDER S
PICTURE HANGER FOR USE WITH GYPSUM BOARD
SMALL
0
ACCEPTED
B32B
2,005
10,539,029
ACCEPTED
Power saving method for portable streaming devices
A method (2) of controlling memory usage in a portable streaming device (100), a portable streaming device (100) and a computer readable medium (110). The portable streaming device (100) comprises at least one memory (102), at least one processing unit (101), and at least one storage device (103) being operatively connected with said memory (102) under control of said processing unit (101). The size of a disk scheduler buffer memory within said memory in said portable streaming device is adaptively maximised by said method (2) at all times. Free memory available within the portable streaming device is continuously allocated (50) and at least a portion of said allocated free memory is designated as disk scheduler buffer memory (60). Thus results improved solid state memory utilisation of the portable streaming device, and due to larger available disk buffer memory size, less start-stop-cycles of the storage device are initiated, which leads to a longer life-cycle of said portable streaming device.
1. A method of controlling memory usage in a portable streaming device, said device comprising at least one memory, at least one processing unit, and at least one storage device being operatively connected with said memory under control of said processing unit, said method comprising the steps of adaptively maximizing the size of a disk scheduler buffer memory within said memory in said portable streaming device by continuously allocating available free memory in said portable streaming device, designating and using at least a portion of said allocated free memory as disk scheduler buffer memory. 2. A method according to claim 1, whereby the step of maximising the disk scheduler buffer size comprises enhancing the total amount of available disk scheduler buffer memory in said portable streaming device in that allocated free memory is used as disk scheduler buffer memory in combination with existing disk scheduler buffer memory in said portable streaming device. 3. A method according to claim 1 whereby individual buffer sizes are designated within the disk scheduler buffer memory to individual streams and buffer memory sizes depend on the streams bit-rate. 4. A method according to claim 1 whereby the step of adaptively maximising the size of a disk scheduler buffer memory comprises the step of continuously arranging the total memory in the portable streaming device in subsections comprising a first memory section being a fixed part entirely reserved to a disk scheduler as buffer memory, a second memory section being a variable part used by the disk scheduler as further buffer memory, a third memory section being used by all applications of the portable streaming device, except the scheduler, as well as by an operating system OS, and a fourth memory section in between the second section and the third section, being a safety margin, whereby the third memory section increases or decreases by allocating memory from respectively to the fourth memory section, and the second memory section increases or decreases by allocating memory from respectively to the fourth memory section, 5. A method according to claim 4, whereby at least one of said four memory sections has a memory size equal to zero. 6. A method according to claims 4, further comprising a continuous memory pool management comprising the steps of increasing and/or decreasing of the second and/or the third memory section depending on memory requirements of said applications and said OS, and allocating at least a part of the available memory of the fourth memory section to said second memory section. 7. A method according to claim 6, whereby the scheduler buffer comprising the first memory section and the second memory section is arranged as a queue. 8. A method according to claim 6, whereby the continuous memory pool management further comprises the step of tracking memory usage over time, and controlling the size of said fourth memory section based on memory usage statistics based on said tracking of memory usage. 9. A method according to claim 8, whereby said usage statistics is stored persistently, preferably in a file system. 10. A method according to claim 1, whereby the first, second, third or fourth memory section are non-contiguous memory sections of said portable streaming device. 11. A portable streaming device comprising memory, at least one processing unit, and a storage device being operatively connected with said memory under control of said processing unit, whereby said processing unit adaptively maximises the size of a disk scheduler buffer memory within said memory in said portable streaming device. 12. A portable streaming device according to claim 11, whereby said storage device is an optical disk drive. 13. A portable streaming device according to claim 11, whereby said storage device is a hard-disk-based disk drive. 14. A portable streaming device according to claim 11, whereby said memory comprises non-volatile solid state memory not suffering from hot spots. 15. A portable streaming device according to claim 14, whereby said memory comprises magnetoresistive random access memory. 16. A computer readable medium having embodied thereon a computer program for processing by a processing unit, the computer program comprising: a code segment for adaptively maximising the size of a disk scheduler buffer memory within memory of a portable streaming device. 17. Use of a portable streaming device according to claim 11. 18. Use of a method according to claim 1.
FIELD OF THE INVENTION This invention relates in general to the field of portable storage devices and more particularly to the field of disc based portable electronic streaming devices and even more particularly to reduction of power consumption in storage media based portable electronic streaming devices. BACKGROUND OF THE INVENTION Portable disc based streaming devices such as portable audio players or video players are getting more and more widespread. These devices are, when e.g. carried along by its user, battery driven and total playing time before having to recharge or replace the batteries is a crucial feature distinguishing the acceptance of such devices. Total playing time depends directly on the devices' battery life, which again depends on the battery's capacity and the power consumption of the portable storage device. The portable devices are equipped with storage devices, such as a hard disk drive or an optical disk drive for storing the data, such as music clips or video sequences, to be streamed by the portable storage device. These storage devices comprise an electrically driven motor unit mechanically propelling the storage media. This operation is with regard to other units comprised in the portable storage devices a major power consumer responsible for a substantial part of the total dissipated power. In order to minimise power consumption of these storage devices, disk scheduling has been introduced. Hereby, the portable storage device comprises a cache memory and data is transferred from the disk drive to the cache memory and therefrom for further processing, and vice versa. A disk scheduler in the portable streaming device optimises the ratio between standby time and active time of the bit-engine, which is reading data from the storage device. Controlled by the disk scheduler, the storage device is spun down, i.e. the motor unit is switched off, as often and as long as possible by transferring the data to and from the storage medium of the storage device in a burst-like manner. This is achieved by using large scheduling buffers that allow the portable storage device to maximise the standby time between two accesses to the storage medium. A fixed part of the solid state memory totally available in the portable storage device is reserved for this purpose. Often, a dedicated separate hardware comprising memory circuit is arranged in the portable streaming devices as buffer memory. The larger the buffer is, the longer the drive can be switched off and hence the bigger the power savings. Although memory tends to become cheaper over time for the same amount of memory, it is still desirable to minimise the amount of hardware that is reserved for one single application, in the present case disk scheduling buffer, in order to reduce the cost and to increase the performance of portable streaming devices. Moreover, a further problem associated with the above-described strategy of switching the storage device of the portable streaming device off and on is that the life-time of the storage devices is limited to a certain number of start-stop cycles due to the mechanical part of the storage devices suffering from wearing out. Therefore it is even for this purpose desirable to have an as large as possible buffer in order to decrease the number of start-stop cycles over time and therefore increase life-time of the storage device and thus of the portable streaming device as a whole. SUMMARY OF THE INVENTION The present invention overcomes the above-identified deficiencies in the art and solves the above problems by maximising the memory buffer size at all times. According to preferred embodiments of the invention a method, a portable streaming apparatus, and a computer-readable medium are disclosed according to the appended independent claims. According to a first aspect of the invention, a method of controlling memory usage in a portable streaming device is provided. The portable streaming device comprises at least one memory, at least one processing unit, and at least one storage device which is operatively connected with the memory under control of the processing unit. According to the method, the size of a disk scheduler buffer memory within said memory in said portable streaming device is adaptively maximised. At least a portion of the available free memory is continuously allocated and designated and used as disk scheduler buffer memory. According to another aspect of the invention, a portable streaming apparatus is provided, which comprises memory, at least one processing unit, and a storage device being operatively connected with said memory under control of said processing unit. The processing unit allocates continuously free memory in the memory and designates at least a portion of the free memory as disk scheduler buffer. According to a further aspect of the invention, a computer readable medium is provided, which comprises a code segment instructing a processing unit to adaptively maximise the size of a disk scheduler buffer memory within memory of a portable streaming device. An object of the invention is to use existing memory of a portable streaming device more efficiently. A further object of the invention is to extend life cycle of a portable streaming device without modification of the existing hardware. Yet another object of the invention is to minimise the amount of necessary dedicated memory reserved for disk buffering. Furthermore, an object of the invention is to improve and to be compatible with existing disk scheduling schemes. BRIEF DESCRIPTION OF THE DRAWINGS Preferred embodiments of the present invention will be described in the following detailed disclosure, reference being made to the accompanying drawings, in which FIG. 1 shows a schematic view of the memory handling principle according to an embodiment of the invention, FIG. 2 illustrates in a flowchart a method according to an aspect of the invention, FIG. 3 illustrates a portable streaming device according to another aspect of the invention, and FIG. 4 shows a computer readable medium according to yet another aspect of the invention. DESCRIPTION OF PREFERRED EMBODIMENTS According to the invention, buffer size of the disk scheduling buffer is adaptively maximised in its size at all times. According to a preferred embodiment, a fixed size part of a scheduling buffer is provided, as in conventional schedulers, and an extra variable size part that adaptively changes in size depending on the availability of free solid state memory space in the portable streaming device. The fixed size part can be zero as well, whereby the device in this case only works with a variable memory part. FIG. 2 illustrates in a flowchart a method 2 according to an aspect of the invention. In a portable streaming device, the size of a disk scheduler buffer memory is adaptively maximised within a memory in said portable streaming device. Free memory is in step 50 continuously allocated. In step 60, at least a portion of said allocated free memory is designated and used as disk scheduler buffer memory. The allocation is repeated continuously or terminated in step 70. The total amount of solid state memory (e.g. DRAM or SRAM) available in a device is inherently limited and fixed in size and shared by a number of different components in the system. The scheduling buffer is only one of these, other users of the same memory pool are the application, operating system and possibly other internal devices in the system, such as video codecs, connected to an internal bus. By allocating free memory space, i.e. memory currently not in use, to the disk scheduler buffer, the average scheduler buffer size is significantly increased leading to longer standby times of the bit engine and hence reduced power consumption and increased life-time. This leads as well to an improved solid state memory utilisation of the portable streaming device. In typical mobile real-time applications, such as audio and/or video playback and/or recording, memory usage of non-scheduling tasks will be substantially stationary over time. In that situation the unused memory can easily be added to the scheduling buffers. As mobile infotainment devices are flexible devices that can execute a vast array of different applications, the available free memory is usually significant. The total available memory is targeted at the most demanding application in terms of memory usage which generally is not play back or recording of video material. Considering play back of encoded video in a non-limiting example, the total memory used for temporarily storing the uncompressed frames is often less than 8 MB for standard definition video material. For a portable streaming device having typically 64 MB of total memory, given a fixed scheduler buffer size of e.g. 32 MB, an extra 24 MB of memory can be added to the buffer leading to a total scheduler buffer size of 56 MB. This doubles almost the ratio between standby time and active time for this particular example of the invention, without any costly modification of the existing hardware, whereby the life cycle of the device is still almost doubled. In case of multiple audio/video streams, such as with layered encoding formats, the available free solid-state memory is divided over multiple streams, whereby the memory is not necessarily distributed equally over the streams. Buffer sizes for each stream also depend on the bit-rate of the individual streams. Streams with lower bit-rates require smaller buffer sizes, hence available memory is preferably spent on high bit-rate streams. In case applications which are running concurrently to the real-time streaming application, start requesting more memory, the scheduler buffer sizes can be gradually reduced to the original fixed size. For applications or background tasks that are bursty in terms of memory usage, and which are running concurrently to the streaming application, a number of extra provisions are taken. However it is to be noted that play back or recording of video material on-the-go, i.e. when power saving is most important, is a task that generally entirely takes up the attention of the portable streaming device. It is not very likely that there will be many other tasks consuming a lot of memory. This is mainly due to the fact that watching or recording video is generally speaking an activity that requires the full attention of the user of the portable streaming device. Therefore, no other tasks will be running and hence not a lot of additional memory will be required. However, when playing back video with maximal scheduler buffers, it is possible that non-streaming application or the OS requests memory that is not available because it is being used by the scheduler buffer. This situation is resolved by arranging and organising the total memory in the device available in such a particular manner as described below, so that the number of these occurrences can be reduced. FIG. 1 shows a conceptual diagram, which illustrates a virtual memory space of a preferred embodiment of the invention. The total memory available 1 in the portable streaming device is subdivided into sections 10, 20, 30, 40 which are either reserved for reserved for a particular purpose, such as streaming applications, or which are available for general use, e.g. by other applications or the OS. Memory sections 10, 20, 30 and 40 need not be contiguous memory sections in the portable streaming device. The illustration according to FIG. 1 is purely illustrative and shall not be interpreted in such a way that memory sections 10, 20, 30 and 40 are necessarily contiguous memory sections in the portable streaming device. On the contrary, the four memory sections can be distributed over different memory ranges and memory devices within the portable streaming devices. In addition, at least some of the memory sections 10, 20, 30, 40 can equally be zero, as already indicated above. The proportion of memory sections in FIG. 1 is also purely illustrative and not necessarily to scale. Memory section 10 is used as a fixed part entirely reserved to the scheduler as buffer memory. Memory section 20 is a variable part used by the disk scheduler as further buffer memory. Memory section 40 is used by all applications, except the scheduler, as well as by the OS. Memory section 40 grows from the bottom up according to arrow B, and the scheduler buffers grow from the top down according to arrow A, leaving a certain safety margin 30 in between the sections 20, 40. The scheduler part 10, 20 is implemented in such a way that the video data in the scheduler buffer that is needed first, either for writing to the disc or transferring to a decoder or networked connection, is located nearest to the top of the buffer. In order to achieve this, some central entity, e.g. an extension of the OS, needs to manage the total memory pool 1 used by all the memory consuming entities in the mobile device in a centralised way. In the case of reading from the storage medium, also called playback, the following applies. In the case of reading data from the medium, i.e. during playback, it is to be avoided that scheduler buffer content with an early deadline is overwritten with memory allocated by the application or OS. Only data required furthest in the future should be overwritten in case the safety margin is exceeded. In other words data for which there is still plenty of time to retrieve it again from the medium, which will be earlier than originally planned, preferably at the next medium access. This only occurs when the entire safety margin 30 is completely consumed. By reserving a minimum scheduler buffer size 10 as discussed above, equal to the buffer size for conventional scheduler buffer sizes, the overall performance in terms of power usage of cycle times will never be worse than with conventional schedulers. The scheduler buffer 10, 20 depicted in the FIG. 1 is conceptually a queue, preferably implemented as a circular buffer. Fragmentation of data is not an issue since data is always added to the front and read from the back, preferably in relatively large chunks. Only data at the end of the queue, i.e. data which is most recently added, will be overwritten, if needed for other applications. For the other tasks, i.e. non scheduler buffer usage, in the device this is different because for instance a chunk of allocated memory will be freed later than more recently allocated data which might lead to gaps and hence fragmentation of the bottom part of the memory pool. De-fragmentation in the bottom part, i.e. application and OS memory 40, is reduced by either performing active de-fragmentation or using more advanced memory pool management methods, such as scatter-gather like memory allocation that utilises smaller gaps in between allocated parts. In case of writing to the storage medium, also called recording, the following applies. In recording mode generally a larger buffer size is needed. There exists a risk of losing data because of either power failure or because part of the scheduler buffer memory is claimed by the portable streaming device for other tasks during recording, e.g. for the OS or various applications. In the latter case it could be necessary to preemptively flush part of the scheduler buffer to the storage medium in order to save up memory for the other task. This might lead to the stalling of applications that cannot claim access to the memory for the brief moment, when writing to the storage medium. However, the stalling of applications for a brief moment is not a big issue since these applications are considered to be non real-time applications in the first place. Loosing valuable data being recorded on the other hand is a much bigger issue which justifies this trade-off. Still, since there is a minimum buffer size, and by choosing an appropriate safety margin the occurrence of these situations can be reasonably controlled, especially if the implementer has complete control of all the tasks running on the device. In the other case of power failure, the amount of data loss can be significantly larger because of the large buffer sizes used for optimising power consumption scheduling. Especially for recording applications this can be a major issue as we will see in the following illustrative example. Assuming a buffer size of 64 MB and a recording of video by the portable streaming device, such as a camcorder, at a rate of 12 Mbps, after a power failure in total over 40 seconds of video are lost with conventional memory circuits. This might possibly contain a unique emotional valuable event being shot by the user operating the camcorder. According to an embodiment of the invention, these recording devices comprise non-volatile solid state memory not suffering from so called hot-spots, i.e. a limited number of writes per memory cell. Preferably MRAM (magnetoresistive random access memory), being of the above mentioned memory type, is used for this task. MRAM is a solid state memory that is both fast and does not suffer from hot-spots. Conventional random access memory (RAM) computer chips store information as long as electricity flows through them and is therefore not suitable for this task. As power is lost, the information is also. MRAM, however, retains data after a power supply is cut off MRAM works according to a principle of storing data bits using magnetic charges instead of the electrical charges used by DRAM (dynamic random access memory). Replacing DRAM with MRAM prevents data loss in portable streaming devices in the recording case. In this way, even after power failure, the video information stored in the MRAM is stored persistently and can be recovered after reconnecting the power. In order for the memory-pool manager, which is responsible for the allocation of memory for all processes in the device, to limit the number of occurrences where safety margin 30 is consumed, the memory-pool manager keeps track of the memory usage of different tasks and applications by tracking memory usage over time. These memory usage statistics are subsequently used to control the safety margin 30 or possibly even eliminate the need for it entirely. When this information is stored persistently, e.g. in the file system, it can be referred to when playing back the same content or using the same application and/or codecs. If needed the memory usage information could not only be limited to the software, but also the played back content as well, i.e. some content will require larger intermediate buffers than other content. FIG. 3 shows a portable streaming device according to another aspect of the invention. A portable streaming device 100 comprises a memory 102, at least one processing unit 101, and a storage device 103 being operatively connected with said memory 102 under control of said processing unit 101. The processing unit 101 adaptively maximises the size of a disk scheduler buffer memory within said memory 102 in said portable streaming device 100, preferably according to the method described above. FIG. 4 shows a computer readable medium 110 according to yet another aspect of the invention. The computer readable medium 110 includes a computer program 111 for processing by a processing unit 112. The computer program 111 comprises a code segment for adaptively maximising the size of a disk scheduler buffer memory within memory of a portable streaming device, preferably according the method described above. The optical disk can e.g. be a rewritable CD, DVD or a small form factor optical disc (SFFO). Small-form-factor optical (SFFO) disc drives are miniaturised optical disk drives having a high capacity. SFFO technology is specially suitable for portable devices, such as portable streaming devices. In certain cases, portable streaming devices comprise so called ESP memory, which stands for electronic shock protection memory. Here, the memory is used in a portable streaming device, e.g. a CD player or car CD player, which suffers a noise problem because of external shocks. To get clean sound, an electronic shock protection (ESP) system is used, buffering a certain amount of data in said buffer memory. An ESP system cannot clear noises if the external shock continues too long as it runs out of memory. The time limitation is dependent on the memory buffer size and the data-compression ratio. Here again, the buffer size is desirable to be as large as possible, and the method according to the invention can be used for ESP memory instead of a disk scheduler memory as well as the ESP memory can be allocated to one of the above described memory sections when implementing the method of the invention. It is possible to use the present invention in combination with existing disk scheduling schemes for reducing power consumption. Applications and use of the above described power saving strategy according to the invention are various and include exemplary fields such as portable MP3 players and portable camcorders, but also portable computers such as handhelds, notebooks or laptops for streaming data. The present invention has been described above with reference to specific embodiments. However, other embodiments than the above are equally possible within the scope of the appended claims, e.g. different kinds of memories, OS, portable devices than those described above, performing the above method by hardware or software, etc. Furthermore, the term “comprising” does not exclude other elements or steps, the terms “a” and “an” do not exclude a plurality and a single processor or other unit may fulfil the functions of several of the units or circuits recited in the claims. The invention can be summarised as a method (2) of controlling memory usage in a portable streaming device (100), a portable streaming device (1 00) and a computer readable medium (110). The portable streaming device (100) comprises at least one memory (102), at least one processing unit (101), and at least one storage device (103) being operatively connected with said memory (102) under control of said processing unit (101). The size of a disk scheduler buffer memory within said memory in said portable streaming device is adaptively maximised by said method (2) at all times. Free memory available within the portable streaming device is continuously allocated (50) and at least a portion of said allocated free memory is designated as disk scheduler buffer memory (60). Thus results improved solid state memory utilisation of the portable streaming device, and due to larger available disk buffer memory size, less start-stop-cycles of the storage device are initiated, which leads to a longer life-cycle of said portable streaming device.
<SOH> BACKGROUND OF THE INVENTION <EOH>Portable disc based streaming devices such as portable audio players or video players are getting more and more widespread. These devices are, when e.g. carried along by its user, battery driven and total playing time before having to recharge or replace the batteries is a crucial feature distinguishing the acceptance of such devices. Total playing time depends directly on the devices' battery life, which again depends on the battery's capacity and the power consumption of the portable storage device. The portable devices are equipped with storage devices, such as a hard disk drive or an optical disk drive for storing the data, such as music clips or video sequences, to be streamed by the portable storage device. These storage devices comprise an electrically driven motor unit mechanically propelling the storage media. This operation is with regard to other units comprised in the portable storage devices a major power consumer responsible for a substantial part of the total dissipated power. In order to minimise power consumption of these storage devices, disk scheduling has been introduced. Hereby, the portable storage device comprises a cache memory and data is transferred from the disk drive to the cache memory and therefrom for further processing, and vice versa. A disk scheduler in the portable streaming device optimises the ratio between standby time and active time of the bit-engine, which is reading data from the storage device. Controlled by the disk scheduler, the storage device is spun down, i.e. the motor unit is switched off, as often and as long as possible by transferring the data to and from the storage medium of the storage device in a burst-like manner. This is achieved by using large scheduling buffers that allow the portable storage device to maximise the standby time between two accesses to the storage medium. A fixed part of the solid state memory totally available in the portable storage device is reserved for this purpose. Often, a dedicated separate hardware comprising memory circuit is arranged in the portable streaming devices as buffer memory. The larger the buffer is, the longer the drive can be switched off and hence the bigger the power savings. Although memory tends to become cheaper over time for the same amount of memory, it is still desirable to minimise the amount of hardware that is reserved for one single application, in the present case disk scheduling buffer, in order to reduce the cost and to increase the performance of portable streaming devices. Moreover, a further problem associated with the above-described strategy of switching the storage device of the portable streaming device off and on is that the life-time of the storage devices is limited to a certain number of start-stop cycles due to the mechanical part of the storage devices suffering from wearing out. Therefore it is even for this purpose desirable to have an as large as possible buffer in order to decrease the number of start-stop cycles over time and therefore increase life-time of the storage device and thus of the portable streaming device as a whole.
<SOH> SUMMARY OF THE INVENTION <EOH>The present invention overcomes the above-identified deficiencies in the art and solves the above problems by maximising the memory buffer size at all times. According to preferred embodiments of the invention a method, a portable streaming apparatus, and a computer-readable medium are disclosed according to the appended independent claims. According to a first aspect of the invention, a method of controlling memory usage in a portable streaming device is provided. The portable streaming device comprises at least one memory, at least one processing unit, and at least one storage device which is operatively connected with the memory under control of the processing unit. According to the method, the size of a disk scheduler buffer memory within said memory in said portable streaming device is adaptively maximised. At least a portion of the available free memory is continuously allocated and designated and used as disk scheduler buffer memory. According to another aspect of the invention, a portable streaming apparatus is provided, which comprises memory, at least one processing unit, and a storage device being operatively connected with said memory under control of said processing unit. The processing unit allocates continuously free memory in the memory and designates at least a portion of the free memory as disk scheduler buffer. According to a further aspect of the invention, a computer readable medium is provided, which comprises a code segment instructing a processing unit to adaptively maximise the size of a disk scheduler buffer memory within memory of a portable streaming device. An object of the invention is to use existing memory of a portable streaming device more efficiently. A further object of the invention is to extend life cycle of a portable streaming device without modification of the existing hardware. Yet another object of the invention is to minimise the amount of necessary dedicated memory reserved for disk buffering. Furthermore, an object of the invention is to improve and to be compatible with existing disk scheduling schemes.
20050615
20071016
20060629
68109.0
G06F1200
0
EDUN, MUHAMMAD N
POWER SAVING METHOD FOR PORTABLE STREAMING DEVICES
UNDISCOUNTED
0
ACCEPTED
G06F
2,005
10,539,251
ACCEPTED
Electric device comprising phase change material
The electric device (1, 100) has a body (2, 101) with a resistor (7, 250) comprising a phase change material being changeable between a first phase and a second phase. The resistor (7, 250) has an electric resistance which depends on whether the phase change material is in the first phase or the second phase. The resistor (7, 250) is able to conduct a current for enabling a transition from the first phase to the second phase. The phase change material is a fast growth material which may be a composition of formula Sb1-cMc with c satisfying 0.05≦c≦0.61, and M being one or more elements selected from the group of Ge, In, Ag, Ga, Te, Zn and Sn, or a composition of formula SbaTebX100-(a+b) with a, b and 100-(a+b) denoting atomic percentages satisfying 1≦a/b≦8 and 4≦100-(a+b)≦22, and X being one or more elements selected from Ge, In, Ag, Ga and Zn.
1. An electric device with a body having a resistor comprising a phase change material being changeable between a first phase and a second phase, the resistor having an electric resistance which depends on whether the phase change material is in the first phase or the second phase, the resistor being able to conduct a current for enabling a transition from the first phase to the second phase, the phase change material being a fast growth material. 2. An electric device as claimed in claim 1, wherein the phase change material has a crystallization speed of at least 1 m/s. 3. An electric device as claimed in claim 1, wherein the phase change material is a composition of formula Sb1-cMc, with c satisfying 0.05≦c≦0.61, and M being one or more elements selected from the group of Ge, In, Ag, Ga, Te, Zn and Sn. 4. An electric device as claimed in claim 3, wherein c satisfies 0.05≦c≦0.5. 5. An electric device as claimed in claim 4, wherein c satisfies 0.10≦c≦0.5. 6. An electric device as claimed in claim 1, wherein the phase change material is substantially free of Te. 7. An electric device as claimed in claim 3, wherein the phase change material comprises Ge or Ga in concentrations which range in total between 5 and 35 atomic percent. 8. An electric device as claimed in claim 3, wherein the phase change material comprises In or Sn in concentrations which range in total between 5 and 30 atomic percent. 9. An electric device as claimed in claim 1, wherein the phase change material is a composition of formula SbaTebX100-(a+b), with a, b and 100-(a+b) denoting atomic percentages satisfying 1≦a/b≦8 and 4≦100-(a+b)≦22 , and X being one or more elements selected from the group of Ge, In, Ag, Ga, Zn and Sn. 10. An electric device as claimed in claim 9, wherein the phase-change material comprises at least 10% and less than 22% Ge. 11. An electric device as claimed in claim 9, wherein the resistor has a first contact area and a second contact area the first contact area being smaller than or equal to the second contact area, the first contact area having a characteristic dimension d (in nm), d being larger than 6·a/b. 12. An electric device as claimed in claim 1, wherein the phase change material of the resistor is in direct contact with a crystallization layer for expediting the transition from an amorphous phase to a crystalline phase. 13. An electric device as claimed in claim 12, wherein the crystallization layer is in direct contact with the first contact area and/or in direct contact with the second contact area. 14. An electric device as claimed in claim 1, wherein the resistor a first conductor and a second conductor electrically connected to the resistor constitute a memory element and the body comprises: an array of memory cells, each memory cell comprising a respective memory element and a respective selection device, and a grid of selection lines, each memory cell being individually accessible via the respective selection lines connected to the respective selection device. 15. An electric device as claimed in claim 14, wherein: the selection device comprises a metal oxide semiconductor field effect transistor having a source region, a drain region and a gate region, and the grid of selection lines comprises N first selection lines, M second selection lines, N and M being integers, and an output line, the first conductor of each memory element being electrically connected to a first region selected from the source region and the drain region of the corresponding metal oxide semiconductor field effect transistor, the second conductor of each memory element being electrically connected to the output line, a second region of the corresponding metal oxide semiconductor field effect transistor which is selected from the source region and the drain region and which is free from the first region, being electrically connected to one of the N first selection lines, the gate region being electrically connected to one of the M second selection lines. 16. An electric apparatus comprising a processor, a memory coupled to the processor, and a display coupled to an output terminal of the processor, wherein the memory comprises an electrical device as claimed in claim 1.
The invention relates to an electric device with a body having a resistor comprising a phase change material being changeable between a first phase and a second phase, the resistor having an electric resistance which depends on whether the phase change material is in the first phase or the second phase, the resistor being able to conduct a current for enabling a transition from the first phase to the second phase. WO-A 00/57,498 discloses an embodiment of an electric device having a resistor comprising a phase change material, which has approximately a composition of Sb2Te5Ge2. It maybe, e.g., Sb22Te56Ge22 or Sb29Te57Ge14. The phase change material is able to be in a first phase, which may be, e.g., crystalline, both of the first phase and/or the second phase may be partly amorphous and partly crystalline, provided that the resistor with the phase change material in the first phase and the resistor with the phase change material in the second phase have different values of the electric resistance. The resistor is electrically connected to a first conductor and a second conductor such that the value of the electric resistance can be measured. The first conductor and the second conductor may comprise, e.g., one or more of the following materials: titanium, titanium nitride, titanium aluminum nitride, titanium carbon nitride, titanium silicon, molybdenum, carbon, tungsten, and titanium tungsten. The resistor, the first conductor and the second conductor are able to conduct a current which via heating enables transitions of the phase change material between the first phase and the second phase. It is believed that for a transition from a phase with a relatively good conductivity, such as a crystalline phase or a mainly crystalline phase, to a phase with a relatively poor conductivity such as an amorphous phase or a mainly amorphous phase, use is made of heating by a sufficiently strong current causing melting of the phase change material. Hereinafter, the terms “crystalline” and “amorphous” are used to refer to a crystalline phase or a mainly crystalline phase, and to an amorphous phase or a mainly amorphous phase, respectively. Said heating may be achieved by the resistance of the first conductor, the second conductor, the resistor itself and the contact resistance between these elements. Which of these resistances contributes most to said heating depends in general on the materials and shapes of these elements. The heating ends when the current is switched off. The phase change material then cools down and assumes a more amorphous order. When inducing a transition from a phase with a relatively low electric conductivity to a phase with a relatively high electric conductivity, said heating is initially counteracted by the poor conductivity, which limits the current conducted through the phase change material. It is believed that by applying a sufficiently high voltage, the so-called breakdown voltage, across the resistor it is possible to locally induce electrical breakdown in the phase change material, which leads to a high local current density. The corresponding heating is then sufficient to increase the temperature of the phase change material to a value above its crystallization temperature, thereby enabling the phase transition from the amorphous phase to the crystalline phase. The known electric device can be used as a resistor with an electrically adjustable resistance. This type of device may be used in all types of circuits and integrated circuits which require a resistor with a resistance switchable between a first value and a second value. The known electric device is particularly suited for use as an electrically writable and erasable memory cell, which carries information encrypted in the value of the electrical resistance. The memory cell is assigned, e.g., a “0” when the resistance is relatively low and a “1” when the resistance is relatively high. The resistance may be easily measured by applying a voltage across the resistor and measuring the corresponding current. The memory element can be written and erased by inducing a transition from a first phase to a second phase as described above. It is a disadvantage of the known electric device that the switching time from the amorphous phase to the crystalline phase is relatively long. This limits the rate at which the resistor value can be set. It is an object of the invention to provide an electric device as described in the opening paragraph which has a relatively short switching time from the amorphous phase to the crystalline phase. The invention is defined by the independent claims. The dependent claims define advantageous embodiments. The invention is based on the insight that the class of phase change materials used in the present invention has a different crystal growth mechanism than the known phase change materials. In the known phase change materials used for electrical devices, the phase transition from the amorphous phase to the crystalline phase takes place by nucleation, i.e. the crystallization starts from several randomly distributed points within the amorphous phase. The crystallization time in the known device is therefore independent of the volume of the amorphous phase. It is restricted by the nucleation time which is in the order of 50 ns for the known phase change materials. In contrast to this, the electric device according to the invention comprises a phase change material which is a so-called fast growth material. In fast growth materials the crystalline phase grows at a high speed, the so-called crystallization speed, from the interface between the amorphous phase and the crystalline phase. For these materials the crystallization time depends on the volume of the amorphous phase. This allows the switching time from the amorphous phase to the crystalline phase to be relatively short, in particular when the size of the amorphous phase is relatively small, e.g. below 50 nm. In the field of optical recording, these advantageous properties related to the phase transition between the amorphous phase and the crystalline phase of Sb69Te31 are known from the article “Phase-change media for high-numerical-aperture and-blue-wavelength recording” by H. J. Borg et al., Japanese Journal of Applied Physics, volume 40, pages 1592-1597, 2001. This article, however, does not mention that fast growth materials surprisingly have other properties which make them suitable as phase change material in the electrical device according to the invention. The inventors of the present invention have established in particular that these fast growth phase change materials are changeable between a first phase and a second phase, the resistor having an electrical resistance which depends on whether the phase change material is in the first phase or the second phase, the resistor being able to conduct a current for enabling a transition from the first phase to the second phase. Preferably, the electric device according to the invention comprises a phase change material with a crystallization speed of at least 1 m/s. The amorphous phase change material of the known electric device has dimensions in the order of 10 to 20 nm. Applying the phase change material according to the invention in such a device results in a switching time of 10 to 20 ns or less. In an embodiment the phase change material is a composition of formula Sb1-c Mc, with c satisfying 0.05≦c≦0.61, and M being one or more elements selected from the group of Ge, In, Ag, Ga, Te, Zn and Sn. Optionally, the material may comprise relatively small amounts, e.g. less than 5 atomic percent, of other elements such as, e.g. As, S, Se which do not significantly change the crystallization and the electrical breakdown behavior. The electric device according to the invention has the additional advantage that the breakdown voltage required for switching from the high resistive amorphous state to the low resistive crystalline phase is lower than that of the known electric device. This is particularly advantageous when using advanced transistors to switch the electric device because the advanced transistors have smaller dimensions and are therefore able to provide only a relatively small voltage. The inventors have established that the breakdown voltage scales approximately with the band gap of the phase change material in the amorphous state, and that the band gap decreases with increasing Sb amount. Preferably, the phase change material comprises at least 50 atomic percent of Sb. It is further preferred that the phase change material comprises at least 10 atomic percent of one or more elements M because in this way the stability of the amorphous phase is increased and the phase change material in the amorphous phase can be subjected to relatively high temperatures before spontaneous re-crystallization occurs. A further advantage of the electric device according to the invention resides in the fact that the resistivity of the crystalline phase is lower than that in the known electric device. Therefore, the ohmic losses in the crystalline phase are smaller than those in the known electric device, allowing the saving of power. Moreover, the contact resistance between the first conductor and the phase change material, and between the second conductor and the phase change material in the electric device according to the invention is lower than that in the known electric device. This allows one to use a smaller first contact area and/or second contact area, which for the electric device according to the invention results in a shorter switching time between the amorphous phase and the crystalline phase. In the electric device according to the invention a smaller amount of Te is used than in the known electric device. This has the advantage that the phase change material is less reactive which improves the stability of the electric device. In particular, reactions at the interface between the phase change material and the conductors connected to it are reduced. In addition the phase change material of the electric device according to the invention has a relatively low vapor pressure due to the reduced Te amount, so that higher processing temperatures can be applied. Preferably, the phase change material is substantially free of Te. Preferably, the one or more elements M comprise Ge and/or Ga. An electric device comprising a phase change material comprising Ge and/or Ga has the advantage that the crystallization temperature is relatively high and, therefore, the amorphous phase is stable up to relatively high temperatures. The crystallization temperature and thus the stability of the amorphous phase increases with increasing Ge and/or Ga concentration. Preferably, the phase change material comprises Ge and/or Ga in concentrations which range in total between 5 and 35 atomic percent, more preferred between 15 and 25 atomic percent. It is often preferred that the phase change material comprises less than 30 atomic percent of Ge because otherwise the crystallization temperature and the melting temperature are so high that a relatively high energy is required to induce a phase transition from the amorphous phase to the crystalline phase, and back. The crystallization speed decreases when increasing the total concentration of Ge and Ga. This dependence of the crystallization speed upon the Ge and/or Ga concentration may be used to adjust the crystallization speed. Moreover, it is also preferred that the phase change material comprises less than 35 atomic percent of Ga because at higher Ga concentrations the difference between the electric resistance in the amorphous phase and in the crystalline phase is relatively small which may lead to errors when measuring the resistance. Preferably, the phase change material comprises less than 25 atomic percent of Ga. In one embodiment, the phase change material comprises In and/or Sn. Preferably, the phase change material comprises In-and/or Sn in concentrations which range in total between 5 and 30 atomic percent. A phase change material comprising In and/or Sn has a relatively high crystallization speed and a relatively low melting temperature which implies that a relatively small energy is required for inducing the transition from the first phase to the second phase. It is often advantageous if the phase change material comprises in total between 15 and 25 atomic percent of In and/or Sn. Preferably, the phase change material comprises approximately 20 atomic percent of these materials. When the phase change material comprises in total more than 20 atomic percent of Ge and/or Ga, it is preferred that the phase change material further comprises one or more elements selected from In and Sn in concentrations which are less than 30 atomic percent. The electric device according to this embodiment has a relatively high stability of the amorphous phase due to the presence of Ge and/or Ga and a relatively low melting temperature due to the presence of one or more elements selected from In and Sn. In a variation of this embodiment the phase change material is a composition of formula SbaTebX100-(a+b), with a, b and 100-(a+b) denoting atomic percentages satisfying 1≦a/b≦8 and 4≦100-(a+b)≦2 , and X being one or more elements selected from the group of Ge, In, Ag, Ga, Zn and Sn. Adding the latter element has the advantage that the phase change material has a relatively high crystallization speed. Optionally, the material may comprise relatively small amounts, e.g. less than 5 atomic percent, of other elements such as, e.g. As, S, Se which do not significantly change the crystallization and the electrical breakdown behavior. It is advantageous if the element X comprises Ge. An electric device comprising a phase-change material comprising Ge has the advantage that the crystallization temperature is relatively high and, therefore, the amorphous phase is stable up to relatively high temperatures. In an embodiment the phase-change material comprises more than 10 atomic percent and less than 22 atomic percent of Ge. In this case the crystallization temperature of the phase-change material is between 180 and 250 degrees Celsius. When the crystallization temperature is lower than 180 degrees Celsius, the stability of the amorphous phase may be insufficient, in particular when the electric device may be subjected to relatively high temperatures. When the crystallization temperature is higher than 200 degrees Celsius such as, e.g. 250 degrees Celsius, a relatively high switching power is required to induce a phase transition from the amorphous phase to the crystalline phase. It is advantageous if the first contact area is smaller than or equal to the second contact area, the first contact area having a characteristic dimension d (in nm), 6·a/b being smaller than d. This embodiment of the invention is based on the following insight: in order to be able to perform a phase transition from the crystalline phase to the amorphous phase it is required that the cooling time, i.e. the time in which the phase change material cools down to a temperature below the crystallization temperature, is smaller than the crystallization time, i.e. the time required for a transition from the amorphous phase back to the crystalline phase. If this condition is not met, the melted amorphous material re-crystallizes during cooling down, resulting in the same phase as before the heating, i.e. the phase transition from the crystalline phase to the amorphous phase is not possible. For the phase change material of the electric device according to the invention the crystallization starts at the interface between the amorphous phase and the crystalline phase. Therefore, the crystallization time is given by the characteristic dimension of the amorphous volume divided by the crystallization speed. Here, the characteristic dimension is the largest distance between the point which is the last to crystallize and the interface between the amorphous phase and the crystalline phase at the start of the phase transition. This dimension can be approximated by the characteristic dimension of the first contact area provided that the first contact area is not larger than the second contact area. The inventors have determined the cooling time from simulations and the crystallization speed as a function of the composition of the phase change material from experiments. Using the results of these simulations and measurements combined with the above described criterion it can be shown that 6·a/b has to be smaller than d (d is in nm) in order to prevent complete re-crystallization during cooling down of the amorphous phase. In some cases the characteristic dimension of the amorphous phase change volume extends beyond the first contact area, the amorphous phase being approximately twice the size of the first contact area. The requirement can then be relaxed to 3·a/b being smaller than d (d is in nm). In this case a first contact area with a two times smaller surface area can be used. In an embodiment the phase change material of the resistor is in direct contact with a crystallization layer having a crystal structure. This crystallization layer is advantageous in situations where a volume with the amorphous phase has a surface area which is in direct contact with a material different from the phase change material. When performing a phase transition from the amorphous phase to the crystalline phase, the phase change material of the electric device according to the invention starts growing from the interface between the crystalline phase and the amorphous phase. At the surface area which is in direct contact with a material being different from the-phase change material, the crystallization is therefore delayed, leading to a relatively long crystallization time. By introducing a crystallization layer having a crystal structure the crystal growth at the surface area can be expedited. Preferably, the crystal structure of the crystallization layer is similar to that of the phase change material. It is advantageous if the crystallization layer has a thickness smaller than 100 nm. The crystallization layer is a potential heat sink, in particular due to its crystal structure. In order to limit the corresponding heat flow out of the phase change material during heating for promoting a phase transition, the crystallization layer should be relatively thin. Crystallization layers with a thickness larger than 100 nm lead to a relatively large heat flow out of the phase change material. Preferably, the thickness of the crystallization layer is smaller than 50 nm. Preferably, the crystallization layer is in direct contact with the first contact area and/or in direct contact with the second contact area because the phase change material is often amorphous in the vicinity of the first contact area and/or the second contact area It is often advantageous if the crystallization layer is electrically conductive and electrically connects the first contact area and the second contact area. In this case the crystallization layer constitutes an electrical bypass arranged in parallel with the phase change material. The crystallization layer is then able to conduct a current which can be used to indirectly heat the phase change material for promoting the transition from the first phase to the second phase. Preferably, a melting temperature of the crystallization layer is higher than a melting temperature of the phase change material. Preferably, the crystallization layer is chemically relatively stable to reduce the chance that the material of the crystallization layer mixes with the phase change material. The crystallization layer is particularly advantageous if a plurality of bits are stored in one electric device. In this case the volume of the phase change material undergoing the phase transition determines which bit is stored. It is then often convenient to use a volume undergoing the phase transition which extends beyond the first contact area and/or the second contact area In particular in these cases the crystallization layer is beneficial. In an embodiment of the electric device according to the invention the first conductor, the second conductor, the resistor and the layer constitute a memory element, and the body comprises an array of memory cells, each memory cell comprising a respective memory element and a respective selection device, and a grid of selection lines, each memory cell being individually accessible via the respective selection lines connected to the respective selection device. Such an electric device can be used as a non-volatile, electrically writable, electrically readable and electrically erasable memory. Because each memory cell comprises a selection device, individual memory elements can be conveniently selected for reading, i.e. for measuring the value of the electrical resistance, and for writing and erasing, i.e. for inducing a transition from a first phase to a second phase. The memory elements of the present invention may be electrically coupled to selection devices and to selection lines in order to form a memory array. The selection devices permit each discrete memory cell to be read and written without interfering with information stored in adjacent or remote memory cells of the array. Generally, the present invention is not limited to the use of any specific type of selection device. Examples of selection devices include field-effect transistors, bipolar junction transistors, and diodes such as known from, e.g., WO-A 97/07550. Examples of field-effect transistors include JFET and metal oxide semiconductor field effect transistor (MOSFET) such as known from, e.g., WO-A 00/39028. Examples of MOSFET include NMOS transistors and PMOS transistors. Furthermore NMOS and PMOS may even be formed on the same chip for CMOS technologies. Usually, such types of electric devices are as compact as possible which implies that the mutual distance between adjacent resistors is small. In these electric devices comprising a dielectric material according to the invention, crosstalk is reduced. In a embodiment the selection device comprises a MOSFET having a source region, a drain region and a gate region, and the grid of selection lines comprises N first selection lines, M second selection lines, N and M being integers, and an output line, the first conductor of each memory element being electrically connected to a first region selected from the source region and the drain region of the corresponding metal oxide semiconductor field effect transistor, the second conductor of each memory element being electrically connected to the output line, a second region of the corresponding metal oxide semiconductor field effect transistor which is selected from the source region and the drain region and which is free from the first region, being electrically connected to one of the N first selection lines, the gate region being electrically connected to one of the M second selection lines. In this type of device the resistor can be conveniently integrated with the selection device. These and other aspects of the electric-device according to the invention will be further elucidated and described with reference to the drawings, in which: FIG. 1 is a cross section of an embodiment of the electric device; FIGS. 2A and 2B are plots of the switching from the amorphous phase to the crystalline phase, and from the crystalline phase to the amorphous phase, respectively; FIG. 3 is a plot of the current as a function of the applied voltage when switching from the amorphous phase to the crystalline phase; FIG. 4 is a plot of the crystallization speed as a function of the Sb/Te ratio; FIG. 5 is a plot of the crystallization speed as a function of the Ge content; FIGS. 6A and 6B are plots of the sheet resistance R as a function of the temperature of Sb85Ga15 and Sb85Ge15, respectively; and FIG. 7 is a cross section of another embodiment of the electric device, and with reference to a few tables, in which: Table 1 shows embodiments of the phase change material comprising Te used in the electric device; Table 2 shows the crystallization temperature for various compositions; Table 3 shows examples of the phase change material being a composition of formula Sb1-cMc, with c satisfying 0.05≦c≦0.61, and M being one or more elements selected from the group of Ge, In, Ag, Ga, Te, Zn and Sn; and Table 4 shows minimum characteristic dimensions for the phase change materials of Table 1. The Figures are not drawn to scale. In general, identical components are denoted by the same reference numerals. The electric device 1, shown in FIG. 1, has a body 2 which comprises a substrate 10 which may comprise, e.g. a single crystal p-doped silicon semiconductor wafer. On a main surface of the substrate 10 a resistor 7 is embedded in a dielectric 13, e.g. silicon oxide. The resistor 7 comprises a phase change material changeable between a first phase and a second phase. The phase change material of the electric device 1 is a fast growth material which preferably has a crystallization speed of at least 1 m/s. In an embodiment the phase change material is a composition of formula Sb1-cMc, with c satisfying 0.05≦c0.61, and M being one or more elements selected from the group of Ge, In, Ag, Ga, Te, Zn and Sn. Preferably, c satisfies 0.05≦c≦0.5. Even more, preferably; c satisfies 0.10≦c≦0.5. A group of advantageous phase change materials has one or more elements M other than Ge and Ga in concentrations which in total are smaller than 25 atomic percent and/or comprise in total less than 30 atomic percent of Ge and/or Ga. Phase change materials comprising more than 20 atomic percent of Ge and Ga and one or more elements selected from In and Sn in concentrations which in total are between 5 and 20 atomic percent have a relatively high crystallization speed and at the same time a relatively high stability of the amorphous phase. In another embodiment the phase change material is a composition of formula SbaTebX100-(a+b), with a, b and 100-(a+b) denoting atomic percentages satisfying 1≦a/b≦8 and 4≦100-(a+b)≦22, and X being one or more elements selected from Ge, In, Ag, Ga and Zn. The phase change material may be, e.g. Sb72Te20Ge8, other embodiments of the above mentioned class of phase change materials will be described below. The resistor 7 has a surface with a first contact area 5 and a second contact area 6, and an electrical resistance R between these two contact areas. The electrical resistance has a first value when the phase change material is in the first phase and a second value when the phase change material is in the second phase. The phase change material may be deposited by sputtering as descried in the article “Phase-change media for high-numerical-aperture and blue-wavelength recording” by H. J. Borg et al., Japanese Journal of Applied Physics, volume 40, pages 1592-1597, 2001. The body 2 further comprises a first conductor 3 of, e.g., titanium disilicide (TiSi2) which is electrically connected to the first contact area 5, and a second conductor 4 of titanium nitride (TiN), which is electrically connected to the second contact area 6. The first conductor 3 and the second conductor 4 are connected to metal lines 8 and 9, respectively. The metal lines 8 and 9 comprise tungsten and have contact pads 12 and 11, respectively; they allow conduction of a current through the first conductor 3, the second conductor 4 and the resistor 7 for heating of the phase change material to enable a transition from the first phase to the second phase. For a good stability of the interface at the first contact area 5 and the second contact area 6 it is preferred that the phase change material is substantially free of Te. To characterize the switching behavior of the electric device 1, a voltage U was applied between contact pads 11 and 12, and the current I flowing due to this voltage was measured. Typical results of such measurements are shown in FIGS. 2A and 2B, where the solid line and the dotted line denote the voltage U and the current I, respectively. For the measurement of FIG. 2A the resistor 7 was initially at t=0 in the amorphous phase. At t=50 ns a first voltage pulse of approximately 0.15 V was applied which did not lead to any significant current I during this voltage pulse. This demonstrates that the phase change material of the resistor 7 was indeed in the high resistive amorphous state. At t=200 ns a second voltage pulse of approximately 0.5 V was applied which did lead to a current I of 300 μA during this voltage pulse. Here, the supplied voltage was larger than the breakdown voltage and therefore, a significant current I is detected. At t=370 ns a third voltage pulse substantially identical to the first voltage pulse was applied which did lead to a detectable current I of approximately 80 μA. This shows that the phase change material is in a more crystalline phase with a lower resistance during the third voltage pulse. The current conducted through the resistor 7 during the second voltage pulse was sufficient to heat the phase change material for promoting the transition from the amorphous phase to the crystalline phase. For the measurement of FIG. 2B the resistor 7 was initially at t=0 in the crystalline phase. At t=50 ns a fourth voltage pulse substantially identical to the first voltage pulse was applied which did lead to a detectable current I of approximately 80 μA. This shows that the phase change material is in a more crystalline phase with a lower resistance analogous to the situation at the third voltage pulse. At t=200 ns a fifth voltage pulse of approximately 0.8 V was applied which does lead to a current I of 700 μA during this voltage pulse. Here, the applied voltage was large enough to melt the crystalline phase and the cooling down of the melted amorphous phase took place fast enough to freeze the phase change material in an amorphous phase. As a result, a sixth voltage pulse substantially identical to the first voltage pulse provided at t=370 ns does no longer lead to a detectable current I. The voltage pulses each had a duration of 10 ns. The results of FIG. 2A and 2B show that the electric device 1 according to the invention can be switched from the amorphous phase to the crystalline phase, and from the crystalline phase to the amorphous phase with a switching time of at most 10 ns which is approximately a factor of 3 to 5 faster than that of the known electrical device. The electrical breakdown behavior of the electric device 1 according to the invention and that of the known electric device are compared in FIG. 3. For both devices the current I is measured as a function of the applied voltage U. At the start of the measurements, the phase change material was in the amorphous phase. A voltage of 0.1 V was applied to the devices which resulted in a small current I. Subsequently the voltage was increased and for each voltage the corresponding current was measured. In the electric device 1 according to the invention, breakdown occurred approximately at Ubd=0.45 V leading to a substantially increased current I. In the known electric device, breakdown occurred at approximately Ubd=0.6 V. A further increase of the voltage U results in a linearly increasing current I. The corresponding differential resistance for voltages U larger than the breakdown voltage Ubd is denoted Rbd. The result shown in FIG. 3 illustrates that the electric device 1 according to the invention has a smaller breakdown voltage than the known electric device. When the phase change material is a composition of formula SbaTebX100-(a+b), with a, b and 100-(a+b) denoting atomic percentages satisfying 1≦a/b≦8 and 4≦100-(a+b)≦22, and X being one or more elements selected from Ge, In, Ag, Ga and Zn, the crystallization speed of the phase change material used in the electric device 1 can be tuned by varying the Sb/Te ratio as shown in FIG. 4. The crystallization speed is 1 m/s or higher and it increases approximately linearly if the amount of Sb is increased with respect to the amount of Te. The phase change material of the electric device 1 according to the invention comprises Sb and Te in a ratio Sb/Te larger than 1 and smaller than 8. Preferably, the ratio is smaller than 4 because for larger ratios the crystallization speed is above approximately 4.5 m/s. In many cases it is then impossible to obtain an amorphous phase because the phase change material crystallizes before it is cooled down to below the crystallization temperature. The phase change material further comprises 4 to 22 atomic percent of an element X selected from Ge, In, Ag, Ga and Zn. The element X may comprise one or more of these elements. Examples of this type of phase change material are given in Table 1. The crystallization speed of the phase change material is above 1 m/s and increases as the Sb/Te ratio increases, independent of the choice of the element X and its concentration. TABLE 1 Examples of the phase change material being a composition of formula SbaTebX100−(a+b), with a, b and 100 − (a + b) denoting atomic percentages satisfying 1 ≦ a/b ≦ 8 and 4 ≦ 100 − (a + b) ≦ 22, and X being one or more elements selected from Ge, In, Ag, Ga and Zn. Ge, In, Ag and Ga denote the atomic percentage of these elements comprised in the phase change material, Sb/Te denotes the ratio of the atomic percentage of Sb and Te. Sb/Te Ge In Ag Zn Ga composition 3.6 8 Sb72Te20Ge8 1.7 15 Sb54Te31Ge15 1.5 15 Sb51Te34Ge15 1.7 10 Sb57Te33Ge10 3.6 8 Sb72Te20Ag8 3.6 8 Sb72Te20Ga8 5.1 8 Sb77Te15Ga8 3.6 8 Sb72Te20In8 4 5 Sb76Te19In5 4 10 Sb72Te18In10 3.6 6 2 Sb72Te20Ge6Zn2 3.6 6 2 Sb72Te20Ge6In2 3.6 2 7 Sb72Te19Ge2In7 3.6 4 4 Sb72Te20Ga4In4 3.3 1 4 Sb73Te22Ge1Ga4 3.3 2 3 Sb73Te22Ge2Ga3 6.7 8 Sb80Te12Ge8 8 10 Sb80Te10Ge10 4.5 11 Sb73Te16Ge11 When the phase change material is a composition of formula Sb1-cMc, with c satisfying 0.05≦c≦0.61, and M comprising Ge, the crystallization speed of the phase change material used in the electric device 1 can be tuned by varying the Ge content as shown in FIG. 5. The phase change materials being a composition of formula Sb1-cMc with c satisfying 0.05≦c≦0.61, and M being one or more elements selected from the group of Ge, In, Ag, Ga, Te, Zn and Sn have crystallization temperatures, shown in Table 2, which are typically 50-100° C. higher than those of the compositions near the GeTe—Sb2Te3 tie-line. Additional advantages of these materials are that the high crystallization temperature is relatively high and that the sheet resistance of the crystalline phase is substantially independent of the temperature for temperatures up to 400° C. TABLE 2 Crystallization temperature for various compositions of the phase change material. Tc (amorphous Tc (as deposited mark in crystalline Compound amorphous) (° C.) layer) (° C.) Ga10Sb90 210 165 Ga17Sb83 233 210 Ga30Sb70 251 Ge12Sb88 235 154 Ge15Sb85 250 208 Ge22Sb78 271 246 Ge30Sb70 281 Ge5In20Sb85 200 134 Ga20In15Sb65 215 190 Ge15Sn20Sb65 212 180 The phase change materials being a composition of formula Sb1-cMc, with c satisfying 0.05≦c≦0.61, and M being one or more elements selected from the group of Ge, In, Ag, Ga, Te, Zn and Sn have a sheet resistance R shown in FIGS. 6A and 6B for Sb85Ga15 and Sb85Ge15, respectively, which changes by at least two orders of magnitude upon crystallization. TABLE 3 Examples of the phase change material being a composition of formula Sb1−cMc, with c satisfying 0.05 ≦ c ≦ 0.61, and M being one or more elements selected from the group of Ge, In, Ag, Ga, Zn and Sn. c M composition 0.15 Ge Sb85Ge15 0.15 In Sb85In15 0.15 Ga Sb85Ga15 0.12 Ge Sb88Ge12 0.22 Ge Sb78Ge22 0.15 In, Ga Sb85In10Ga5 0.08 Ge Sb92Ge8 0.1 Ga Sb90Ga10 0.15 In, Ge Sb85In10Ge5 0.15 In, Ga Sb85In7.5Ga7.5 0.2 In Sb80In20 0.35 Ge, Sn Sb65Ge15Sn20 0.55 Ge, Sn Sb45Ge25Sn30 0.3 Ge Sb70Ge30 0.3 Ga Sb70Ga30 0.5 Ga, Sn Sb50Ga25Sn25 0.5 In, Ge Sb51In20Ge29 0.35 Zn, Ge, In Sb65Ge20In10Zn5 0.35 Ag, Ge, In Sb65Ge20In10Ag5 0.35 In, Ge, Sn Sb65Ge20Sn10In5 In another embodiment, shown in FIG. 7, the electric device 100 is formed in body 101 comprising a semiconductor substrate 102 analogous to substrate 10 of FIG. 1. It comprises an N×M array of memory cells which array is identical to that known from WO-A 00/57498, see in particular FIG. 4 of that patent application. Here, N and M are integers. Each memory cell comprises a respective memory element 103 and a respective selection device 104. In the embodiment shown in FIG. 7 each memory cell comprises two independent memory elements 103A and 103B. The first conductor 130A, the second conductor 270A, the resistor 250 and the layers 127A and 128 constitute memory element 103A, and the first conductor 130B, the second conductor 270B, the resistor 250 and the layers 127B and 128 constitute memory element 103B. In other words, the memory elements 103A and 103B share the same resistor 250 and the same layer 128. In another embodiment, not shown, layer 128 is omitted and layer 250 is in direct contact with layer 260. In yet another embodiment, also not shown, layer 127A and/or 127B are omitted. The resistor 250 comprises one of the phase change materials described above. It has a surface with first contact areas 132A and 132B, and second contact areas 272A and 272B. As part of memory element 103A, the resistor 250 has an electrical resistance between the first contact area 132A and the second contact area 272A which has a first value when the phase change material is in the first phase and a second value when the phase change material is in the second phase. As part of memory element 103B, the resistor 250 has an electrical resistance between the first contact area 132B and the second contact area 272B which has a first value when the phase change material is in the first phase and a second value when the phase change material is in the second phase. The contact areas 132A and 132B are smaller than or equal to the second contact areas 272A and 272B, respectively. The first contact areas 132A and 132B each have a characteristic dimension d. In an embodiment the atomic percentages a and b of Sb and Te, respectively, are smaller than d/3, d being in nm. For a given ratio a/b this implies that the minimum characteristic dimension of the first contact area 132 is dmin,1=6·a/b, where d is in nm. Typical values of dmin,1 for various ratios of a/b are given in Table 4. When the amorphous volume extends beyond the first contact area, the minimum characteristic dimension of the first contact area 132 can be relaxed to approximately dmin,2=3·a/b, where d is in nm. Typical values are also shown in Table 4. TABLE 4 Minimum characteristic dimension of an electric device 1 in which the phase change material does not extend beyond the first contact area 132 and in which it extends to approximately twice the characteristic dimension of the contact area. In the first case the minimum allowable characteristic dimension is dmin, 1, in the latter it is dmin, 2. Sb/Te dmin, 1 (nm) dmin, 2 (nm) 1.5 9 4.5 1.7 10.2 5.1 3.3 19.8 9.9 3.6 21.6 10.8 4 24 12 4.5 27 13.5 5.1 30.6 15.3 The first conductors 130A and 130B are electrically connected to the first contact areas 132A and 132B, respectively. The second conductors 270A and 270B are electrically connected to the second contact areas 272A and 272B, respectively. The first conductor 130A, the second conductor 270A and the resistor 250 are able to conduct a current for heating of the phase change material to enable a transition from the first phase to the second phase, thereby changing the electrical resistance of the first memory element 103A. Analogously, the first conductor 130B, the second conductor 270B and the resistor 250 are able to conduct a current for heating of the phase change material to enable a transition from the first phase to the second phase, thereby changing the electrical resistance of the second memory element 103B. As shown in the embodiment shown in FIG. 7, a layer 260 of a dielectric material provides electrical isolation between the resistor 250 and the output line 271 such that the resistor 250 is connected to the output line 271 only via the second conductors 270A and 270B. The dielectric layer 140 electrically isolates the first conductor 130A from the first conductor 130B. A-dielectric layer 180 which may comprise borophosphosilicate glass (BPSG) is deposited on top of the electric device 100. Analogous to the electric device known from WO-A 00/57498, the first conductors 130A and 130B are conductive sidewall spacers, also referred to as conductive spacers, formed along the sidewall surfaces 126S of the dielectric regions 126. The areas of contact between the resistor 250 and the first conductors 130A and 130B are the first contact area 132A and 132B, respectively. Hence, the only electrical coupling between the resistor 250 and the first conductors 130A and 130B is through all or a portion of the first contact area 132A and 132B, respectively. The remainder of the first conductors 130A and 130B is electrically isolated from the resistor 250 by dielectric layers 126 and 140. Alternatively, the first conductor 130A and/or 130B may be formed as conductive sidewall spacers by conformally depositing one or more contact layers onto the sidewall surface or surfaces of a via hole as known from WO-A 00/57498. The via hole may be round, square, rectangular or irregularly shaped. The conductive sidewall spacers may also be formed by conformally depositing one or more contact layers onto the sidewall surfaces of a pillar or mesa. The remaining space in the via is filled with a layer of dielectric material. In the electric device 100, shown in FIG. 7, the phase change material of the resistor 250 is in direct contact with crystallization layers 127A, 127B and 128, each of which has a crystal structure. The crystallization layer has a crystal structure. It may be a conductor, a semiconductor or a dielectric. It may comprise, e.g., PbTe, Ag2Te, CrTe Pb, Ge and Si. It has a thickness between 2 and 100 nm. The crystallization layers 127A and 127B are in direct contact with the first contact area 132A and 132B, respectively. The crystallization layer 128 is in direct contact with the second contact area 272A and 272B. The crystallization layer 127B is electrically conductive and electrically connects the first contact area 132B and the second contact area 272B. The crystallization layer 127B constitutes an electrical bypass arranged in parallel with the phase change material. The body 101 comprises a grid of selection lines comprising N first selection lines 190, M second selection lines 120 and an output line 271 such that each memory cell is individually accessible via the respective selection lines 120 and 190 connected to the respective selection device 104. Each of the memory elements 103A and 103B of electric device 100 is electrically coupled to a selection device 104 which is a MOSFET, and more specifically an NMOS transistor. The MOSFET has n-doped source regions 110, n-doped drain regions 112, and gate regions 118. The source regions 110 and the drain regions 112 may comprise more than one portion of n-doped material, namely a lightly doped n-portion and a more heavily doped n+ portion. The n-doped source regions 110 and drain regions 112 are separated by channel regions 114. The gate regions 118, formed above the channel regions 114, control the flow of current from the source regions 110 to the drain regions 112 through the channel regions 114. The gate regions 118, preferably comprise a layer of polysilicon. The gate regions 118 are separated from the channel regions 114 by dielectric regions 116. Channel stop regions 113 are formed in the n-doped drain regions 112 creating two neighboring, electrically isolated drain regions 112 for separate NMOS transistors. Generally, the channel stop regions 113 have a conductivity type opposite to that of the source and drain regions 110, 112. In the NMOS embodiment shown, the channel stop regions 113 comprises p-doped silicon. Formed above the gate regions 118 are selection lines 120 which preferably comprise a layer of tungsten silicide. Selection lines 120 are used to deliver the electrical signal to the gate regions 118. Formed above the selection lines 120 are the dielectric regions 122 which electrically insulate the selection lines 120 from neighboring regions of the electric device 100. The stacks of layers 116, 118, 120 are collectively referred to as the gate stacks. Dielectric regions 126 are formed on the sidewall surfaces of the gate stacks. Selection lines 190 are formed on top of the upper insulation regions 180. The selection lines 190 may be formed from a conductive material such as aluminum or copper. Tungsten plugs 144 electrically connect the selection lines 190 to the drain regions 110. It is noted that in the particular embodiment shown in FIG. 2, two NMOS transistors share each of the tungsten plugs 144. A layer of titanium silicide (not shown) may be formed on the surface of the silicon substrate to improve the conductivity between the substrate 102 and the conductive sidewall spacers 130A and 130B as well as between the substrate 102 and the conductive plugs 144. The conductive plugs 144 are electrically insulated from the gate stacks by dielectric layers 126. The first conductors 130A and 130B of memory element 103A and 103B, respectively, are electrically connected to a first region selected from the source region 110 and the drain region 112 of the corresponding metal oxide semiconductor field effect transistor. In the embodiment of FIG. 2 the first region is the drain region 112. The second conductor 270 of each memory element 103A and 103B is electrically connected to the output line 271, which may comprise, e.g., the same material as the second conductor 270. A second region of the corresponding metal oxide semiconductor field effect transistor which is selected from the source region 110 and the drain region 112 and which is not in contact with the first region, is electrically connected to one of the N first selection lines 190. The gate region 116 is electrically connected to one of the M second selection lines 120. In an alternative embodiment, the electric device has a structure as shown in any of the Figures of WO-A1-02/09206 or as disclosed in the description of WO-A1-02/09206. The electric device according to the invention is advantageously used in an electric apparatus such as, e.g. a computer, a television receiver or a mobile phone, comprising a processor for, e.g. data processing, to which processor a memory is coupled for storing information. The electric apparatus further comprises a display coupled to an output terminal. In summary, the electric device 1, 100 has a body 2, 101 with a resistor 7, 250 comprising a phase change material being changeable between a first phase and a second phase. The resistor 7, 250 has an electrical resistance which depends on whether the phase change material is in the first phase or the second phase. The resistor 7, 250 is able to conduct a current for enabling a transition from the first phase to the second phase. The phase change material is a fast growth material which may be a composition of formula Sb1-cMc, with c satisfying 0.05≦c≦0.61, and M being one or more elements selected from the group of Ge, In, Ag, Ga, Te, Zn and Sn, or a composition of formula SbaTebX100-(a+b), with a, b and 100-(a+b) denoting atomic percentages satisfying 1≦a/b≦8 and 4≦100-(a+b)≦2, and X being one or more elements selected from Ge, In, Ag, Ga and Zn. It should be noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the appended claims. In the claims, any reference signs placed between parentheses shall not be construed as limiting the claim. The word “comprising” does not exclude the presence of elements or steps other than those listed in a claim. The word “a,” or “an” preceding an element does not exclude the presence of a plurality of such elements.
20050615
20140715
20060309
77251.0
H01L2902
0
LEE, EUGENE
ELECTRIC DEVICE COMPRISING PHASE CHANGE MATERIAL
UNDISCOUNTED
0
ACCEPTED
H01L
2,005
10,539,299
ACCEPTED
Self-propelled vehicle, in particular a road-building machine and a method for driving and controlling a vehicle with the aid of a rotatable driver seat
The inventive self-propelled vehicle, in particular a road-building machine, comprises a traction drive, a steering device and a rotatable driver seat (5) in which a traction drive control unit (6) is arranged. Adjustment signals for the traction drive are generated according to the direction of the adjustment of the control elements of said control unit (6). Said road-building machine also comprises a device for detecting the rotation angle μ of the instant rotating position of the seat and for correcting the directional components of the adjustment signals of the control elements to a −μ angle in such a way that the direction of the adjustment thereof corresponds to the direction of the vehicle motion at each rotating position of the seat.
1-9. (canceled) 10. A self-propelled vehicle, in particular a road-building machine, comprising: a driver's cab arranged on a chassis (4), a traction drive, a steering means, a rotatable driver's seat (5) provided in the driver's cab with an integrated control unit (6) for the driving operation, which generates actuation signals for the traction drive and the steering means in dependence on the direction of actuation of control elements of the control unit (6), characterized in that means detect the instantaneous rotation angle μ of the rotational position of the seat and correct the direction components of the actuation signals of the control elements by an angle −μ such that the direction of actuation of the control elements corresponds to the direction of movement of the vehicle in any rotational position of the seat. 11. The self-propelled vehicle as defined in claim 10 wherein the means for detecting the instantaneous rotation angle μ of the rotational position of the seat transmits the rotation angle μ mechanically, electromechanically, optically or electrically to the control elements of the control unit (6). 12. The self-propelled vehicle as defined in claim 10 wherein, in the control unit (6), the actuation signals for the traveling direction and the steering may be continuously corrected in dependence on the rotation angle μ of the instantaneous rotational position of the seat. 13. The self-propelled vehicle as defined in claim 11 wherein, in the control unit (6), the actuation signals for the traveling direction and the steering may be continuously corrected in dependence on the rotation angle μ of the instantaneous rotational position of the seat. 14. The self-propelled vehicle as defined in claim 10, wherein the control unit (6) comprises a single control lever (8) as the control element for the selection of the traveling direction, the traveling speed and the steering. 15. The self-propelled vehicle as defined in claim 11, wherein the control unit (6) comprises a single control lever (8) as the control element for the selection of the traveling direction, the traveling speed and the steering. 16. The self-propelled vehicle as defined in claim 12, wherein the control unit (6) comprises a single control lever (8) as the control element for the selection of the traveling direction, the traveling speed and the steering. 17. The self-propelled vehicle as defined in claim 14 wherein the control lever (8) is supported in a universal joint (28) and the universal joint (28) rests on a turnover (26) rotatable about a rotation angle −μ when the rotational position of the driver's seat (5) assumes a rotation angle μ. 18. The self-propelled vehicle as defined in claim 10 wherein the vehicle has two steerable axes and wherein, at the control unit (8), the steering control may be switched to one of both axes or to both axes. 19. The self-propelled vehicle as defined in claim 14 wherein the control lever (8) is guided in two mutually orthogonal slotted links (24). 20. The self-propelled vehicle as defined in claim 17 wherein the control lever (8) is guided in two mutually orthogonal slotted links (24). 21. The self-propelled vehicle as defined in claim 18 wherein the control lever (8) is guided in two mutually orthogonal slotted links (24). 22. The self-propelled vehicle as defined in claim 10 wherein the vehicle is a road roller (1). 23. A method for driving and steering a vehicle, in particular a road-building machine, with a rotatable driver's seat (5) provided in a driver's cab and a control unit (6) for the driving operation which is integrated in the driver's seat (5) and comprises control elements, characterized by the detection of the instantaneous rotation angle μ of the rotational position of the seat and the continuous correction of the actuation signals of the control elements by an angle −μ, such that the direction of actuation of the control elements corresponds to the direction of movement of the vehicle in any rotational position of the seat.
BACKGROUND OF THE INVENTION Self-propelled vehicle, in particular a road-building machine and a method for driving and controlling a vehicle with the aid of a rotatable driver seat The invention refers to a self-propelled vehicle according to the preamble of claim 1 and to a method according to the preamble of claim 9. Such vehicles that have a rotatable driver's seat are known, for example, from road-building machines and in particular from road rollers. It is a requirement with road rollers to develop a driver's seat that is freely rotatable around its vertical axis, since the operational conditions of a roller require a continuous change of the seat position of the operator relative to the travelling direction of the road roller. A prerequisite for a feasibility in terms of costs and functionality is that the control elements rotate with the driver's seat. Otherwise, a plurality of redundant control elements would have to be used, which would be expensive. Typically, an asphalt roller, for example, works behind a paver that places the material and performs a pre-compaction. The roller travels several times over the surfaces laid by the paver to provide the final compacting and the planarity of the surface. In doing so, the direction of travel is changed frequently—the number of forward and backward travels is almost equal. To provide for or improve upon the visibility of the working area, the security and the ergonomics of the operation of the machine, it is necessary to rotate the driver's seat by 180° every time the direction of travel is changed. Here, the roller may cab still on the hot asphalt only for the short duration taken by the change of the travelling direction. Therefore and for reasons of time, the driver's seat should be rotated while driving. For respective short distances with different travelling directions, a seat position rotated by 90° relative to the travelling direction is feasible. Depending on the course to be travelled, seat positions between 0 and 90° relative to the travelling direction may also be ergonomically feasible. For a safe operation of the machines, the essential control elements, such as travelling direction transmitters (steering wheel, joystick) and drive lever, for selecting the travelling direction and the speed must be associated with the travelling direction in a manner unambiguous to the operator. Existing systems do not solve this problem. Accordingly, a free rotation of the driver's seat including the control elements while the roller travels—which is feasible in terms of application technology—was hereinbefore impossible. EP 0935025 describes a system with a rotatable driver's seat, wherein the driving operation is controlled dependent on the rotational position of the driver's seat such that a control device reverses the direction of the drive presettings when the driver's seat is swivelled into a preset region. However, this reversal can only be effected with the roller at cabstill. Would the roller be travelling, rotating the driver's seat could for instance cause a reversal of the travelling direction of the roller that might not be intended by the driver. From EP 0935023 A2, a method for a roller with two steerable drums that comprises a control device controlling the steering drive of both drums such that the respective front drum, seen in the travelling direction, is automatically controlled as the active drum through the steering presettings. Again, this method does not solve the problem of the sense of direction of the control elements when the seat position changes during travel. SUMMARY OF THE INVENTION It is an object of the present invention to improve a self-propelled vehicle with a rotatable driver's seat of the above mentioned type, as well as a method for driving and steering a vehicle with a rotatable driver's seat such that the association of the travelling direction of the control elements with the travelling direction of the vehicle is maintained in any rotation angle position of the driver's seat. The object is solved with the features of claim 1 and 9, respectively. The invention advantageously provides that, in a control unit for the driving operation which generates actuation signals for the drive and the steering means in dependence on the direction of actuation of the control elements of the control unit, a means detects the instantaneous rotation angle μ of the rotational position of the seat and corrects the direction of the actuation signals of the control elements by an angle −μ such that the direction of actuation of the control elements corresponds to the travelling direction of the vehicle in any rotational position of the seat. The invention advantageously allows that the control elements of the control unit always maintains a direction of actuation that corresponds to the travelling direction of the machine, even if the driver's seat is rotated during traction drive. Thus, the driver's seat is freely rotatable during travel without having to interrupt the driving operation. The means for detecting the instantaneous rotation angle of the rotational seat position transmits the rotation angle mechanically, electro-mechanically, optically or electrically to the control unit. Transmitting the rotation angle to the elements allows to correct the actuation signals generated by the control elements of the control unit by a value corresponding to the rotation angle of the driver's seat so that a change of the rotational position of the seat has no influence on the direction of actuation. The direction of actuation of the control elements is thus always the same and corresponds to the travelling direction of the vehicle. In the control unit, the actuation signals for the selection of the travelling direction and the steering are continuously corrected in dependence on the rotation angle of the instantaneous rotational position of the seat. The continuous correction of the direction of the actuation signals allows for a free optional rotation of the driver's seat during travel. The control unit comprises a single control lever for the selection of the travelling direction, the travelling speed and the steering. The control lever is supported by a universal joint provided on a turnover that may be rotated by an angle −μ when the driver's seat takes a seat position under an angle of μ. The transmission of the rotation angle to the control unit may be effected, for example, using a flexible transmission shaft, an electromotor drive or a torsion bar. The housing of the control unit is preferably connected with the driver's seat in a stationary manner. The vehicle may have two steerable axes, the steering control being adapted to switch the control lever to one of the two axes or to both axes. Preferably, the control lever is guided in two mutually orthogonal slotted links. The vehicle is a road-building machine, preferably a road roller. The following is a detailed description of an embodiment of the invention with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 illustrates a road roller with a rotatable driver's seat according to prior art. FIG. 2 is a view similar to FIG. 1 with the travelling direction being reversed. FIG. 3 illustrates the actuation direction of the control lever according to the invention. FIG. 4 shows the present control lever of the control unit. FIGS. 5 and 6 illustrate different rotational positions of the driver's seat. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIGS. 1 to 3 schematically illustrate a road roller 1 with two roller drums 2, 3, at least one of which is steerable. The roller drums are interconnected through a chassis 4 on which a driver's cab for an operator is arranged. The driver's cab is provided with a rotatable driver's seat 5 with an integrated control unit for the drive operation. The control unit 6 preferably comprises a control lever 8 whose functions will be detailed in connection with FIG. 4. FIG. 1 illustrates a road roller 1 with at least one steerable drum 2. The drum steered is the front drum 2, seen in the travelling direction. In the left portion of the Figure, the position of the seat is aligned with the travelling direction. In this case, turning the steering wheel 7 to the left causes a change of the travelling direction towards the left, the drive lever 9 is deflected in the travelling direction of the road roller 1. When the driver's seat, including the control unit 6, is swivelled by 90° to the left or the right (middle portion of the Figure), it is already impossible to unambiguously associate the direction of actuation at the control elements of the control unit to the travelling direction. When the seat position is rotated by 180° while the travelling direction remains the same (right portion of the Figure), the direction of the actuation of the control elements does not correspond to the travelling direction. Consequently, the machine cannot be operated safely. FIG. 2 illustrates the same situation, but with the travelling direction changed. Again, swivelling the driver's seat results in a loss of association between the travelling direction of the road roller and the respective direction of actuation of the control elements drive lever 9 and steering wheel 7. FIG. 3 describes the solution underlying the invention, which integrates the drive lever 9 and, preferably, the steering function in one control lever. In the case illustrated, the control lever 8 is deflected in the direction of the arrow (20) and remains in this position—the machine travels in the direction of the arrow. Moving the control lever 8 in the direction of the arrow (18) causes a steering motion of the drum—the machine travels to the left. When the driver's seat is rotated by 90° during travel, the control lever 8 is tracked such that its sense of deflection still corresponds to the travelling direction. The direction of movement of the control lever 8 for steering corresponds to the direction of movement of the road roller 1. The same is true for the rotation of the driver's seat 5 by 180°. The driver's seat 5 may further be rotated freely by more than 180°. FIG. 4 illustrates the control unit 6 with its components, the control functions and the device for transmitting the rotary motion of the driver's seat 5 to the control unit. The control lever 8 comprises switching means 10 for the functions of lifting and lowering the edge pressing device, a switch means 12 for the rear wheel steering or dog's movement, a switch means 14 for turning vibration on and off, a switch means 16 for unlocking the immobilizer, as well as a switch means 18 with two degrees of freedom for the setting of the steering direction and a switch means 20 for the travelling direction. To make it easier on the operator to differentiate between a steering motion and a travelling motion during the deflection of the control lever, the steering motion is actuated against a spring force towards the neutral position and the travelling deflection is actuated against a friction force. Preferably, the essential mentioned control functions are integrated in one control unit 6. The housing 22 is fixedly connected to the driver's seat 5. Deflecting the control lever 8 in the direction of travel or steering causes a deflection of the respective slotted link (not illustrated in the drawings) for the travelling or steering motion, respectively. The slotted link for the travelling motion slides on the turnover 26 that also limits the outer position thereof. Shifted by 90°, the steering motion slides on the slotted link for the travelling motion. In the upper portion, the control lever 8 is guided by a universal joint 28. In the embodiment illustrated, the rotary motion of the driver's seat 5 about its vertical axis is transmitted to the turnover 26 through a flexible shaft 30 acting as a transmission shaft. The rotary motion may also be transmitted by an electromotor or through a torsion bar. Swivelling the driver's seat 5 by an angle μ causes a turning of the turnover 26 in the housing 22 about an angle −μ (same value of the rotation angle, but different sign). Together with the turnover 26, the slotted links for the travelling and the steering motion turn. Thus, the association of the direction of actuation of the control lever 8 with the travelling direction of the road roller 1 is guaranteed. The deflection of the control lever 8 for steering and travelling is detected by two potentiometers 32 (direction x) and 34 (direction y) in the universal joint 28 (pivot point of the control lever 8). A third potentiometer 36 is mounted below the turnover 26 on the axis of rotation thereof, measuring the rotation angle of the turnover 26 relative to the housing 22 and thus the seat position. The potentiometers 32 and 34 are connected to the housing 22 in a manner secured against rotation, i.e. swivelling the driver's seat 5 changes the association of the respective potentiometer 32 and 34 to the deflection of the drive lever. For example, in the initial position of the seat, the steering deflection of the control lever 8 is detected for 100% by the potentiometer 34. Swivelling the driver's seat 5 causes a change of the position of the control lever 8 relative to the potentiometers—i.e., the twisting of the universal joint 28 in its two axes changes. Corresponding to the rotation angle of the seat measured by the rotation angle potentiometer, the steering deflection of the control lever 8 is then sensed in part by both potentiometers 32, 24 in the directions x and y. Since the rotation angle μ is known, the resulting signal can be calculated. The signal portion of the potentiometers 32, 34 in the directions x and y, which changes with the swivelling of the seat, and the association of the control lever 8 to the seat position is illustrated in FIGS. 5 and 6. FIG. 5 schematically illustrates four different seat positions of the seat 5, shifted by 90° each, with the corresponding control unit 6. For each respective seat position, direction arrows illustrate in which direction the control lever 8 has to be moved for the functions indicated. It is evident from the illustration that the direction of actuation of the control lever 8 remains the same in all seat positions. FIG. 6 also illustrates the direction of actuation of the control lever 8, the arrow representing the direction for forward travel in all seat positions.
<SOH> BACKGROUND OF THE INVENTION <EOH>Self-propelled vehicle, in particular a road-building machine and a method for driving and controlling a vehicle with the aid of a rotatable driver seat The invention refers to a self-propelled vehicle according to the preamble of claim 1 and to a method according to the preamble of claim 9 . Such vehicles that have a rotatable driver's seat are known, for example, from road-building machines and in particular from road rollers. It is a requirement with road rollers to develop a driver's seat that is freely rotatable around its vertical axis, since the operational conditions of a roller require a continuous change of the seat position of the operator relative to the travelling direction of the road roller. A prerequisite for a feasibility in terms of costs and functionality is that the control elements rotate with the driver's seat. Otherwise, a plurality of redundant control elements would have to be used, which would be expensive. Typically, an asphalt roller, for example, works behind a paver that places the material and performs a pre-compaction. The roller travels several times over the surfaces laid by the paver to provide the final compacting and the planarity of the surface. In doing so, the direction of travel is changed frequently—the number of forward and backward travels is almost equal. To provide for or improve upon the visibility of the working area, the security and the ergonomics of the operation of the machine, it is necessary to rotate the driver's seat by 180° every time the direction of travel is changed. Here, the roller may cab still on the hot asphalt only for the short duration taken by the change of the travelling direction. Therefore and for reasons of time, the driver's seat should be rotated while driving. For respective short distances with different travelling directions, a seat position rotated by 90° relative to the travelling direction is feasible. Depending on the course to be travelled, seat positions between 0 and 90° relative to the travelling direction may also be ergonomically feasible. For a safe operation of the machines, the essential control elements, such as travelling direction transmitters (steering wheel, joystick) and drive lever, for selecting the travelling direction and the speed must be associated with the travelling direction in a manner unambiguous to the operator. Existing systems do not solve this problem. Accordingly, a free rotation of the driver's seat including the control elements while the roller travels—which is feasible in terms of application technology—was hereinbefore impossible. EP 0935025 describes a system with a rotatable driver's seat, wherein the driving operation is controlled dependent on the rotational position of the driver's seat such that a control device reverses the direction of the drive presettings when the driver's seat is swivelled into a preset region. However, this reversal can only be effected with the roller at cabstill. Would the roller be travelling, rotating the driver's seat could for instance cause a reversal of the travelling direction of the roller that might not be intended by the driver. From EP 0935023 A2, a method for a roller with two steerable drums that comprises a control device controlling the steering drive of both drums such that the respective front drum, seen in the travelling direction, is automatically controlled as the active drum through the steering presettings. Again, this method does not solve the problem of the sense of direction of the control elements when the seat position changes during travel.
<SOH> SUMMARY OF THE INVENTION <EOH>It is an object of the present invention to improve a self-propelled vehicle with a rotatable driver's seat of the above mentioned type, as well as a method for driving and steering a vehicle with a rotatable driver's seat such that the association of the travelling direction of the control elements with the travelling direction of the vehicle is maintained in any rotation angle position of the driver's seat. The object is solved with the features of claim 1 and 9 , respectively. The invention advantageously provides that, in a control unit for the driving operation which generates actuation signals for the drive and the steering means in dependence on the direction of actuation of the control elements of the control unit, a means detects the instantaneous rotation angle μ of the rotational position of the seat and corrects the direction of the actuation signals of the control elements by an angle −μ such that the direction of actuation of the control elements corresponds to the travelling direction of the vehicle in any rotational position of the seat. The invention advantageously allows that the control elements of the control unit always maintains a direction of actuation that corresponds to the travelling direction of the machine, even if the driver's seat is rotated during traction drive. Thus, the driver's seat is freely rotatable during travel without having to interrupt the driving operation. The means for detecting the instantaneous rotation angle of the rotational seat position transmits the rotation angle mechanically, electro-mechanically, optically or electrically to the control unit. Transmitting the rotation angle to the elements allows to correct the actuation signals generated by the control elements of the control unit by a value corresponding to the rotation angle of the driver's seat so that a change of the rotational position of the seat has no influence on the direction of actuation. The direction of actuation of the control elements is thus always the same and corresponds to the travelling direction of the vehicle. In the control unit, the actuation signals for the selection of the travelling direction and the steering are continuously corrected in dependence on the rotation angle of the instantaneous rotational position of the seat. The continuous correction of the direction of the actuation signals allows for a free optional rotation of the driver's seat during travel. The control unit comprises a single control lever for the selection of the travelling direction, the travelling speed and the steering. The control lever is supported by a universal joint provided on a turnover that may be rotated by an angle −μ when the driver's seat takes a seat position under an angle of μ. The transmission of the rotation angle to the control unit may be effected, for example, using a flexible transmission shaft, an electromotor drive or a torsion bar. The housing of the control unit is preferably connected with the driver's seat in a stationary manner. The vehicle may have two steerable axes, the steering control being adapted to switch the control lever to one of the two axes or to both axes. Preferably, the control lever is guided in two mutually orthogonal slotted links. The vehicle is a road-building machine, preferably a road roller. The following is a detailed description of an embodiment of the invention with reference to the drawings.
20050616
20081028
20060601
75416.0
B60K2600
0
COKER, ROBERT A
SELF-PROPELLED VEHICLE, IN PARTICULAR A ROAD-BUILDING MACHINE AND A METHOD FOR DRIVING AND CONTROLLING A VEHICLE WITH THE AID OF A ROTATABLE DRIVER SEAT
UNDISCOUNTED
0
ACCEPTED
B60K
2,005
10,539,490
ACCEPTED
Recording liquid, liquid cartridge, liquid discharge apparatus and method of liquid discharge
According to the present invention, an ink (2) containing an EO adduct of a dihydric alcohol, having a hydrocarbon group with 9 or less carbon atoms and having an I/O ratio ranging between 1 and 1.37, is supplied via nozzles (42a) in the form of liquid droplets i onto a recording paper sheet P, so that fine bubbles may be suppressed from being generated in the ink (2) to prevent emission defects such as non-emission or warped emission, and hence a high quality image free of blurring or white spots may be produced.
1. A recording liquid deposited on a support in the state of liquid droplets for recording thereon, comprising a dyestuff; a solvent for dispersing said dyestuff; and an ethylene oxide adduct of a a dihydric alcohol, containing a hydrocarbon group with 9 or less carbon atoms and having a ratio I/V of an inorganic value (IO) to an organic value (OV) not less than 1 and not larger than 1.37. 2. The recording liquid according to claim 1 wherein said ethylene oxide adduct of a dihydric alcohol at least includes a branched hydrocarbon group. 3. The recording liquid according to claim 1 wherein said ethylene oxide adduct of a dihydric alcohol includes at least one or more of organic compounds represented by the chemical formulas 1 to 3: 4. The recording liquid according to claim 1 wherein the dynamic surface tension (20) at 20 Hz is not less than 30 mN/m and wherein the dynamic surface tension (1) is not larger than 38 mN/m. 5. A liquid cartridge mounted to a liquid supply device for operating as a supply source for said recording liquid for said liquid supply device, said liquid supply device being provided to a liquid emitting device adapted for emitting the recording liquid, held in a liquid vessel, in the form of liquid droplets, and depositing the emitted ink on a support, for effecting the recording, wherein said recording liquid comprises a dyestuff, a solvent for dispersing said dyestuff and an ethylene oxide adduct of a dihydric alcohol, containing a hydrocarbon group with 9 or less carbon atoms and having a ratio I/V of an inorganic value (IO) to an organic value (OV) not less than 1 and not larger than 1.37. 6. The liquid cartridge according to claim 5 wherein said ethylene oxide adduct of a dihydric alcohol at least includes a branched hydrocarbon group. 7. The liquid cartridge according to claim 5 wherein said ethylene oxide adduct of a dihydric alcohol includes at least one or more of organic compounds represented by the chemical formulas 1 to 3: 8. The recording liquid according to claim 5 wherein the dynamic surface tension (20) at 20 Hz is not less than 30 mN/m and wherein the dynamic surface tension (1) is not larger than 38 mN/m. 9. The liquid cartridge according to claim 5 wherein said liquid vessel includes a liquid reservoir for accommodating said recording liquid, a connecting part for connecting the liquid cartridge to a liquid supply device so that, when the liquid cartridge is connected to the liquid supply device, the recording liquid contained in said liquid reservoir may be supplied to said liquid supply device, a communication port for taking in outside air in an amount corresponding to a decreased amount of the recording liquid in said liquid reservoir when the liquid cartridge is mounted on the liquid supply device and said recording liquid is supplied from said liquid reservoir to said liquid supply device, an air inlet duct for establishing communication between said liquid reservoir and the communication port for introducing air taken in via said communication port into said liquid reservoir, and a storage arranged between said communication port and the air inlet duct for storing the recording liquid flowing out from said liquid reservoir. 10. A liquid emitting device comprising emitting means including a liquid chamber for storing a recording liquid, a supply part for supplying said recording liquid to said liquid chamber, one or more pressure generating element(s) provided to said liquid chamber for thrusting said recording liquid stored in said liquid chamber, and an emitting opening for emitting said recording liquid, thrust by said pressure generating element, onto the major surface of a support from said liquid chamber as a liquid droplet; and a liquid cartridge connected to said emitting means for operating as a supply source for said recording liquid; said recording liquid comprising a dyestuff, a solvent for dispersing said dyestuff and an ethylene oxide adduct of a dihydric alcohol, containing a hydrocarbon group with 9 or less carbon atoms and having a ratio I/V of an inorganic value (IO) to an organic value (OV) not less than 1 and not larger than 1.37. 11. The liquid emitting device according to claim 10 wherein said ethylene oxide adduct of a dihydric alcohol, at least includes a branched hydrocarbon group. 12. The liquid emitting device according to claim 10 wherein said ethylene oxide adduct of a dihydric alcohol in said recording liquid includes at least one or more of organic compounds represented by the chemical formulas 1 to 3: 13. The liquid emission device according to claim 10 wherein the recording liquid has a dynamic surface tension (20) at 20 Hz not less than 30 mN/m and a dynamic surface tension (1) at 1 Hz not larger than 38 mN/m. 14. The liquid emission device according to claim 10 wherein said emitting openings of said emission means are juxtaposed in a line. 15. A liquid emitting method employing a liquid emitting device comprising emitting means including a liquid chamber for storing the recording liquid, a supply part for supplying said recording liquid to said liquid chamber, one or more pressure generating element(s) provided to said liquid chamber for thrusting said recording liquid stored in said liquid chamber, and an emitting opening for emitting said recording liquid, thrust by said pressure generating element, onto the major surface of a support from said liquid chamber as liquid droplets; and a liquid cartridge connected to said emitting means for operating as a supply source for said recording liquid; said recording liquid comprising a dyestuff, a solvent for dispersing said dyestuff and an ethylene oxide adduct of a dihydric alcohol, containing a hydrocarbon group with 9 or less carbon atoms and having a ratio I/V of an inorganic value (IO) to an organic value (OV) not less than 1 and not larger than 1.37. 16. The liquid emitting method according to claim 15 wherein said ethylene oxide adduct of a dihydric alcohol in said recording liquid at least includes a branched hydrocarbon group. 17. The liquid emitting method according to claim 15 wherein at least one or more of organic compounds represented by the chemical formulas 1 to 3: is used as said ethylene oxide adduct of the dihydric alcohol in said recording liquid. 18. The liquid emission method according to claim 15 wherein the recording liquid has a dynamic surface tension (20) at 20 Hz not less than 30 mN/m and a dynamic surface tension (1) at 1 Hz not larger than 38 mN/m. 19. The liquid emission method according to claim 15 wherein said emitting openings of said emission means are juxtaposed in a line.
TECHNICAL FIELD This invention relates to a recording liquid deposited on a support in the state of droplets for recording thereon, a liquid cartridge for holding the recording liquid, and to a liquid emitting device and a liquid emitting method for emitting the recording liquid, contained in the liquid cartridge, as droplets through an emitting opening onto the support. This application claims priority of Japanese Patent Application No. 2003-360027, filed in Japan on Oct. 20, 2003, the entirety of which is incorporated by reference herein. BACKGROUND ART As a liquid emitting device, there is an ink jet printer apparatus in which a recording liquid, or a so-called ink, is emitted via an ink emitting head to a recording paper sheet, as a support, to record an image or a letter/character thereon. The printer apparatus of the ink jet system has advantages such as low running costs, small size, and ease in printing a colored image. The ink jet system, emitting the ink via an ink emitting head, may be implemented by, for example, a deflection system, a cavity system, a thermo-jet system, a bubble-jet system (registered trademark), thermal ink jet system, a slit jet system, or a spark jet system. Based on these various operating principles, the ink is turned into fine liquid droplets, which are then emitted via emitting openings, that is, nozzles, of an ink emitting head, so as to be deposited on the sheet for recording an image or a letter/character thereon. Meanwhile, a demand is raised for the nozzles not to be stopped up with the recorded liquid used in the ink jet recording system. It has so far been felt that fine bubbles in the ink represent one of the factors possibly responsible for nozzle clogging. In the ink, a preset quantity of a gas, such as air, remains dissolved. If, with rise in temperature, the gas is lowered in solubility, the gas which may not be dissolved in the liquid is separated to form fine bubbles in the liquid. Specifically, when the ink present in an ink tank adapted for supplying the ink to e.g. an ink emitting head, in an ink duct or in an ink emitting duct rises in temperature, the gas dissolved in the liquid is released to form fine bubbles. When these fine bubbles are present in the ink emitting head, emission troubles, such as non-emission of the ink from the nozzle or warped emission of the ink, that is, the ink being emitted from the nozzle along a path offset from the intended path, are produced, with the result that printed image suffers from white spots or becomes blurred to degrade the printing quality. In the recording system in which the ink is turned into fine liquid droplets, under the action of thermal energy, and the so formed liquid droplets are emitted from the nozzle, that is, in the recording system of the thermal type or the bubble jet type, the ink is heated rapidly by a heater and emitted in the form of liquid droplets under the pressure of air bubbles generated by film boiling of the ink. Thus, heat is accumulated in the vicinity of the heater, and hence the ink in the ink duct is extremely liable to be raised in temperature, with the result that emission troubles, such as the aforementioned non-emission or warped emission, tend to be produced to a pronounced extent. For combating such problem, it is proposed in e.g. the JP Patent Publications 1 and 2 to use an aqueous pigment ink doped with a propylene oxide adduct polymer of lower alcohol. However, these proposals are not up to sufficient suppression of fine bubbles and further improvement has been desired. It has also been proposed in Patent Publication 3 to add an ethylene oxide adduct of a higher dehydrate alcohol alkoxylate in an aqueous pigment ink. The ink proposed in this Patent Publication 3 is alleged to be superior in emission stability during high frequency driving, penetrability to the recording paper sheet and in drying properties. However, if a compound obtained on adding only ethylene oxide to the higher alcohol a dihydric alcohol alkoxylate is contained in the ink, in association with the teaching by Patent Publication 1, it has not been possible to cope successfully with the problem of the nozzles being stopped with fine bubbles. Specifically, the ink obtained on adding 7 mol or more only of ethylene oxide undergoes vigorous foaming to cause severe nozzle clogging. On the other hand, with the ink used for the ink jet recording system, a demand has been raised not only for prohibiting nozzle clogging but also for preventing the optical density from being lowered or for preventing the boundary bleeding or speckled color mixing in all-over printing, even in case of printing on a medium grade paper sheet, such as copy paper sheet or report paper sheet, or a high grade paper sheet. For meeting the demand, it has been proposed in e.g. Patent Publication 4 to use a compound, obtained on treating a water-insoluble colorant with a high polymer material containing a sulfonic acid (sulfonate) group and/or with a high polymer material containing phosphoric acid (phosphate) group, as a colorant, and also to add a high polymer material, including a carboxylic acid (carboxylate) to the ink. It has also been proposed in Patent Publication 5 to get the ink doped with an alginic acid having a D-mannuronic acid to L-guluronic acid ratio ranging between 0.5 and 1.2. It has also been proposed in Patent Publication 6 to add at least one surfactant selected from the group of fluorine-based surfactants and silicon-based surfactants and alginates to the ink. However, neither of these Publications is sufficient to meet the aforementioned demand and further improvement has been desired. On the other hand, the aforementioned problem, related with the bubbles, occurs more pronouncedly with a printer apparatus capable of performing high-speed printing on a recording paper sheet, that is, a line-based printer apparatus having an ink emitting range substantially equal to the width of the recording paper sheet (for example, see Patent Publications 7 to 9). More specifically, with a line-based printer apparatus, having one or more rows of nozzles juxtaposed in a direction substantially at right angles to the width-wise direction of the recording paper sheet, as distinct from a serial-based printer apparatus in which an ink emitting head is scanned in a direction substantially at right angles to the feed direction of the recording paper sheet, an ink duct for conducting the ink from an ink tank is formed for traversing the feed direction of the recording paper sheet, and in which a plural number of ink emitting heads, each having a nozzle, are arrayed on one or both sides of the ink duct, the number of ink heating sites is correspondingly increased with the number of the nozzles, so that fine bubbles tend to be generated. Moreover, the ink tank is separated from the ink emitting head a long distance, whilst the structure from the ink tank to the ink emitting head is complicated to render it difficult to remove the fine bubbles generated, with the result that inconveniences ascribable to the fine bubbles occur most pronouncedly. With the line-based printer apparatus, the period of emission of liquid droplets from one nozzle line to the next is that short and hence an ink exhibiting superior penetration characteristics into the recording paper sheet needs to be used. If the ink of this sort is used for a paper sheet of medium quality, the ink exhibits the tendency to seep into the paper sheet along its depth, that is, along its thickness, with the result that the optical density tends to be lowered. In addition, if so-called color printing of emitting inks of different colors on a recording paper sheet, is to be carried out with the line-based printer apparatus, where the period of emission of liquid droplets from one nozzle line to the next is short, a color liquid droplet is deposited before the previously deposited color liquid droplet sufficiently seeps into the bulk part of the paper sheet, with the consequence that boundary bleeding or speckled color mixing in all-over printing tends to be produced between different colors. Patent Publication 1: Japanese Laid-Open Patent publication 2001-2964 Patent Publication 2: Japanese Laid-Open Patent publication H10-46075 Patent Publication 3: Japanese Laid-Open Patent publication H7-70491 Patent Publication 4: Japanese Laid-Open Patent publication 2000-154342 Patent Publication 5: Japanese Laid-Open Patent publication H8-290656 Patent Publication 6: Japanese Laid-Open Patent publication H8-193177 Patent Publication 7: Japanese Laid-Open Patent publication 2002-36522 Patent Publication 8: Japanese Laid-Open Patent publication 2001-315385 Patent Publication 9: Japanese Laid-Open Patent publication 2001-301199 DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a recording liquid whereby the aforementioned problems of the related art may be overcome. It is another object of the present invention to provide a recording liquid suffering from foaming only to a lesser extent, superior in emission stability, exhibiting high optical density in case of multi-color printing of an image or a letter/character on a paper sheet of a medium quality, as a support, and which is free from boundary bleeding or speckled color mixing in all-over printing to lend itself to high-quality printing, a liquid cartridge containing the recording liquid, and a method and a device capable of effecting high quality printing using the recording liquid contained in the liquid cartridge. The present invention provides a recording liquid deposited on a support in the state of liquid droplets for recording thereon, comprising a dyestuff, a solvent for dispersing the dyestuff, and an ethylene oxide adduct of a a dihydric alcohol, containing a hydrocarbon group with 9 or less carbon atoms and having a ratio I/V of an inorganic value (IO) to an organic value (OV) not less than 1 and not larger than 1.37. The present invention also provides a liquid cartridge mounted to a liquid supply device for operating as a supply source for the recording liquid for the liquid supply device, the liquid supply device being provided to a liquid emitting device adapted for emitting the recording liquid, held in a liquid vessel, in the form of liquid droplets, and depositing the emitted ink on a support, for effecting the recording. The recording liquid comprises a dyestuff, a solvent for dispersing the dyestuff and an ethylene oxide adduct of a dihydric alcohol, containing a hydrocarbon group with 9 or less carbon atoms and having a ratio I/V of an inorganic value (IO) to an organic value (OV) not less than 1 and not larger than 1.37. The present invention also provides a liquid emitting device comprising emitting means including a liquid chamber for storing a recording liquid, a supply part for supplying the recording liquid to the liquid chamber, one or more pressure generating element(s) provided to the liquid chamber for thrusting the recording liquid stored in the liquid chamber, and an emitting opening for emitting the recording liquid, thrust by the pressure generating element, onto the major surface of a support from the liquid chamber as liquid droplets, and a liquid cartridge connected to the emitting means for operating as a supply source for the recording liquid. The recording liquid comprises a dyestuff, a solvent for dispersing the dyestuff and an ethylene oxide adduct of a dihydric alcohol, containing a hydrocarbon group with 9 or less carbon atoms and having a ratio I/V of an inorganic value (IO) to an organic value (OV) not less than 1 and not larger than 1.37. The present invention also provides a liquid emitting method employing a liquid emitting device comprising emitting means including a liquid chamber for storing the recording liquid, a supply part for supplying the recording liquid to the liquid chamber, one or more pressure generating element(s) provided to the liquid chamber for thrusting the recording liquid stored in the liquid chamber, and an emitting opening for emitting the recording liquid, thrust by the pressure generating element, onto the major surface of a support from the liquid chamber as liquid droplets, and a liquid cartridge connected to the emitting means for operating as a supply source for the recording liquid. The recording liquid comprises a dyestuff, a solvent for dispersing the dyestuff and an ethylene oxide adduct of a dihydric alcohol, containing a hydrocarbon group with 9 or less carbon atoms and having a ratio I/V of an inorganic value (IO) to an organic value (OV) not less than 1 and not larger than 1.37. Thus, according to the present invention, in which the recording liquid contains an ethylene oxide adduct of a dihydric alcohol, having a hydrocarbon group with 9 or less carbon atoms and having a ratio I/V of an inorganic value (IO) to an organic value (OV) not less than 1 and not larger than 1.37, it becomes possible to prevent fine bubbles from being generated in the recording liquid, while it also becomes possible to prevent emission defects, such as non-emission or warped emission of the recording liquid from the emitting openings. The result is that, according to the present invention, the emission defects ascribable to fine bubbles generated in the recording liquid may be prevented to eliminate blurring or generation of white spots, and that, since the recording liquid may exhibit superior wettability for the support, it is possible to achieve high quality recording of high optical density free of boundary bleeding or speckled color mixing in all-over printing. Other objects and specified advantages of the present invention will become more apparent from the following explanation of preferred embodiments thereof especially when read in conjunction with the drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view showing a printer apparatus embodying the present invention. FIG. 2 is a perspective view showing a head cartridge provided to the printer apparatus. FIG. 3 is a cross-sectional view showing the head cartridge. FIGS. 4A and 4B show an ink supply part when an ink tank is fitted to the head cartridge, where FIG. 4A is a schematic view showing the closed state of the ink supply part and FIG. 4B is a schematic view showing the opened state of the ink supply part. FIG. 5 is a schematic view showing the relationship between the ink tank and an ink emitting head in the head cartridge. FIGS. 6A and 6B show a valving mechanism in a connecting part of the ink tank, where FIG. 6A is a cross-sectional view with a valve in the closed state and FIG. 6B is a cross-sectional view with the valve in the opened state. FIG. 7 is a cross-sectional view showing the structure of the ink emitting head. FIGS. 8A and 8B show the ink emitting head, where FIG. 8A is a schematic cross-sectional view showing the state in which an air bubble has been formed on a heater resistor and FIG. 8B is a schematic cross-sectional view showing the state in which the ink liquid droplet has been discharged from the nozzle. FIG. 9 is a partial see-through side view of the printer apparatus. FIG. 10 is a schematic block diagram showing a control circuit of the printer apparatus. FIG. 11 is a flowchart showing the printing operation of the printer apparatus. FIG. 12 is a partial see-through side view of the printer apparatus, shown with a head cap opened. BEST MODE FOR CARRYING OUT THE INVENTION Referring to the drawings, a recording liquid, a liquid cartridge, a liquid emitting device and a liquid emitting method, embodying the present invention, will be explained in detail. An ink jet printer apparatus, referred to below as a printer apparatus 1, shown in FIG. 1, emits e.g. the ink to a recording paper sheet P, running in a preset direction, for printing an image or a letter/character thereon. Also, the printer apparatus 1 is a so-called line-based printer including a plural number of ink emitting openings (nozzles) juxtaposed substantially in a line along the width of the recording paper sheet P, that is, in a direction indicated by arrow W in FIG. 1, in keeping with the printing width on the recording paper sheet P. Referring to FIGS. 2 and 3, this printer apparatus 1 includes an ink jet printer head cartridge, referred to below as a head cartridge 3, for emitting an ink 2, as a recording liquid for recording an image or a letter/character on the recording paper sheet P, and a main printer body unit 4 for loading the head cartridge 3 thereon. In the present printer apparatus 1, the head cartridge 3 may be mounted on or dismounted from the main printer body unit 4, whilst ink tanks 11y, 11m, 11c and 11k may be mounted on or dismounted from the head cartridge 3. These ink tanks are liquid cartridges containing the ink 2, and operate as ink supply sources for the head cartridge 3. With the printer apparatus 1, the ink tank 11y for yellow, the ink tank 11m for magenta, the ink tank 11c for cyan and the ink tank 11k for black, are usable. The head cartridge 3, that may be mounted on or dismounted from the main printer body unit 4, and the ink tanks 11y, 11m, 11c and 11k, that may be mounted on or dismounted from the head cartridge 3, are consumable items. With the printer apparatus 1, the recording paper sheet P, housed in a tray 55a, adapted for accommodating a stack of the plural recording paper sheets P therein, may be mounted in a tray loading unit 5, provided on the front bottom part of the main printer body unit 4, for supplying the recording paper sheets P into the inside of the main printer body unit 4. When the tray 55a is loaded on the tray loading unit 5 on the front surface of the main printer body unit 4, the recording paper sheet P is supplied by a paper sheet supplying/discharging mechanism 54 via paper sheet supply port 55 to the back surface side of the main printer body unit 4. The recording paper sheet P, forwarded to the back surface side of the main printer body unit 4, has its running direction reversed by a reversing roll 83, as later explained, and is forwarded on the upper forward running path from the back surface side towards the front side of the main printer body unit 4. Before the recording paper sheet P, forwarded from the back surface side of the main printer body unit 4 towards its front surface, is discharged from a discharge opening 56 provided in the front surface of the main printer body unit 4, printing data, corresponding to input letter/character data, entered from an information processing apparatus 69, such as a personal computer, which will be explained subsequently, is printed as letter/character on the so forwarded recording paper sheet P. The ink 2, used as a recording liquid in printing, contains a colorant material, such as various pigments or water-soluble dyes, acting as dyestuff, a solvent for dispersing the colorant material, and an ethylene oxide (EO) adduct of a dihydric alcohol with a ratio of an inorganic value (IO) to an organic valur (OV), referred to below as I/O ratio, ranging between 1 and 1.37. As the colorant material, fine particles of dyes, pigments or colored polymers, well-known in the art, may be used alone or as a mixture. In particular, the water-soluble dyes are preferred. As the water-soluble dyes, any of acidic dyes, direct dyes, basic dyes, reactive dyes or edible dyes may be selected and used, mainly from the perspective of solubility in water, coloration and color fastness. Specifically, the yellow water-soluble dyes may be enumerated by, for example, C.I. Acid Yellow 17, 23, 42, 44, 79 and 142, C.I. Food Yellow 3 and 4, C.I. Direct Yellow 1, 12, 24, 26, 33, 44, 50, 86, 120, 132, 142 and 144, C.I. Direct Orange 26, 29, 62 and 102, C.I. Basic yellow 1, 2, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 40, 41, 45, 49, 51, 53, 63, 64, 65, 67, 70, 73, 77, 87 and 91, C.I. Reactive Yellow 1, 5, 11, 13, 14, 20, 21, 22, 25, 40, 47, 51, 55, 65 and 67. The magenta water-soluble dyes may be enumerated by, for example, C.I. Acid Red 1, 8, 13, 14, 18, 26, 27, 35, 37, 42, 52, 82, 87, 89, 92, 97, 106, 111, 114, 115, 134, 186, 249, 254 and 289, C.I. Food Red, 7, 9 and 14, C.I. Direct Red 1, 4, 9, 13, 17, 20, 28, 31, 39, 80, 81, 83, 89, 225 and 227, C.I. Basic Red 2, 12, 13, 14, 15, 18, 22, 23, 24, 27, 29, 35, 36, 38, 39, 46, 49, 51, 52, 54, 59, 68, 69, 70, 73, 78, 82, 102, 104, 109 and 112, and C.I. Reactive Red 1, 14, 17, 25, 26, 32, 37, 44, 46, 55, 60, 66, 74, 79, 96 and 97. The cyan water-soluble dyes may be enumerated by, for example, C.I. Acid blue 9, 29, 45, 92 and 249, C.I, Direct Blue 1, 2, 6, 15, 22, 25, 71, 76, 79, 86, 87, 90, 98, 163, 165, 199 and 202, C.I. Basic Blue 1, 3, 5, 7, 9, 21, 22, 26, 35, 41, 45, 47, 54, 62, 65, 66, 67, 69, 75, 77, 78, 89, 92, 93, 105, 117, 120, 122, 124, 129, 137, 141, 147 and 155, and C.I. Reactive Blue 1, 2, 7, 14, 15, 23, 32, 35, 38, 41, 63, 80 and 95. The black water-soluble dyes may be enumerated by, for example, C.I. Acid Black 1, 2, 7, 24, 26 and 94, C.I. Food Black 1 and 2, C.I. Direct Black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168 and 171, and C.I. Basic Black 3, 4, 7, 11, 12 and 17. The amount of addition of the aforementioned colorant to the ink 2 ranges between 1 mass wt % to 10 mass wt %, preferably between 3 mass wt % and 5 mass wt %, to the total mass weight of the ink 2, and is determined in consideration of, for example, the viscosity, drying performance, emitting stability of coloration properties of the ink and preservation stability of the printed product. Although the ink 2 is used dissolved in water, as a solvent, it is also possible to use well-known organic solvents, either singly or in combination, for the purpose of imparting desirable physical properties to the ink 2, improving dispersibility and solubility in water of the colorant and preventing the ink 2 from drying. More specifically, the organic solvents, usable as solvents, may be enumerated by, for example, lower alcohols, such as ethanol, 2-propanol, polyhydric alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerin, 1,2,6-hexanetriol, 1,2,4-butanetriol or petriol, polyhydric alcohol alkylethers, such as ethyleneglycol monoethylether, ethyleneglycol monobuthylether, diethyleneglycol monomethylether, diethyleneglycol monoethylether, diethyleneglycol monobuthylether, tetraethyleneglycol monomethylether, or propyleneglycol monophenylether, polyhydric alcohol allylethers, such as ethyleneglycol monophenylether or ethyleneglycol monobenzylether, nitrogen-containing heterocyclic compounds, such as N-methyl-2-pyrrolidone, N-hydroxyethyl-pyrrolidone, 1,3-dimethylimidazoline, -caprolactam or -butyrolactone, amides, such as formamide, N-methyl formamide, N,N-dimethylformamide, aimes, such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine or triethylamine, and sulfur-containing compounds, such as dimethyl sulfoxide, sulfolane or thiodiethanol. The amount of addition of the aforementioned organic solvents in the ink 2 ranges between 5 mass wt % to 50 mass wt %, preferably between 10 mass wt % and 35 mass wt %, based on the total mass weight of the ink 2, and is determined in consideration of the viscosity, drying performance or emission stability of the ink 2, as in the case of the colorant. Examples of the EO adduct of the a dihydric alcohol, with a hydrocarbon group with the number of carbon atoms not larger than 9, and with the range of the I/O ratio between 1 and 37, include organic compounds shown by the chemical formulas 4 to 8, which may be used either singly or in combination: Although the reason is not clear, with the ink 2 containing the aforementioned EO adducts of the a dihydric alcohols, described above, fine bubbles may be suppressed from being generated to prevent a nozzles 42a as later explained from being stopped with the fine bubbles, with the result that failure in ink emission such as the ink not being emitted from the nozzles 42a or the ink being emitted in a direction offset from the intended direction to cause emission deviation, may be prohibited to achieve superior emission stability. Moreover, although the reason is again not clear, in the ink 2, containing the EO adduct of a dihydric alcohol, described above, the optical density of an image obtained on recording by deposition thereof on the recording paper sheet P, that is, on printing, becomes higher to suppress boundary bleeding or speckled color mixing in allover printing to achieve an image printed to high quality. Moreover, with the ink 2, containing, as the EO adduct of a dihydric alcohol with the number of carbon atoms not larger than 9 and with the I/O ratio ranging between 1 and 1.37, the EO adduct of the dihydric alcohol, with hydrocarbon groups with an iso-branching or a tert-branching, as indicated by the chemical formulas 9 to 16, the ink may further be improved in emission stability, so that a printed image obtained may be of higher quality, because the steric chemical structure of the EO adduct of the a dihydric alcohol is further deterrent to the generation of fine bubbles. In particular, as the ink 2, the compounds indicated by the chemical formulas 11 to 16 are preferably contained as the EO adduct of a dihydric alcohol with the number of carbon atoms not larger than 9 and with the I/O ratio ranging between 1 and 1.37. With the ink containing these compounds either alone or in combination, outstanding operation and effects may be produced. If, with the EO adduct of the dihydric alcohol, contained in the ink 2, the number of carbon atoms exceeds 9, the ink 2 is increased in viscosity and, depending on the content of the organic compound, the ink 2 tends to be deteriorated in penetrability into the recording paper sheet P. Meanwhile, in the EO adduct of the dihydric alcohol, the number of carbon atoms is spontaneously determined by the value of the I/O ratio. The EO adduct of a dihydric alcohol, with the number of carbon atoms not larger than 9 and with the I/O ratio ranging between 1 and 1.37, is preferably contained in an amount ranging between 0.1 mass wt % and 5 mass wt %, more preferably, in an amount ranging between 0.5 mass wt % and 3 mass wt %, based on the total mass weight of the ink 2. If the amount of content of the EO adduct of a dihydric alcohol is smaller than 0.1 mass wt %, it becomes difficult to achieve the aforementioned favorable operation and results. If conversely the amount of content of the EO adduct of a dihydric alcohol is larger than 5 mass wt %, the ink 2 tends to be higher in viscosity and deteriorated in penetrability into the recording paper sheet P. This EO adduct of a dihydric alcohol has the ratio of the inorganic value (IV) to the organic value (OV) not less than 1 and not larger than 1.37, as described above. These inorganic value (IV) and organic value (OV) may be found from discussions on an organic conceptual diagram shown e.g. in Yoshio Koda: “Systematic Organic Qualitative Analysis-Fundamentals and Application”, published by SANKYO Publishing Co. Ltd., 1984, Fujita and Akatsuka, “Systematic Organic Qualitative Analysis (for Mixtures)”, published by Kazama-Shobou (1974), Nonuhiko Kuroki, “Theoretical Chemistry on Dyes”, published by Maki-Shoten, 1966, Tobita and Uchida, “Fine Chemicals”, Maruzen (1982) and in Inoue, Uehara and Minami, “Method for Separating Organic Compounds”, published by Shoukabou, 1990. The discussions on an organic conceptual diagram are relative with a technique of grasping the physical properties of a subject organic compound by combining ‘inorganic properties’, denoting the degree of the physical and chemical properties of an organic compound by the force of electrical affinity, and ‘organic properties’, denoting the degree of the physical and chemical properties of the organic compound by the Van Der Waals force. That is, with the I/O, if the inorganic value (IV) of a given compound is increased, it is apt to be polarized to be more readily soluble in water and, if the organic value (OV) of a given compound is increased, the compound is increased in oleophilicity and lowered in solubility in water, while being more readily soluble in an organic solvent. Thus, in the EO adduct of a dihydric alcohol, contained in the ink 2, if the I/O ratio is less than 1, the compound tends to be lowered in hydrophilicity and separated in the ink 2, with the compound then forming oil droplets to deteriorate emission stability of the ink such as by clogging the nozzle 42. If conversely the I/O ratio exceeds 1.37, the EO adduct tends to be lowered in hydorphobicity to produce the tendency for generating fine bubbles in the ink 2, thus again lowering the emission stability. In the following Table 1, the inorganic values (IV), the organic values (OV) and the I/O values for the EO adducts of a dihydric alcohol, shown by the above chemical formulas 4 to 16, are shown. It is noted that the I/O values have been calculated on the basis of Table 1.1, page 13 of the aforementioned Yoshio Koda: “Systematic Organic Qualitative Analysis-Fundamentals and Application”. TABLE 1 EO adducts of a Inorganic value Organic Value dihydric alcohols (IV) (OV) I/O Compound 4 240 230 1.04 Compound 5 360 290 1.24 Compound 6 480 350 1.37 Compound 7 240 190 1.26 Compound 8 300 220 1.36 Compound 9 240 200 1.20 Compound 10 300 230 1.30 Compound 11 240 240 1.00 Compound 12 480 360 1.33 Compound 13 240 220 1.10 Compound 14 420 310 1.35 Compound 15 240 240 1.00 Compound 16 480 360 1.33 It will be seen from Table 1 that the I/O value is not less than 1 and not larger than 1.37 for the EO adducts of a dihydric alcohol, shown by the above chemical formulas 4 to 16, and, when contained in the ink 2, such adduct suppresses generation of oil droplets or fine bubbles in the ink 2, so that it is possible to prevent failure in emission, such as non-emission or deviation in emission. As the EO adducts of a dihydric alcohol, having the hydrocarbon groups with the number of carbon atoms not larger than 9, and having the I/O values ranging between 1 and 1.37, the organic compounds shown by the chemical formulas 4 to 16 are shown. The present invention is, however, not limited to these organic compounds. That is, such EO adducts of a dihydric alcohol, having the I/O values ranging between 1 and 1.37 and the hydrocarbon groups with the number of carbon atoms not larger than 9, may be used as a surfactant for the ink 2 with favorable operation and effect comparable with those of the compounds of the chemical formulas 4 to 16. In a 25° C. atmosphere, the dynamic surface tension of the ink 2 at 20 Hz (20), that is, the surface tension when air bubbles are generated every 50 msec, and that at 1 Hz (1), that is, the surface tension when air bubbles are generated every sec, are set to not less than 30 mN/m and to not larger than 38 mN/m, respectively. With the ink 2, having these values of the dynamic surface tension, the optical density becomes higher, while the boundary bleeding and speckled color mixing in all-over printing may further be suppressed. The reason is that, in conjunction with the above-described operation and effect of having contained in the ink 2 the EO adducts of a dihydric alcohol, having the hydrocarbon groups with the number of carbon atoms not larger than 9, and having the I/O values ranging between 1 and 1.37, the rate of penetration of the ink 2 into the recording paper sheet P, in other words, the spreading of the ink 2 from its deposited position along the direction of thickness and along the planar direction of the recording paper sheet P, along its pulp fibers, becomes uniform. It is noted that the dynamic surface tension may be measured by e.g. a dynamic surface tension meter produced on the basis of the known principle for measuring the dynamic surface tension as disclosed in, for example the Japanese Laid-Open Patent Publication 63-31237. For example, a dynamic bubble pressure surface tension meter, manufactured by KRUSS, capable of measuring the dynamic surface tension by the maximum bubble pressure method (Trade name: BP-2), or a dynamic surface tension measurement device, manufactured by LAUDA (trade name: MPT2), may be used. In the ink 2, the dynamic surface tension may basically be adjusted by selecting the sort of the EO adduct of the dihydric alcohol, having a hydrocarbon group with 9 or less carbon atoms and having the I/O ratio ranging between 1 and 1.37, or by adjusting the amount of the adduct to be contained in the ink 2. However, in case it is difficult to adjust the dynamic surface tension satisfactorily, it is possible to add routinely used surfactants insofar as such known surfactants are not deterrent to the operation and effect that may be accrued from the EO adduct of a dihydric alcohol having a hydroxyl group with 9 or less carbon atoms and having the value of the I/O value ranging between 1 and 1.37. Examples of the routinely used surfactants include special phenol based nonionic surfactants, such as polycyclic phenol ethoxylates, ester-based nonionic surfactants, such as ethylene oxide adducts of glyceride, polyethylene glycol oleate, polyoxyalkylene taloate, sorbitan laurylester, sorbitan oleylester, and polyoxyethylene sorbitane oleylester, amide-based non-ionic surfactants, such as coconut oil fatty acid diethanol amide, or polyoxyethylene coconut oil fatty acid diethanol amide and polyoxyethylene coconut oil fatty acid monoethanol amide, acetylene glycol and ethylene oxide adducts thereof, anionic surfactants, such as alcohol sulfate sodium salts, higher alcohol sulfate sodium salts, polyoxyethylene alkyl phenylether sulfuric acid ester ammonium salts, and alkylbenzene sulfonic acid sodium salts, cationic surfactants, such as mono long chain alkyl cation, di long chain alkyl cation or alkylamine oxide, and amphoteric surfactants, such as laurylamido propyl acetic acid betaine and laurylamino acetic acid betaine. These known surfactants may be used alone or as a mixture. The aforementioned known surfactants are added in an amount not larger than 30 mass wt % and preferably not larger than 20 mass wt %, based on the total weight of the EO adduct of a dihydric alcohol having a hydrocarbon group with 9 or less carbon atoms and having the I/O ratio value ranging between 1 and 1.37, contained in the ink 2. If the known surfactants are added in an amount exceeding 30 mass wt % of the total weight of the EO adduct of a dihydric alcohol, having a hydrocarbon group with 9 or less carbon atoms and having the I/O ratio value ranging between 1 and 1.37, the risk is high that the optical density is lowered and boundary bleeding or speckles in color mixing in all-over printing. In addition to the aforementioned colorants, solvents, EO adducts of a dihydric alcohols, functioning as a surfactant, having hydrocarbon groups with 9 or less carbon atoms and also having the I/O ratio value ranging between 1 and 1.37, and the routinely used surfactants, viscosity adjustment agents, pH adjustment agents, antiseptics, rust-proofing agents or mildew-preventatives, may also be added to the ink 2. Specifically, the viscosity adjustment agents and the pH adjustment agents may be exemplified by proteins, such as gelatin and casein, natural rubber, such as gum Arabic, cellulose derivatives, such as methyl cellulose, carboxy methyl cellulose or hydroxylmethyl cellulose, natural high polymeric materials, such as ligninsulfonates or shellac, polyacrylates, styrene-acrylate copolymer, polyvinyl alcohol and polyvinyl pyrrolidone. These may be used alone or in combination. The antiseptics, rust-proofing agents or mildew-preventatives may be exemplified by benzoic acid, dichlorophene, hexachlophene, sorbic acid, p-hydroxybenzoate and ethylene diamine tetraacetate (EDTA), these being used either alone or in combination. The above ink 2 may be prepared by mixing the aforementioned colorant, solvent and the EO adduct of a dihydric alcohol, having a hydrocarbon group with 9 or less carbon atoms and having the I/O ratio ranging between 1 and 1.37, by predetermined proportions, and by agitating and dispersing the resulting mass, such as by a screw, under heating to ambient temperature or to a temperature on the order of 40° C. to 80° C. Referring to FIGS. 2 and 3, the ink 2, prepared as described above, is accommodated in each ink tank. It is noted that the ink with a yellow color is accommodated in the ink tank 11y, the ink with a magenta color is accommodated in the ink tank 11m, the ink with a cyan color is accommodated in the ink tank 11c and the ink with a cyan color is accommodated in the ink tank 11k. The head cartridge 3, that may be mounted to and dismounted from the main printer body unit 4, making up the printer apparatus 1, and the ink tanks 11y, 11m, 11c and 11k, will now be explained with reference to the drawings. The head cartridge 3 for printing on the recording paper sheet P is loaded from the side of the upper surface of the main printer body unit 4, that is, from the direction of an arrow A in FIG. 1, and emits the ink 2 onto the recording paper sheet P, fed by the paper sheet supplying/discharging mechanism 54, in order to emit the ink 2 to effect printing. The head cartridge 3 pulverizes the ink 2 into extremely fine particles, by the pressure generated by pressure generating means of, for example the electro-thermal transducing type or an electromechanical transducing type device, to spray the ink as fine droplets onto the major surface of the support, such as the recording paper sheet P. Specifically, the head cartridge 3 includes a main cartridge body unit 21, on which are loaded the ink tanks 11y, 11m, 11c and 11k, as vessels, each of which is charged with the ink 2. In the following, the ink tanks 11y, 11m, 11c and 11k are also simply referred to as an ink tank 11. The ink tank 11, which may be mounted to and dismounted from the head cartridge 3, includes a tank vessel 12, prepared on injection molding e.g. a resin material, such as polypropylene, exhibiting strength and resistance against the ink. The tank vessel 12 is formed to a substantially rectangular shape, having a dimension substantially equal to the width-wise size of the recording paper sheet P, traveling along its longitudinal direction, for thereby increasing the capacity of the ink stored therein. Specifically, the tank vessel 12, forming the ink tank 11, is provided with an ink reservoir 13, accommodating the ink 2, an ink supplying unit 14 for supplying the ink 2 from the ink reservoir 13 into the main cartridge body unit 21 of the head cartridge 3, a series of communication ports 15 for taking in air from outside into the ink reservoir 13, an air inlet duct 16 for introducing air taken in via communication ports 15 into the ink reservoir 13, an ink storage 17 for transient storage of the ink 2 between the communication ports 15 and the air inlet duct 16, a retention lug 18 for retaining the ink tank 11 by the main cartridge body unit 21 and an engagement step 19. The ink reservoir 13, formed of a material of high air tightness, delimits a spacing in which to accommodate the ink 2. The ink reservoir 13 is formed to a substantially rectangular shape having a long-side dimension substantially equal to the width-wise size of the recording paper sheet P, traveling along its longitudinal direction, that is, along the direction indicated by arrow W in FIG. 3. The ink supplying unit 14 is provided at a mid part on the lower surface of the ink reservoir 13. This ink supplying unit 14 is a substantially protuberantly-shaped nozzle kept in communication with the ink reservoir 13. The distal end of the nozzle is fitted to a connecting part 26 of the head cartridge 3 as later explained to connect the tank vessel 12 of the ink tank 2 with the main cartridge body unit 21 of the head cartridge 3. Referring to FIGS. 4A and 4B, the ink supplying unit 14 is provided with a supply port 14b for supplying the ink 2 to a bottom surface 14a of the ink tank 11. On this bottom surface 14a, there are provided a valve 14c for opening/closing the supply port 14b, a coil spring 14d for biasing the valve 14c in a direction of closing the supply port 14b, and an opening/closing pin 14e for opening/closing the valve 14c. In a stage prior to loading the ink tank 11 to the main cartridge body unit 21 of the head cartridge 3, the supply port 14b, connected to the connecting part 26 of the head cartridge 3 for supplying the ink 2, is closed by the valve 14c being biased in a direction of closing the supply port 14b, under the bias of the coil spring 14d, as a biasing member, as shown in FIG. 4A. When the ink tank 11 is loaded on the main cartridge body unit 21, the opening/closing pin 14e is uplifted in a direction opposite to the biasing direction of the coil spring 14d, by an upper part of the connecting part 26 of the main cartridge body unit 21 forming the head cartridge 3, as shown in FIG. 4B. The opening/closing pin 14e, thus uplifted, uplifts the valve 14c, against the bias of the coil spring 14d, for opening the supply port 14b. This connects the ink supplying unit 14 of the ink tank 11 to the connecting part 26 of the head cartridge 3, for establishing communication between the ink reservoir 13 and an ink well 31 to enable the ink 2 to be supplied to the ink well 31. When the ink tank 11 is extracted from the connecting part 26 of the head cartridge 3, that is, when the ink tank 11 is dismounted from a loading part 22 of the head cartridge 3, the uplifted state of the valve 14c by the opening/closing pin 14e is canceled, such that the valve 14c is moved in the biasing direction of the coil spring 14d to close the supply port 14b. This prohibits the ink 2 from leaking from the inside of the ink reservoir 13 even in a state in which the distal end of the ink supplying unit 14 is directed downwards just before the ink tank 11 is loaded on the main cartridge body unit 21. When the ink tank 11 is extracted from the main cartridge body unit 21, the valve 14c immediately closes the supply port 14b, and hence the ink 2 may be prohibited from leaking from the distal end of the ink supplying unit 14. Referring to FIG. 3, the communication port 15 is an air take-in port for taking in air from outside the ink tank 11 into the ink reservoir 13. The communication port 15 is provided at a preset location in the upper surface of the tank vessel 12 facing the outside when the ink tank is loaded on the loading part 22, here at a mid part on the upper surface of the vessel, so that the communication port faces the outside to take in outside air even when the ink tank is mounted on the loading part 22. The communication port 15 takes in air into the ink tank in an amount corresponding to a decreased amount of the ink 2 in the ink reservoir 13 when the ink tank 11 is loaded on the main cartridge body unit 21 and the ink 2 has flown down from the ink reservoir 13 towards the main cartridge body unit 21. The air inlet duct 16 sets up communication between the ink reservoir 13 and the communication port 15 to introduce air taken in at the communication port 15 into the ink reservoir 13. Thus, even if, when the ink tank 11 is loaded on the main cartridge body unit 21, the ink 2 is supplied to the main cartridge body unit 21 of the head cartridge 3, such that the amount of the ink 2 in the ink reservoir 13 is decreased to decrease the internal pressure, air is introduced via air inlet duct 16 into the ink reservoir 13, so that the internal pressure is maintained in a state of equilibrium to assure proper supply of the ink 2 into the main cartridge body unit 21. The ink storage 17 is provided between the communication port 15 and the air inlet duct 16 for transiently storing the ink 2, so that, when the ink 2 has leaked out from the air inlet duct 16 communicating with the ink reservoir 13, the ink 2 will not flow outwards precipitously. This ink storage 17 is lozenge shaped, with the long diagonal line extending along the longitudinal direction of the ink reservoir 13. The inlet duct 16 is located at an apex point of the ink storage, lying at a lowermost point of the ink reservoir 13, that is, at the lower end of the short diagonal line of the lozenge shape, such that the ink 2 introduced from the ink reservoir 13 will again be restored into the ink reservoir 13. The communication port 15 is provided at the uppermost end of the short diagonal line of the lozenge shape such that the ink 2 introduced from the ink reservoir 13 will hardly leak to outside through the port 15. The retention lug 18 is provided on one lateral short side of the ink tank 11 and is engaged in an engagement opening 24a formed in a latch lever 24 of the main cartridge body unit 21 of the head cartridge 3. This retention lug 18 has an upper surface formed as a planar surface extending substantially at right angles to the lateral surface of the ink reservoir 13, while having a lower surface inclined from the lateral surface to the upper surface. The engagement step 19 is provided at an upper part of the ink tank 11 on the opposite lateral side with respect to the lateral side carrying the retention lug 18. The engagement step 19 is made up by an inclined surface 19a, connecting to the upper surface of the tank vessel 12, and by a planar surface 19b consecutive to the other end of the inclined surface 19a and extending substantially parallel to the upper surface of the tank vessel 12. Since the ink tank 11 is provided with the engagement step 19, the lateral surface thereof provided with the planar surface 19b is lower by one step than the upper surface of the tank vessel 12. It is by this step that the ink tank is engaged with an engagement part 23 of the main cartridge body unit 21. The engagement step 19 is provided on the inserting side lateral surface of the ink tank when the ink tank is inserted into the loading part 22 of the head cartridge 3. The engagement step is engaged with the engagement part 23 of the loading part 22 of the head cartridge 3 so as to act as a fulcrum point of rotation when the ink tank 11 is mounted on the loading part 22. The above-described ink tank 11 includes, in addition to the above component parts, a residual ink quantity detection unit for detecting the residual quantity of the ink 2 in the ink reservoir 13, and a discriminating unit for discriminating the ink tanks 11y, 11m, 11c and 11k. The head cartridge 3, on which to load the ink tanks 11y, 11m, 11c and 11k, accommodating the yellow, magenta, cyan and black inks 2, respectively, as described above, will now be explained in detail. The head cartridge 3 is made up by the aforementioned ink tank 11 and the main cartridge body unit 21, as shown in FIGS. 2 and 3. The main cartridge body unit 21 includes loading zones 22y, 22m, 22c and 22k, on which is loaded the ink tank 11. When these loading zones are denoted in their entirety, they are simply referred to below as the loading part 22. The main cartridge body unit 21 also includes the engagement part 23 and the latch lever 24 for securing the ink tank 11, a biasing member 25 for biasing the ink tank 11 in a takeout direction, the connecting part 26 connected to the ink supplying unit 14 so as to be supplied with the ink 2, an ink emitting head 27 for emitting the ink 2, and a head cap 28 for protecting the ink emitting head 27. The loading part 22, on which to load the ink tank 11, has a substantially recessed upper surface for use as an inserting/ejecting opening for the ink tank 11. In this recessed upper surface, there are arrayed the four ink tanks 11 in juxtaposition in a direction substantially perpendicular to the width of the recording paper sheet P, that is, in a direction along the feed direction of the recording paper sheet P. The loading part 22, in which is loaded the ink tank 11, is of a length elongated along the printing width, as is the ink tank 11. The ink tank 11 is housed and loaded in the main cartridge body unit 21. The loading part 22 is a zone in which the ink tank 11 is loaded, as shown in FIG. 2. The zones of the loading part, on which are loaded the ink tank 11y for yellow, the ink tank 11m for magenta, the ink tank 11c for cyan and the ink tank 11k for black, are labeled 22y, 22m, 22c and 22k, respectively. The loading zones 22y, 22m, 22c and 22k are separated from each other by partitions 22a. Meanwhile, the ink tank 11k for black is of a larger thickness in order to accommodate a larger quantity of the ink in view of the generally larger consumption of the black ink, and hence the ink tank 11k for black is larger in width than the remaining ink tanks. Consequently, the loading zone 22k is broader in width than the remaining loading zones 22y, 22m, 22c, 22k in keeping with the thickness of the ink tank 11k. The opening end of the loading part 22, on which is loaded the ink tank 11, is provided with the engagement part 23, as shown in FIG. 3. This engagement part 23 is provided at a longitudinal end of the loading part 22 so as to be engaged with the engagement step 19 of the ink tank 11. The ink tank 11 may be mounted on the loading part 22 by obliquely inserting the ink tank 11 into the loading part 22, with the engagement step 19 of the ink tank 11 first. The side of the ink tank 11 not provided with the engagement step 19 may then be rotated towards the loading part 22, with the location of engagement of the engagement step 19 of the ink tank 11 as the fulcrum point of rotation, for loading the ink tank on the loading part 22. In this manner, the ink tank 11 may readily be mounted on the loading part 22. The latch lever 24 is formed by bending a spring sheet and is provided on the lateral surface of the loading part 22 opposite to the engagement part 23, that is, on the opposite longitudinal end of the loading part 22. The proximal end of the latch lever 24 is provided as one with the bottom surface of the opposite lateral surface along the longitudinal end of the loading part 22 so that the distal end thereof is resiliently flexed in a direction towards and away from the aforementioned lateral surface. The distal end of the latch lever 24 is provided with an engagement opening 24a. The latch lever 24 is resiliently deflected the instant the ink tank 11 is mounted on the loading part 22, with the retention lug 18 of the ink tank 11 then engaging with the engagement opening 24a to prevent the ink tank 11 from becoming detached from the loading part 22 on which has been loaded the ink tank. The biasing member 25 is a spring sheet provided on the bottom surface towards the lateral surface provided with the engagement step 19 of the ink tank 11, with the spring sheet being bent for biasing the ink tank 11 in the direction of dismounting the ink tank 11. The biasing member 25 includes a top formed by bending and may be resiliently deflected in a direction towards and away from the aforementioned bottom surface, in order to thrust the bottom surface of the ink tank 11 at the top to bias the ink tank 11 loaded on the loading part 22 in a direction of being dismounted from the loading part 22. When the retention lug 18 is disengaged from the engagement opening 24a of the latch lever 24, the biasing member 25 ejects the ink tank 11 from the engagement part 23. On mid parts along the longitudinal direction of the loading zones 22y, 22m, 22c and 22k, there is provided a connecting part 26 the ink supplying units 14 of the ink tanks 11y, 11m, 11c and 11k are connected to when the ink tanks 11y, 11m, 11c and 11k are mounted to the loading zones 22y, 22m, 22c and 22k, respectively. This connecting part 26 operates as an ink supply duct for delivery of the ink 2 from the ink supplying unit 14 of the ink tank 11 mounted on the loading part 22 to the ink emitting head 27 provided to the bottom surface of the main cartridge body unit 21. Specifically, the connecting part 26 includes an ink well 31 for storing the ink 2 supplied from the ink tank 11, a sealing member 32 for sealing the ink supplying unit 14 connected to the connecting part 26, a filter 33 for removing impurities in the ink 2 and a valving mechanism 34 for opening/closing the supply duct to the ink emitting head 27, as shown in FIG. 5. The ink well 31 is a spacing connecting to the ink supplying unit 14 and in which the ink 2 is stored. The sealing member 32 is provided on the top of the ink well 31 and, when the ink supplying unit 14 of the ink tank 11 is connected to the ink well 31 of the connecting part 26, the sealing member hermetically seals the boundary between the ink well 31 and the ink supplying unit 14 in order to prevent the ink 2 from leaking to outside. The filter 33 removes dust and dirt, eventually mixed into the ink 2, such as during the mounting and the dismounting of the ink tank 11, and is provided downstream of the ink well 31. Referring to FIGS. 6A and 6B, the valving mechanism 34 includes an ink inlet duct 34a, the ink 2 is supplied to from the ink well 31, an ink chamber 34b, the ink 2 flows to from the ink inlet duct 34a, an ink effluent duct 34c, on which the ink 2 flows out from the ink chamber 34b, an opening 34d provided between the ink inlet duct 34a and the ink effluent duct 34c of the ink chamber 34b, a valve 34e for opening/closing the opening 34d, a biasing member 34f for biasing the valve 34e in the direction of closing the opening 34d, a negative pressure adjustment screw 34g for adjusting the biasing force of the biasing member 34f, a valve shaft 34h connected to the valve 34e and a diaphragm 34i connected to the valve shaft 34h. The ink inlet duct 34a is a supply duct connecting to the ink reservoir 13 for supplying the ink in the ink reservoir 13 in the ink tank 11 through the ink well 31 to the ink emitting head 27. The ink inlet duct 34a is provided for extending from the bottom side of the ink well 31 to the ink chamber 34b. The ink chamber 34b is a substantially rectangular spacing, formed as one with the ink inlet duct 34a, ink effluent duct 34c and with the opening 34d. The ink 2 flows via the ink inlet duct 34a into the ink chamber 34b to flow out through the opening 34d and the ink effluent duct 34c. The ink effluent duct 34c, supplied with the ink 2 from the ink chamber 34b through the opening 34d, connects to the ink emitting head 27. The ink effluent duct 34c extends from the bottom side of the ink chamber 34b to the ink emitting head 27. The valve 34e closes the opening 34d to separate the side of the ink inlet duct 34a and the side of the ink effluent duct 34c from each other. The valve 34e is moved in the up-and-down direction under the biasing force of the biasing member 34f, the force of restoration of the diaphragm 34i, connected to the valve shaft 34h, and under the negative pressure of the ink 2 on the side of the ink effluent duct 34c. When at the lower end of the valve stroke, the valve 34e closes the opening 34d for separating the ink inlet duct 34a and the side of the ink effluent duct 34c of the ink chamber 34b from each other for interrupting the supply of the ink 2 to the ink effluent duct 34c. When located at the lower end of the valve stroke, the valve 34e, against the bias of the biasing member 34f, the valve 34e does not separate the ink inlet duct 34a and the side of the ink effluent duct 34c of the ink chamber 34b from each other to enable the ink 2 to be supplied to the ink emitting head 27. Although there is no limitation to the sort of the material of the valve 34e, it is formed e.g. of an elastic rubber, such as elastomer, in order to assure sufficient closing characteristics. The biasing member 34f is e.g. a compression coil spring and interconnects the negative pressure adjustment screw 34g and the valve 34e between the upper surface of the valve 34e and the upper surface of the ink chamber 34b to bias the valve 34e in a direction of closing the opening 34d under its force of elasticity. The negative pressure adjustment screw 34g adjusts the biasing force of the biasing member 34f. By adjusting the negative pressure adjustment screw 34g, it is possible to adjust the biasing force of the biasing member 34f. By so doing, the negative pressure of the ink 2 for actuating the valve 34e, configured for opening/closing the opening 34d, may be adjusted by the negative pressure adjustment screw 34g, as will be explained in detail subsequently. The valve shaft 34h has its one end connected to the valve 34e and its other end to the diaphragm 34i for producing concerted movements thereof. The diaphragm 34i is a thin sheet of an elastic material connected to the opposite side end of the valve shaft 34h. The diaphragm 34i is a thin flexible sheet connected to the valve shaft 34h. This diaphragm 34i includes a major surface towards the ink effluent duct 34c of the ink chamber 34b and the opposite side major surface contacting with atmospheric air, and is elastically deflected towards the atmospheric air side and towards the ink effluent duct 34c side under the atmospheric pressure and under the negative pressure of the ink 2. In the above-described valving mechanism 34, the valve 34e is thrust for closing the opening 34d of the ink chamber 34b under the bias of the biasing member 34f and under the biasing force of the diaphragm 34i, as shown in FIG. 6A. When the ink 2 has been emitted from the ink emitting head 27, such that the negative pressure of the ink 2 in the ink chamber 34b towards the ink effluent duct 34c divided from the ink chamber by the opening 34d, is increased, the diaphragm 34i is uplifted by the atmospheric pressure under the negative pressure of the ink 2, as shown in FIG. 6B, for uplifting the valve 34e, along with the valve shaft 34h, against the bias of the biasing member 34f, as shown in FIG. 6B. At this time, the opening 34d between the ink inlet duct 34a and the ink effluent duct 34c of the ink chamber 34b is opened to supply the ink 2 from the ink inlet duct 34a towards the ink effluent duct 34c. When the negative pressure of the ink 2 is decreased, the diaphragm 34i is restored to its original shape. The biasing force of the biasing member 34f lowers the valve 34e, along with the valve shaft 34h, for closing the ink chamber 34b. Thus, in the valving mechanism 34, the above-described operation is repeated each time the ink 2 is emitted to increase its negative pressure. Moreover, with the present connecting part 26, the amount of the ink 2 in the ink reservoir 13 is decreased when the ink 2 in the ink reservoir 13 is supplied to the ink chamber 34b. At this time, the atmospheric air is introduced into the ink tank 11 from the air inlet duct 16. The air introduced into the ink tank 11 is forwarded to an upper part of the ink tank 11. This restores the state prior to emission of the ink droplets i from nozzles 42a, as later explained, to set up a state of equilibrium. In this state of equilibrium, there is scarcely no ink 2 contained in the air inlet duct 16. The connecting part 26 is of a complicated structure, as described above. It is through this complicated structure that the ink 2 is transported. Since the EO adduct of a dihydric alcohol, having a hydrocarbon group with 9 or less carbon atoms and having the I/O ratio ranging between 1 and 1.37, is contained in the ink 2, fine bubbles may be prevented from being produced in the ink 2 due to the opening/closing operation of the valve 34e or transportation of the ink 2 through ink ducts, such that the ink not admixed with bubbles may be supplied to the ink emitting head 27. The ink emitting head 27 is arranged for extending along the bottom surface of the main cartridge body unit 21, and a plurality of nozzles 42a, as ink emission ports for emitting ink droplets i, supplied from the connecting part 26, are arranged as shown in FIG. 5. Specifically, these nozzles 42a are arrayed substantially in a line along the width of the recording paper sheet P, that is, in a direction indicated by arrow W in FIG. 5, from one color to the next. A head cap 28 is a cover provided for protecting the ink emitting head 27, as shown in FIG. 2. The head cap is retreated from the ink emitting head 27 during the printing operation. The head cap 28 is provided with a pair of engagement ribs 28a on both ends along the opening/closing direction indicated by arrow W in FIG. 2, and with a cleaning roll 28b, extending along the longitudinal direction, for sucking off excess ink 2 deposited on an ink emitting surface 27a of the ink emitting head 27. The engagement ribs 28a of the head cap 28 are engaged in a pair of engagement grooves 27b, formed in the ink emitting surface 27a for extending substantially at right angles to the direction of the arrow W in FIG. 2, so that the head cap is moved for opening/closure along the short side of the ink tank 11, that is, in a direction substantially at right angles to the direction W in FIG. 2. With the head cap 28, excess ink 2 may be sucked off during the opening/closure operation, by the cleaning roll 28b being run in rotation in abutting contact with the ink emitting surface 27a of the ink emitting head 27, thereby cleaning the ink emitting surface 27a of the ink emitting head 27. This cleaning roll 28b is formed of a highly hygroscopic material, specifically, a sponge, a non-woven cloth or a woven cloth. Except during the printing operation, the head cap 28 closes the ink emitting surface 27a to prevent the ink 2 in the ink emitting head 27 from becoming dried. The above-described head cartridge 3 includes, in addition to the above component parts, a residual quantity detection unit for detecting the residual quantity of the ink 2 in the ink tank 11, and a discriminating unit for discriminating the presence/absence of the ink 2 when the ink supplying unit 14 is connected to the connecting part 26. Referring to FIG. 7, the ink emitting head 27 includes a printed circuit board 41, as a base, a nozzle sheet 42, provided with plural nozzles 42a, a film 43 for separating the printed circuit board 41 from the nozzle sheet 42 for each nozzle 42a, an ink liquid chamber 44 for pressurizing the ink 2 supplied via an ink duct 43, a resistance heater 45 for heating the ink 2 supplied to the ink liquid chamber 44, and an ink duct 46 for supplying the ink 2 to the ink liquid chamber 44. The printed circuit board 41 forms a control circuit, formed by a logic IC (integrated circuit) or a driver transistor, on a semiconductor wafer, formed e.g. of silicon, and forms an upper surface of the ink liquid chamber 44. The nozzle sheet 42 is a sheet material, with a thickness on the order of 10 to 15 μm, and is provided with the nozzle 42a, reduced in diameter towards the emitting surface 41, and having a diameter on the ink emitting surface 41 of the order of 20 μm. The nozzle sheet is arranged on the opposite side of the printed circuit board 41, with the film 43 in-between, for forming the lower surface of the ink liquid chamber 44. The film 43 is a dry film resist cured on light exposure, for example, and is formed for surrounding each film 42a except the communicating area with the ink duct 43. The film 43 is interposed between the printed circuit board 41 and the nozzle sheet 42 for forming the lateral surface of the ink liquid chamber 44. The ink liquid chamber 44, surrounded by the printed circuit board 41, nozzle sheet 42 and the film 43, forms a spacing for pressurizing the ink 2 supplied from the ink duct 43 from one nozzle 42a to the next. The resistance heater 45 is arranged on the printed circuit board 41, facing the ink liquid chamber 44, and is electrically connected to e.g. a control circuit provided to the printed circuit board 41. The resistance heater 45 is heated under control by e.g. the control circuit to heat the ink 2 within the ink liquid chamber 44. The ink duct 46 is connected to the ink effluent duct 34c of the connecting part 26 and is supplied with the ink 2 from the ink tank 11 connected to the connecting part 26 to supply the ink 2 to each ink liquid chamber 44 communicating with the ink duct 46. That is, the ink duct 46 communicates with the connecting part 26. Thus, the ink 2, supplied from the ink tank 11, flows into the ink duct 46 so as to be charged into the ink liquid chamber 44. The above-described sole ink emitting head 27 is provided with the resistance heater 45, from one ink liquid chamber 44 to the next, and includes approximately 100 to 5000 ink liquid chambers 44, provided each with the resistance heater 45, from one color ink tank 11 to the next. In the ink emitting head 27, the resistance heaters 45 of the ink liquid chambers 44 are selectively heated, under a command from a controller 68 of the printer apparatus 1, as later explained, to emit the ink 2 in the ink liquid chamber 44, associated with the heated resistance heater 45, from the nozzle 42a, associated with the ink liquid chambers 44, in the from of ink liquid droplets i. Specifically, with the ink emitting head 27, the control circuit of the printed circuit board 41 actuates the resistance heater 45, in a controlled manner, to supply the pulse current for e.g. 1 to 3 μsec to the selected resistance heater 45. By so doing, the resistance heater 45 of the ink emitting head 27 is heated quickly. Then, an air bubble b is generated in the ink 2 in the ink liquid chamber 44, contacting with the resistance heater 45, in the ink emitting head 27, as shown in FIG. 8A. In the ink emitting head 27, the air bubble b is expanded to pressurize the ink 2, with the extruded ink 2 being emitted as the ink liquid droplet i, as shown in FIG. 8B. After emission of the ink liquid droplet i, the ink 2 is supplied through the ink duct 43 into the ink liquid chamber 44, in the ink emitting head 27, so that the state prior to emission is again reached. Meanwhile, the above-described ink emitting head 27 is formed by forming the film 43 on one major surface of the printed circuit board 41, in its entirety, shaping the film 43 in keeping with the ink liquid chamber 44, and by laminating the nozzle sheet 42 thereon. With the above-described ink emitting head 27, the number of heating sites for the ink 2 is increased with the number of the resistance heaters 45, so that fine bubbles tend to be generated correspondingly. However, since the ink 2 contains the EO adducts of a dihydric alcohol having hydrocarbon groups with 9 or less carbon atoms and having the I/O ratio ranging between 1 and 1.37, it is possible to suppress fine bubbles from being produced in the ink 2 in the ink liquid chamber 44 to prevent emission troubles exemplified by non-emission or bent emission of the ink liquid droplet i. Referring to the drawings, the main printer body unit 4, forming the printer apparatus 1, on which to mount the head cartridge 3, constructed as described above, will now be explained. Referring to FIGS. 1 and 9, the main printer body unit 4 includes a head cartridge loading part 51, the head cartridge 3 is mounted to, a head cartridge holding mechanism 52 for holding and securing the head cartridge 3, a head cap opening/closing mechanism 53, a paper sheet supplying/discharging mechanism 54 for feeding/discharging the recording paper sheet P, a paper sheet feed port 55 for supplying the recording paper sheet P to the paper sheet supplying/discharging mechanism 54, and a paper sheet discharge port 56 for outputting the recording paper sheet P from the paper sheet supplying/discharging mechanism 54. The head cartridge loading part 51 is a recess in which to load the head cartridge 3. The head cartridge 3 is loaded so that the ink emitting surface 27a of the ink emitting head 27 will be substantially parallel to the paper sheet surface of the recording paper sheet P, in order to effect printing on the running recording paper sheet P in keeping with the data. There are occasions where the head cartridge 3 needs to be exchanged due to ink clogging in the ink emitting head 27. Since the head cartridge 3 is a consumable commodity, even if it does not have to be exchanged so often as the ink tank 11, the head cartridge 3 is detachably held by the head cartridge holding mechanism 52 relative to the head cartridge 3. The head cartridge holding mechanism 52 is used for detachably holding the head cartridge 3 on the head cartridge loading part 51, and is designed and constructed for holding and securing the head cartridge 3, with the head cartridge 3 pressuring against the reference surface 4a in the main printer body unit 4, with a knob 52a provided to the head cartridge 3 being retained in position by a biasing member, such as a spring, provided in a retention opening 52b of the main printer body unit 4. The head cap opening/closing mechanism 53 includes a driving unit for opening/closing the head cap 28 of the head cartridge 3. For printing, the head cap 28 is opened for exposing the ink emitting head 27 to the recording paper sheet P and, when the printing is finished, the head cap 28 is closed to protect the ink emitting head 27. The paper sheet supplying/discharging mechanism 54 includes a driving unit for transporting the recording paper sheet P. Specifically, the paper sheet supplying/discharging mechanism transports the recording paper sheet P, supplied from the paper sheet feed port 55, to the ink emitting head 27 of the head cartridge 3, and transports the recording paper sheet P, on which the ink liquid droplets i, supplied from the nozzles 42a, have been deposited, to effect the printing, to the paper sheet discharge port 56, to outside the apparatus. The paper sheet feed port 55 is an opening for supplying the recording paper sheet P to the paper sheet supplying/discharging mechanism 54, and is able to stock plural recording paper sheets P in stacked up state on e.g. a tray 55a. The paper sheet discharge port 56 is an opening through which the recording paper sheet P, on which the ink liquid droplets i have been deposited by way of printing, are discharged. A control circuit 61, shown in FIG. 10, for controlling the printing by the printer apparatus, designed and constructed as described above, will now be explained with reference to the drawings. The control circuit 61 includes a printer controller 62 for controlling the driving of the head cap opening/closing mechanism 53 and the paper sheet supplying/discharging mechanism 54 of the main printer body unit 4, an emission controller 63 for controlling e.g. the current supplied to the ink emitting head 27, associated with each color of the ink i, an alarm unit 64 for indicating the residual quantity of the ink i of each color, an input/output terminal 65 for inputting/outputting signals for an external apparatus, a ROM (Read Only Memory) 66 having recorded thereon e.g. a control program, a RAM (Random Access Memory) 67 for transiently recording e.g. a read-out control program and reading out the so recorded control program as necessary, and a controller 68 for controlling various components. The printer controller 62 actuates a driving motor of the head cap opening/closing mechanism 53, based on a control signal from the controlling 68, in order to control the head cap opening/closing mechanism for opening/controlling the head cap 28. The printer controller 62 also actuates a driving motor of the paper sheet supplying/discharging mechanism 54, based on a control signal from the controlling 68, in order to control the paper sheet supplying/discharging mechanism 54 to feed the recording paper sheet P from the paper sheet feed port 55 of the main printer body unit 4 to discharge the printed paper sheet P from the paper sheet discharge port 56 after printing. The emission controller 63 is an electrical circuit including, for example, a switching element for on/off controlling the electrical connection to an external power supply supplying the pulse current to the resistance heater 45, provided to the ink emitting head 27, a resistor for adjusting the value of the pulse current supplied to the resistance heater 45, and a control circuit for controlling the on/off switching of e.g. switching elements. The emission controller 63 adjusts the pulse current e.g. supplied to the resistance heater 45 provided to the ink emitting head 27 to control the ink emitting head 27 adapted for emitting the ink i from the nozzles 42a. The alarm unit 64 is a display means, such as LCD (liquid crystal display), and demonstrates the information exemplified by printing conditions, printing states or residual ink quantities. The alarm unit 64 may also be a voice outputting means, such as a loudspeaker, in which case the information such as the printing conditions, printing states or the residual ink quantities is output by voice. The alarm unit 64 may include the display means and the voice outputting means in combination. The alarm may be issued by, for example a monitor or a loudspeaker of an information processing device 69. The input/output terminal 65 sends the information, such as the printing conditions, printing states or the residual ink quantities, over an interface to e.g. the external information processing device 69. The input/output terminal 65 is also supplied from e.g. the information processing device 69 with printing data or with control signals for outputting the information exemplified by the above-mentioned printing conditions, printing states or the residual ink quantities. The information processing device 69 is an information processing device exemplified by e.g. a personal computer or a PDA (Personal Digital Assistant). The input/output terminal 65, connected to e.g. the information processing device 69, may use e.g. a serial parallel interface or a parallel interface, and is specifically pursuant to standards, such as USB (Universal Serial Bus), RS (Recommended Standard) 232C or IEEE (Institute of Electrical and Electronic Engineers) 1394. The input/output terminal 65 may have data communication, by a wired or wireless route, with the information processing device 69. Among the standards for wireless communication, there are, for example, the IEEE802.11a, 802.11b and 802.11g. Between the input/output terminal 65 and the information processing device 69, there may be interposed a network, such as the Internet. The input/output terminal 65 is connected in this case to a network, exemplified by LAN (Local Area Network), ISDN (Integrated Services Digital Network), xDSL (Digital Subscriber Line), FTHP (Fiber to the Home), CATV (Community Antenna TeleVision) or BS (Broadcasting Satellite), and data communication is carried out in association with various protocols, such as TCP/IP (Transmission Control Protocol/Internet Protocol). The ROM 66 is a memory, such as EP-ROM (Erasable Programmable Read-Only Memory), having stored therein a program for various processing operations carried out by the controller 68. This stored program is loaded by the controller 68 to the RAM 67. The RAM 67 stores the program as read out from the ROM 66 by the controller 68 or various states of the printer apparatus 1. The controller 68 controls various parts based e.g. on printing data supplied from the input/output terminal 65 and on data of the residual quantity of the ink 2, supplied from the head cartridge 3. The controller 68 reads out a processing program, controlling the various parts, based e.g. on the input control signal, from the ROM 66, for storage in the RAM 67, to control or process various parts based on this processing program. In the above-described control circuit 61, the processing program is stored in the ROM 66. However, the program storage medium is not limited to the ROM 66, such that a variety of other recording mediums, such as an optical disc, a magnetic disc, an MO disc or an IC card, having the processing program recorded thereon, may also be used. In this case, the control circuit 61 is connected to drives for actuating the recording mediums either directly or through the information processing device 69 for reading out the processing program from these recording mediums. The printing operation by the printer apparatus 1 will now be explained with reference to a flowchart shown in FIG. 11. It is noted that the present operation is carried out by processing operations by a CPU (central processing unit), not shown, provided in the controller 68, based on a processing program stored in a memory, such as ROM 66. First, a user issues a command, by acting e.g. on an operating panel provided on the main printer body unit 4, in order for the printer apparatus 1 to carry out the printing operation. Then, in a step S1, the controller 68 verifies whether or not the ink tank 11 of a preset color has been loaded on each loading part 22. If the ink tanks 11 of proper colors are mounted on all of the loading zones 22, the controller 68 proceeds to a step S2 and, if otherwise, the controller 68 proceeds to a step S4 to inhibit the printing operation. The controller 68 in the step S2 verifies whether or not the quantity of the ink 2 in the ink tank 11 is less than a predetermined quantity, that is, whether or not the ink tank 11 is in the ink-depleted state. If it is determined that the ink tank 11 is in the ink-depleted state, the alarm unit 64 issues an alarm to that effect and, in the step S4, the printing operation is inhibited. If conversely the quantity of the ink 2 in the ink tank 11 is above the predetermined value, that is, the ink tank is charged with the ink, the printing operation is permitted in a step S3. For carrying out the printing operation, the controller 68 causes the driving units 53, 54 to be driven in a controlled manner, by the printer controller 62, to shift the recording paper sheet P to a printing enabling position. Specifically, the controller 68 causes the actuation of the driving motor, forming the head cap opening/closing mechanism 53, to cause movement of the head cap 28 towards the tray 55a with respect to the head cartridge 3, to expose the nozzles 42a of the ink emitting head 27, as shown in FIG. 12. The controller 68 causes the driving of the driving motor, forming the paper sheet supplying/discharging mechanism 54, to cause the feed movement of the recording paper sheet P. Specifically, the controller 68 controls the paper sheet supplying/discharging mechanism 54 in such a manner that the recording paper sheet P is pulled out from the tray 55a by a paper sheet feed roll 81, the recording paper sheet P, thus pulled out, is transported by paired separating rolls 82a, 82b, rotating in opposite directions, to a direction reversing roll 83 to reverse the transport direction, the recording paper sheet P then is transported to a transport belt 84, and the recording paper sheet P, thus transported, is held at a preset position by retention means 85, to determine the position of deposition of the ink 2. The controller 68 then controls the ink emitting head 27 by the emission controller 63 and causes the ink liquid droplet i to be emitted and deposited via nozzles 42a on the recording paper sheet P, transported to the printing position, to record an image or a letter/character formed by ink dots. Since the ink 2 contains an EO adduct of a dihydric alcohol, having a hydrocarbon group with 9 or less carbon atoms and having an I/O ratio ranging between 1 and 1.37, it is possible in the ink emitting head 27 to suppress fine bubbles from being generated in the ink 2 charged into the ink liquid chamber 44, in such a manner as to prevent emission troubles, such as non-emission or warped emission of the ink liquid droplet i. Moreover, since the ink liquid droplet i deposited contains the EO adduct of a dihydric alcohol, having a hydrocarbon group with 9 or less carbon atoms and having an I/O ratio ranging between 1 and 1.37, the image or the letter/character is of a high quality with high optical density and suffers from boundary bleeding or generation of speckled mixed colors in all-over printing only to a lesser extent. When the ink liquid droplet i has been emitted from the nozzles 42a, the same quantity of the ink 2 as that emitted as the ink liquid droplet i is instantly replenished into the ink liquid chamber 44 from the ink duct 46, so that the original state is restored, as shown in FIG. 6B. When the ink liquid droplet i is emitted from the ink emitting head 27, such that the negative pressure of the ink 2 in the portion of the ink chamber 34b towards the ink effluent duct 34c with respect to the opening 34d is increased, the diaphragm 34i is uplifted by atmospheric pressure under the negative pressure of the ink 2, along with the valve shaft 34h, to uplift the valve 34e, which has so far kept the opening 34d of the ink chamber 34b closed under the bias of the biasing member 34f and the diaphragm 34i, against the bias of the biasing member 34f, as shown in FIG. 6A. The opening 34d between the ink inlet duct 34a and the ink inlet duct 34a of the ink chamber 34b is opened at this time to supply the ink 2 from the ink inlet duct 34a side to the ink effluent duct 34c side to replenish the ink 2 to the ink duct 46 of the ink emitting head 27. The negative pressure of the ink 2 is then decreased so that the diaphragm 34i is reset to its original shape by the restoring force, with the valve 34e then being lowered, along with the valve shaft 34h, such as to close the ink chamber 34b. Thus, with the valving mechanism 34, the above-described operation is repeated each time the ink liquid droplet i is emitted to raise the negative pressure of the ink 2. With the ink emitting head 27, since the ink 2 contains the EO adduct of a dihydric alcohol having hydrocarbon groups with 9 or less carbon atoms and having the I/O ratio ranging between 1 and 1.37, it is possible to suppress fine bubbles from being produced in the ink 2 in the ink liquid chamber 44, even when the ink 2 is repeatedly supplied as described above, that is, when the ink 2 is repeatedly supplied through a flow duct of a complex profile. Thu, the ink 2 free from fine bubbles may be delivered to the ink emitting head 27 to prevent emission troubles exemplified by non-emission or bent emission of the ink liquid droplet i. Consequently, the letter/character or an image consistent with printing data may be printed with superior quality on the recording paper sheet P being fed by the paper sheet supplying/discharging mechanism 54. The recording paper sheet P, on which printing has been made as described above, is then discharged via paper sheet discharge port 56 by the paper sheet supplying/discharging mechanism 54. With the above-described printer apparatus 1, in which the ink 2, containing the EO adduct of a dihydric alcohol, having a hydrocarbon group with 9 or less carbon atoms and having an I/O ratio ranging between 1 and 1.37, as surfactant, is contained in the ink tank 11, with the ink 2 being emitted as ink liquid droplet i from the nozzles 42a, it is possible to suppress fine bubbles from being produced in the ink 2 to prohibit emission troubles, with the result that the image is free from blurring or white spots and hence there may be obtained high-quality printed image or letter/character. With the present printer apparatus 1, in which the ink containing the EO adduct of a dihydric alcohol, having a hydrocarbon group with 9 or less carbon atoms and having an I/O ratio ranging between 1 and 1.37, as surfactant, is deposited on the recording paper sheet P, for printing thereon, it is possible to effect printing of an image of high quality and high optical density, suppressed in boundary bleeding or speckled color mixing in all-over printing. With the above-described head cartridge 3, the ink tank 11 may be mounted to or dismounted from the main cartridge body unit 21. However, the present invention is not limited to this configuration. That is, since the head cartridge 3 itself is a consumable item and may be mounted to or dismounted from the main printer body unit 4, the ink tank 11 may be mounted as one with the main cartridge body unit 21. In the above-described embodiment, the present invention is directed to a printer apparatus. However, the present invention is not limited to this configuration and may broadly be applied to other liquid emitting apparatus, such as facsimile machine, copying machine, an emitting apparatus for DNA chips in the liquid (see Japanese laid-Open Patent Publication 2002-34560) or to a liquid emitting apparatus for emitting a liquid containing electrically conductive particles for forming a wiring pattern for an printed circuit board. In the foregoing, the ink emitting head 27, in which the ink 2 is heated by the sole resistance heater 45, and the ink so heated is emitted, is taken as an example for explanation. However, the present invention is not limited to this configuration and may also be applied to a liquid emitting apparatus provided with emitting means having plural pressure generating elements each of which delivers discrete values or the energy at different timings to control the liquid emitting direction. Moreover, in the foregoing, such an electro-thermal conversion system, in which the ink 2 is emitted from the nozzles 42a as the ink is heated by the sole resistance heater 45, is used. This is merely illustrative and such an electromechanical conversion system may also be used in which the ink is emitted electromechanically from the nozzle by an electromechanical conversion element exemplified by a piezoelectric element. In addition, in the foregoing, a line-based printer apparatus 1 has been explained. The present invention is not limited to this configuration and may also be applied to a serial-based liquid emitting apparatus in which the ink head is moved in a direction substantially at right angles to the traveling direction of the recording paper sheet P. EXAMPLE The present invention will now be explained with reference to samples of an ink actually prepared as a recording liquid embodying the present invention. [Sample 1] In the sample 1, a magenta-based ink was first prepared. For preparing the magenta-based ink, 3 mass wt % of C.I. Acid red, as a colorant, 75 mass wt % of water, as a solvent, 10 mass wt % of glycerin, as another solvent, 5 mass wt % of 1,3-butanediol, as another solvent, 5 mass wt % of neopentyl glycol, as yet another solvent, and 1.5 mass wt % of the compound shown by the above chemical formula 4, were mixed together and filtered by a membrane filter, with a pore size of 0.22 μm (trade name: Millex-0.22), to prepare a magenta-based ink. Then, a cyan-based ink was prepared. For preparing the cyan-based ink, 2.5 mass wt % of C.I. Direct Blue, as a colorant, 76 mass wt % of water, as a solvent, 10 mass wt % of glycerin, as another solvent, 5 mass wt % of 1,3-butanediol, as another solvent, 5 mass wt % of neopentyl glycol, as yet another solvent, and 1.5 mass wt % of the compound shown by the above chemical formula 4, as a surfactant, were mixed together and filtered by a membrane filter, with a pore size of 0.22 μm (trade name: Millex-0.22), to prepare a cyan-based ink. Thus, in the sample 1, a magenta-based ink and a cyan-based ink, each containing an EO adduct of a dihydric alcohol, having a hydrocarbon group with 8 carbon atoms and having an I/O ratio of 1.04, as shown by the chemical formula 4, as the surfactant, were prepared. [Sample 2] With the sample 2, a magenta-based ink and a cyan-based ink were prepared in the same way as with the sample 1, except that the amount of addition of the EO adduct of a dihydric alcohol, shown by the chemical formula 4, as a surfactant, was set to 1 wt %. [Sample 3] With the sample 3, a magenta-based ink and a cyan-based ink were prepared in the same way as with the sample 1, except that the amount of addition of the EO adduct of a dihydric alcohol, shown by the chemical formula 4, as a surfactant, was set to 0.5 wt %. [Sample 4] With the sample 4, a magenta-based ink and a cyan-based ink were prepared in the same way as with the sample 1, except that an EO adduct of a dihydric alcohol, having a hydrocarbon group with 8 carbon atoms and having an I/O ratio of 1.24, as shown by the chemical formula 5, was used as a surfactant, in place of the organic compound shown by the chemical formula 4. [Sample 5] With the sample 5, a magenta-based ink and a cyan-based ink were prepared in the same way as with the sample 1, except that an EO adduct of a dihydric alcohol, having a hydrocarbon group with 8 carbon atoms and having an I/O ratio of 1.37, as shown by the chemical formula 6, was used as a surfactant, in place of the organic compound shown by the chemical formula 4. [Sample 6] With the sample 6, a magenta-based ink and a cyan-based ink were prepared in the same way as with the sample 1, except that an EO adduct of a dihydric alcohol, having a hydrocarbon group with 6 carbon atoms and having an I/O ratio of 1.26, as shown by the chemical formula 7, was used as a surfactant, in place of the organic compound shown by the chemical formula 4. [Sample 7] With the sample 7, a magenta-based ink and a cyan-based ink were prepared in the same way as with the sample 1, except that an EO adduct of a dihydric alcohol, having a hydrocarbon group with 7 carbon atoms and having an I/O ratio of 1.2, as shown by the chemical formula 9, was used as a surfactant, in place of the organic compound shown by the chemical formula 4. [Sample 8] With the sample 8, a magenta-based ink and a cyan-based ink were prepared in the same way as with the sample 1, except that an EO adduct of a dihydric alcohol, having a hydrocarbon group with 9 carbon atoms and having an I/O ratio of 1, as shown by the chemical formula 11, was used as a surfactant, in place of the organic compound shown by the chemical formula 4. [Sample 9] With the sample 9, a magenta-based ink and a cyan-based ink were prepared in the same way as with the sample 1, except that an EO adduct of a dihydric alcohol, having a hydrocarbon group with 8 carbon atoms and having an I/O ratio of 1.1, as shown by the chemical formula 13, was used as a surfactant, in place of the organic compound shown by the chemical formula 4. [Sample 10] With the sample 10, a magenta-based ink and a cyan-based ink were prepared in the same way as with the sample 1, except that an EO adduct of a dihydric alcohol, having a hydrocarbon group with 9 carbon atoms and having an I/O ratio of 1.04, as shown by the chemical formula 15, was used as a surfactant, in place of the organic compound shown by the chemical formula 4. [Sample 11] With the sample 11, a magenta-based ink and a cyan-based ink were prepared in the same way as with the sample 1, except that no EO adduct of a dihydric alcohol was added. [Sample 12] With the sample 12, a magenta-based ink and a cyan-based ink were prepared in the same way as with the sample 1, except that an EO adduct of a dihydric alcohol, shown by the chemical formula 17, was used in place of the organic compound shown by the chemical formula 4. [Sample 13] With the sample 13, a magenta-based ink and a cyan-based ink were prepared in the same way as with the sample 1, except that an EO adduct of a dihydric alcohol, shown by the chemical formula 18, was used in place of the organic compound shown by the chemical formula 4. [Sample 14] With the sample 12, a magenta-based ink and a cyan-based ink were prepared in the same way as with the sample 1, except that an EO adduct of a dihydric alcohol, shown by the chemical formula 19, was used in place of the organic compound shown by the chemical formula 4. [Sample 15] With the sample 15, a magenta-based ink and a cyan-based ink were prepared in the same way as with the sample 1, except that an EO adduct of a dihydric alcohol, shown by the chemical formula 20, was used in place of the organic compound shown by the chemical formula 4. [Sample 16] With the sample 16, a magenta-based ink and a cyan-based ink were prepared in the same way as with the sample 1, except that an EO adduct of a dihydric alcohol, shown by the chemical formula 21, was used in place of the organic compound shown by the chemical formula 4. The inorganic value (IO), organic value (OV) and I/O, for the EO adducts of a dihydric alcohol, shown in the above chemical formulas 17 to 21, are shown in the following Table 2. TABLE 2 EO adduct of a Inorganic value Organic value dihydric alcohol (IV) (OV) I/O Chemical formula 17 240 250 0.96 Chemical formula 18 540 380 1.42 Chemical formula 19 540 390 1.38 Chemical formula 20 240 160 1.50 Chemical formula 21 720 550 1.31 It will be seen from table 2 that the EO adducts of dhhydric alcohol, shown by the chemical formulas 17 to 20, are deviated from the range of I/O from 1 to 1.37. Thus, if the EO adduct of dhhydric alcohol, shown by the chemical formula 17, is contained in the ink, the resultant ink is lowered in hydrophilicity, with the EO adduct being separated in the ink to stop up the nozzle as oil droplets to deteriorate emission stability. On the other hand, if the EO adducts of dhhydric alcohol of the chemical formulas 18 to 20, with the I/O exceeding 1.37, are contained in the ink, the resultant ink is lowered in hydrophilicity, whilst fine bubbles tend to be generated in the ink to deteriorate the emission stability. For the magenta-based and cyan-based inks of the respective samples, evaluation was made of emission stability, intermittent emission stability, optical density, boundary bleeding and speckled color mixing in all-over printing. Meanwhile, emission stability was evaluated as follows: The inks of the respective samples were charged into respective ink tanks and mounted on the head cartridge. After emitting the inks by the line-based ink jet printer apparatus, the head cartridge was transiently dismounted from the ink jet printer apparatus and was preserved in an atmosphere of the temperature of 10° C. and the relative humidity of 50% for five days and then in an atmosphere of the temperature of 40° C. and the relative humidity of 50% for five days so as to be exposed to an environment of the temperature of 20° C. and the relative humidity of 50%. The head cartridge was then mounted again on the line-based ink jet printer apparatus and a preset area of a copy paper sheet manufactured by RICOH (trade name: My Paper) was coated in its entirety, from one color to the next, by way of a so-called all-over printing. The ink tanks were then dismounted from the head cartridge and visual check was then conducted as to whether or not fine bubbles have not been generated in the ink emission head. The image printed was also visually checked. The intermittent emission stability was evaluated by the following method. The inks of respective samples were charged in ink tanks which were then loaded on the head cartridge. The inks were emitted by a line-based ink jet printer apparatus and the head cartridge was transiently dismounted from the ink jet printer apparatus. With the emitting surface of the head cartridge exposed to outside, the head cartridge was allowed to stand stationarily for seven minutes at a temperature of 30° C. and an RH of 10%. The head cartridge was then mounted on the line-based ink jet printer apparatus and all-over printing was then carried out for each color on copy sheets manufactured by RICOH (trade name: MyPaper). A visual check was then conducted of the printed images. The optical density was measured by the following method. The inks of the respective samples were charged in the ink tanks and loaded on the head cartridge. All-over printing was then carried out for each color on copy sheets manufactured by RICOH (trade name: MyPaper) and reflection optical density was measured by an optical density meter, manufactured by MACBETH (trade name: TR924). The boundary bleeding was measured by the following method. The inks of the respective samples were charged in the ink tanks and loaded on the head cartridge. Then, all-over printing was carried out for each color on copy sheets manufactured by RICOH (trade name: MyPaper), with the respective colors lying adjacent to one another. The bleeding state at the boundaries of the colors in the printed image was then visually checked. Evaluation of speckled color mixing in all-over printing was evaluated by the following method. The ink samples were charged in the respective ink samples and loaded on the head cartridge. All-over printing was carried out with blue color several times so that the blue color of each printing will overlap and the evenness of the blue color density, that is, the possible presence of irregular color, in the printed image, was visually checked. The emission stability, intermittent emission stability, optical density, boundary bleeding and speckled color mixing in all-over printing for the respective samples are shown in the following Table 3: TABLE 3 EO adduct of dihydric alcohol Number of Color C atoms of Sort of Intermittent mixing in hydrocarbon hydrocarbon Emission emission Optical Boundary allover Sort I/O group group stability stability density bleeding printing Sanple 1 Chemical 1.04 8 Straight- 1.12 formula 4 chained Sanple 2 Chemical 1.04 8 Straight- 1.21 ⊚ ⊚ formula 4 chained Sanple 3 Chemical 1.04 8 Straight- 1.15 formula 4 chained Sanple 4 Chemical 1.24 8 Straight- 1.15 formula 5 chained Sanple 5 Chemical 1.37 8 Straight- 1.14 formula 6 chained Sanple 6 Chemical 1.26 6 Straight- 1.15 formula 7 chained Sanple 7 Chemical 1.20 7 Branched ⊚ 1.23 ⊚ ⊚ formula 9 Sanple 8 Chemical 1 9 Branched ⊚ 1.23 ⊚ ⊚ formula 11 Sanple 9 Chemical 1.10 8 Branched ⊚ 1.23 ⊚ ⊚ formula 13 Sanple 10 Chemical 1.04 9 Branched ⊚ ⊚ 1.24 ⊚ ⊚ formula 15 Sanple 11 — — — — X Δ 1.01 X X Sanple 12 Chemical 0.96 9 Straight- Δ 1.1 Δ formula 17 chained Sanple 13 Chemical 1.42 8 Straight- X Δ 1.1 Δ Δ formula 18 chained Sanple 14 Chemical 1.38 9 Branched Δ 1.19 Δ formula 19 Sanple 15 Chemical 1.5 5 Branched X Δ 1.2 Δ Δ formula 20 Sanple 16 Chemical 1.31 12 Straight- Δ Δ 1.11 Δ Δ formula 21 chained As for emission stability in Table 3, a symbol ⊚ indicates that there are no white spots in the entire image and that no fine bubbles are generated in the ink in the ink emission head, a symbol indicates that the image quality is not of a problem but there is slight white spot in the image and a minor quantity of bubbles are generated in the ink in the ink emission head, a symbol Δ indicates that a minor quantity of bubbles are generated in the ink in the ink emission head, and a symbol x indicates that there is white spot responsible for degrading the image quality and a large quantity of fine bubbles are generated in the ink in the ink emission head. As for intermittent emission stability in Table 3, a symbol indicates that the image is clear and free of blurring, a symbol indicates that the image suffers from slight blurring and a symbol X indicates that the entire image is blurred and the image quality is severely degraded. As for boundary bleeding in Table 3, a symbol ⊚ indicates that there is no bleeding of each color at the boundary, a symbol indicates that image quality is not of a problem but that there is a minor quantity of bleeding for each color at the boundary, a symbol indicates that there is bleeding of each color on the boundary degrading the image quality and a symbol x indicates that that there is bleeding of each color on the entire boundary significantly degrading the image quality. As for speckled color mixing in all-over printing in Table 3, a symbol ⊚ indicates that an image printed all-over to a blue color is completely free from color irregularities, a symbol indicates that the image quality is not of a problem but the image suffers from color irregularities, even though to a lesser extent, and a symbol x indicates that the entire image suffers from color irregularities such that the image quality is deteriorated significantly. It may be seen from the results of evaluation shown in Table 3 that, as compared to the sample 11 not containing the EO adduct of a dihydric alcohol, the samples 12 to 15 with the I/O off the range of 1 to 1.37 or to the sample containing an EO adduct of a dihydric alcohol having a hydrocarbon group with 12 carbon atoms, the samples 1 to 10 containing an EO adduct of a dihydric alcohol, having a hydrocarbon group with 9 or less carbon atoms and having an I/O ratio ranging between 1 and 1.37 are not of a problem in the image quality in the evaluation of emission stability, intermittent emission stability, boundary bleeding and speckled color mixing in all-over printing, while being superior in optical density. With the samples 1 to 16, not containing an EO adduct of a dihydric alcohol, having a hydrocarbon group with 9 or less carbon atoms and having an I/O ratio ranging between 1 and 1.37, it becomes difficult to suppress fine air bubbles from being generated in the ink emitting head, while emission defects, such as non-emission or warped emission, as well as white spots or blurring, are produced to deteriorate the image quality. Moreover, with the samples 1 to 16, not containing an EO adduct of a dihydric alcohol, having a hydrocarbon group with 9 or less carbon atoms and having an I/O ratio ranging between 1 and 1.37, it becomes difficult to raise the optical density of the image or to suppress generation of boundary bleeding or speckled color mixing in all-over printing, such that no image of high image quality can be produced. With the samples 1 to 10, containing the EO adduct of a dihydric alcohol, having a hydrocarbon group with 9 or less carbon atoms and having an I/O ratio ranging between 1 and 1.37 in contradistinction from the above samples 11 to 16, fine bubbles can be suppressed from being produced in the ink emission head, such that the nozzles may be prevented from being stopped with these fine bubbles to prevent emission troubles, with the result that the image printed may be free from white spots or blurring and of high quality. With the samples 1 to 10, containing the EO adduct of a dihydric alcohol, having a hydrocarbon group with 9 or less carbon atoms and having an I/O ratio ranging between 1 and 1.37, an image printed may be of high image quality, being superior in optical density and suppressed in boundary bleeding or in speckled color mixing in all-over printing. It may be seen from above that addition of the EO adduct of a dihydric alcohol, having a hydrocarbon group with 9 or less carbon atoms and having an I/O ratio ranging between 1 and 1.37, to the ink being prepared, is crucial in producing the ink of high quality superior in emission stability, intermittent emission stability and in optical density and which is suppressed in boundary bleeding and in speckled color mixing in all-over printing. It will also be seen from the results of evaluation of Table 3 that, with the samples 7 to 10, the emission stability is improved further. The reason is that the EO adducts of a dihydric alcohol, represented by the chemical formulas 9, 11, 13 and 15, as used for the samples 7 to 10, contain branched hydrocarbon groups, with the steric chemical structure of the a dihydric alcohol acting for further suppressing the generation of fine bubbles in the ink. It may be seen from this that use of an EO adduct of a dihydric alcohol, having a branched hydrocarbon group, as an EO adduct of a dihydric alcohol, having a hydrocarbon group with 9 or less carbon atoms and having an I/O ratio ranging between 1 and 1.37, is crucial in the preparation of the ink having superior emission stability. Measurement was then made of the dynamic surface tension of the inks of the respective samples. The measured results of the dynamic surface tension of the respective ink samples 1 to 16 are shown in Table 4. TABLE 4 Dynamic surface EO adduct of a Sort of tension (mN/m) dihydric alcohol ink 20 1 Sample 1 Chemical formula 4 Magenta 29.5 28 cyan 29.1 27.3 Sample 2 Chemical formula 4 Magenta 34.1 31.1 cyan 34 30.5 Sample 3 Chemical formula 4 Magenta 38 35.5 cyan 37.9 35 Sample 4 Chemical formula 5 Magenta 38.2 36.1 cyan 37.5 35 Sample 5 Chemical formula 6 Magenta 39 36.8 cyan 38.6 36.4 Sample 6 Chemical formula 7 Magenta 37.8 34.7 cyan 37 34.2 Sample 7 Chemical formula 9 Magenta 36.8 34.5 cyan 36.2 34 Sample 8 Chemical formula 11 Magenta 39.5 37.7 cyan 39 37 Sample 9 Chemical formula 13 Magenta 40 38.5 cyan 39.2 38 Sample 10 Chemical formula 15 Magenta 34.3 32 cyan 34 31.7 Sample 11 — Magenta 55.6 55.5 cyan 54 53.9 Sample 12 Chemical formula 17 Magenta 30.1 29 cyan 29.2 28.5 Sample 13 Chemical formula 18 Magenta 42.5 40.3 cyan 41.8 39.2 Sample 14 Chemical formula 19 Magenta 40 39 cyan 39.1 38 Sample 15 Chemical formula 20 Magenta 53 52.1 cyan 52.4 51.1 Sample 16 Chemical formula 21 Magenta 49.1 48 cyan 48.1 47 Here, the dynamic surface tension (20) at 20 Hz and that (1) at 1 Hz were measured, under measurement conditions of 25° C. atmosphere and a capillary diameter of 0.215 mm, using a bubble pressure dynamic surface tension meter (BP-2) manufactured by KRUSS. It will be seen from measured results shown in Table 4 that, with samples 2 and 10, allowing for printing of further superior printing of higher optical density and lower in boundary bleeding and speckled color mixing in all-over printing, the dynamic surface tension (20) and the dynamic surface tension (1) of each of the magenta-based ink and the cyan-based ink are not less than 30 mN/m and not higher than 38 mN/m, respectively. It may be seen from above that setting the dynamic surface tension at 20 Hz (20) of the ink to 30 mN/m or higher and setting the dynamic surface tension at 1 Hz (1) of the ink to 38 mN/m or lower, in preparing the ink, are crucial for preparing the ink allowing for high quality printing higher in optical density and which is suppressed in boundary bleeding and in speckled color mixing in all-over printing. INDUSTRIAL APPLICABILITY The recording liquid of the present invention suffers from bubbling to a lesser extent and superior in emission stability and, when the recording liquid is used for multi-color printing an image or a letter/character on a paper sheet of medium quality, the recording liquid is high in optical density and free from boundary bleeding or speckled color mixing in all-over printing, and hence the recording liquid of the present invention may be used for high-quality printing.
<SOH> BACKGROUND ART <EOH>As a liquid emitting device, there is an ink jet printer apparatus in which a recording liquid, or a so-called ink, is emitted via an ink emitting head to a recording paper sheet, as a support, to record an image or a letter/character thereon. The printer apparatus of the ink jet system has advantages such as low running costs, small size, and ease in printing a colored image. The ink jet system, emitting the ink via an ink emitting head, may be implemented by, for example, a deflection system, a cavity system, a thermo-jet system, a bubble-jet system (registered trademark), thermal ink jet system, a slit jet system, or a spark jet system. Based on these various operating principles, the ink is turned into fine liquid droplets, which are then emitted via emitting openings, that is, nozzles, of an ink emitting head, so as to be deposited on the sheet for recording an image or a letter/character thereon. Meanwhile, a demand is raised for the nozzles not to be stopped up with the recorded liquid used in the ink jet recording system. It has so far been felt that fine bubbles in the ink represent one of the factors possibly responsible for nozzle clogging. In the ink, a preset quantity of a gas, such as air, remains dissolved. If, with rise in temperature, the gas is lowered in solubility, the gas which may not be dissolved in the liquid is separated to form fine bubbles in the liquid. Specifically, when the ink present in an ink tank adapted for supplying the ink to e.g. an ink emitting head, in an ink duct or in an ink emitting duct rises in temperature, the gas dissolved in the liquid is released to form fine bubbles. When these fine bubbles are present in the ink emitting head, emission troubles, such as non-emission of the ink from the nozzle or warped emission of the ink, that is, the ink being emitted from the nozzle along a path offset from the intended path, are produced, with the result that printed image suffers from white spots or becomes blurred to degrade the printing quality. In the recording system in which the ink is turned into fine liquid droplets, under the action of thermal energy, and the so formed liquid droplets are emitted from the nozzle, that is, in the recording system of the thermal type or the bubble jet type, the ink is heated rapidly by a heater and emitted in the form of liquid droplets under the pressure of air bubbles generated by film boiling of the ink. Thus, heat is accumulated in the vicinity of the heater, and hence the ink in the ink duct is extremely liable to be raised in temperature, with the result that emission troubles, such as the aforementioned non-emission or warped emission, tend to be produced to a pronounced extent. For combating such problem, it is proposed in e.g. the JP Patent Publications 1 and 2 to use an aqueous pigment ink doped with a propylene oxide adduct polymer of lower alcohol. However, these proposals are not up to sufficient suppression of fine bubbles and further improvement has been desired. It has also been proposed in Patent Publication 3 to add an ethylene oxide adduct of a higher dehydrate alcohol alkoxylate in an aqueous pigment ink. The ink proposed in this Patent Publication 3 is alleged to be superior in emission stability during high frequency driving, penetrability to the recording paper sheet and in drying properties. However, if a compound obtained on adding only ethylene oxide to the higher alcohol a dihydric alcohol alkoxylate is contained in the ink, in association with the teaching by Patent Publication 1, it has not been possible to cope successfully with the problem of the nozzles being stopped with fine bubbles. Specifically, the ink obtained on adding 7 mol or more only of ethylene oxide undergoes vigorous foaming to cause severe nozzle clogging. On the other hand, with the ink used for the ink jet recording system, a demand has been raised not only for prohibiting nozzle clogging but also for preventing the optical density from being lowered or for preventing the boundary bleeding or speckled color mixing in all-over printing, even in case of printing on a medium grade paper sheet, such as copy paper sheet or report paper sheet, or a high grade paper sheet. For meeting the demand, it has been proposed in e.g. Patent Publication 4 to use a compound, obtained on treating a water-insoluble colorant with a high polymer material containing a sulfonic acid (sulfonate) group and/or with a high polymer material containing phosphoric acid (phosphate) group, as a colorant, and also to add a high polymer material, including a carboxylic acid (carboxylate) to the ink. It has also been proposed in Patent Publication 5 to get the ink doped with an alginic acid having a D-mannuronic acid to L-guluronic acid ratio ranging between 0.5 and 1.2. It has also been proposed in Patent Publication 6 to add at least one surfactant selected from the group of fluorine-based surfactants and silicon-based surfactants and alginates to the ink. However, neither of these Publications is sufficient to meet the aforementioned demand and further improvement has been desired. On the other hand, the aforementioned problem, related with the bubbles, occurs more pronouncedly with a printer apparatus capable of performing high-speed printing on a recording paper sheet, that is, a line-based printer apparatus having an ink emitting range substantially equal to the width of the recording paper sheet (for example, see Patent Publications 7 to 9). More specifically, with a line-based printer apparatus, having one or more rows of nozzles juxtaposed in a direction substantially at right angles to the width-wise direction of the recording paper sheet, as distinct from a serial-based printer apparatus in which an ink emitting head is scanned in a direction substantially at right angles to the feed direction of the recording paper sheet, an ink duct for conducting the ink from an ink tank is formed for traversing the feed direction of the recording paper sheet, and in which a plural number of ink emitting heads, each having a nozzle, are arrayed on one or both sides of the ink duct, the number of ink heating sites is correspondingly increased with the number of the nozzles, so that fine bubbles tend to be generated. Moreover, the ink tank is separated from the ink emitting head a long distance, whilst the structure from the ink tank to the ink emitting head is complicated to render it difficult to remove the fine bubbles generated, with the result that inconveniences ascribable to the fine bubbles occur most pronouncedly. With the line-based printer apparatus, the period of emission of liquid droplets from one nozzle line to the next is that short and hence an ink exhibiting superior penetration characteristics into the recording paper sheet needs to be used. If the ink of this sort is used for a paper sheet of medium quality, the ink exhibits the tendency to seep into the paper sheet along its depth, that is, along its thickness, with the result that the optical density tends to be lowered. In addition, if so-called color printing of emitting inks of different colors on a recording paper sheet, is to be carried out with the line-based printer apparatus, where the period of emission of liquid droplets from one nozzle line to the next is short, a color liquid droplet is deposited before the previously deposited color liquid droplet sufficiently seeps into the bulk part of the paper sheet, with the consequence that boundary bleeding or speckled color mixing in all-over printing tends to be produced between different colors. Patent Publication 1: Japanese Laid-Open Patent publication 2001-2964 Patent Publication 2: Japanese Laid-Open Patent publication H10-46075 Patent Publication 3: Japanese Laid-Open Patent publication H7-70491 Patent Publication 4: Japanese Laid-Open Patent publication 2000-154342 Patent Publication 5: Japanese Laid-Open Patent publication H8-290656 Patent Publication 6: Japanese Laid-Open Patent publication H8-193177 Patent Publication 7: Japanese Laid-Open Patent publication 2002-36522 Patent Publication 8: Japanese Laid-Open Patent publication 2001-315385 Patent Publication 9: Japanese Laid-Open Patent publication 2001-301199
<SOH> BRIEF DESCRIPTION OF THE DRAWINGS <EOH>FIG. 1 is a perspective view showing a printer apparatus embodying the present invention. FIG. 2 is a perspective view showing a head cartridge provided to the printer apparatus. FIG. 3 is a cross-sectional view showing the head cartridge. FIGS. 4A and 4B show an ink supply part when an ink tank is fitted to the head cartridge, where FIG. 4A is a schematic view showing the closed state of the ink supply part and FIG. 4B is a schematic view showing the opened state of the ink supply part. FIG. 5 is a schematic view showing the relationship between the ink tank and an ink emitting head in the head cartridge. FIGS. 6A and 6B show a valving mechanism in a connecting part of the ink tank, where FIG. 6A is a cross-sectional view with a valve in the closed state and FIG. 6B is a cross-sectional view with the valve in the opened state. FIG. 7 is a cross-sectional view showing the structure of the ink emitting head. FIGS. 8A and 8B show the ink emitting head, where FIG. 8A is a schematic cross-sectional view showing the state in which an air bubble has been formed on a heater resistor and FIG. 8B is a schematic cross-sectional view showing the state in which the ink liquid droplet has been discharged from the nozzle. FIG. 9 is a partial see-through side view of the printer apparatus. FIG. 10 is a schematic block diagram showing a control circuit of the printer apparatus. FIG. 11 is a flowchart showing the printing operation of the printer apparatus. FIG. 12 is a partial see-through side view of the printer apparatus, shown with a head cap opened. detailed-description description="Detailed Description" end="lead"?
20050617
20080101
20060316
98150.0
G01D1100
0
SHAH, MANISH S
RECORDING LIQUID, LIQUID CARTRIDGE, LIQUID DISCHARGE APPARATUS AND METHOD OF LIQUID DISCHARGE
UNDISCOUNTED
0
ACCEPTED
G01D
2,005
10,539,506
ACCEPTED
Automatic, connection-based terminal or user authentication in communication networks
The aim of the invention is to permit the automatic identification of access rights to protected areas in networks, in particular on the Internet. This is achieved by a method for automatically identifying access rights to protected areas in a first network (2) using a unique connection identifier of a second network (1), in particular in the interconnection of networks that constitutes the Internet. According to the invention: a unique identifier of the first network (2) is dynamically or statically assigned to a terminal, during or prior to the latter's connection to the first network (2); a combination of at least the unique connection identifier of the second network (1) and the unique identifier of the first network (2), said combination being stored in an authentication unit (16), is polled when the terminal requests access to the protected area, in order to determine the unique connection identifier of the second network (1) using the unique identifier of the first network (2); and the existence of access rights to the protected area for the unique connection identifier of the second network (1) is then verified.
1. Method for automatically identifying an access right to protected areas in a first network using a unique connection identifier of a second network, with the following procedural steps: dynamic or static assignment of a unique identifier of the first network for a terminal, during or prior to the latter's connection to the first network by means of the second network; storage of a combination of at least the unique connection identifier of the second network by means of which the connection was made, and the unique identifier of the first network in an authentication unit; the provider of the protected area requesting the authentication unit to determine the unique connection identifier of the second network using the unique identifier of the first network when the terminal would like access to the protected area; authentication and/or communication exclusively of the unique identifier of the second network to the provider of the protected area by means of the authentication unit; checking whether an access right for the protected area exists for the unique connection identifier of the second network. 2. Method in accordance with claim 1, wherein the combination stored in the current authentication unit contains further data in addition. 3. Method in accordance with claim 2, characterized in that the additional data has at least one of the following: the dial-in number into the first network, a user name (login) and a password. 4. Method in accordance with claim 1, wherein the authentication unit is only run temporarily. 5. Method in accordance with claim 4, wherein the combination of data is deleted from the authentication unit as soon as the terminal ends its connection with one of the two networks. 6. Method in accordance with claim 1, wherein the unique identifier of the second network is a call-up number. 7. Method in accordance with claim 1, wherein the protected area includes the provision of an online individual connection identification. 8. Method in accordance with claim 7, wherein a individual connection identification takes place automatically for the unique connection identifier of the second network. 9. Method in accordance with claim 7, wherein, before release of a individual connection identification, a further entry on the terminal is necessary in addition. 10. Method in accordance with claim 9, wherein the further entry includes the entry of an invoice number and/or a customer number and/or a PIN. 11. Method in accordance with claim 1, wherein only authorised services have access to the authentication unit. 12. Method in accordance with claim 1, wherein the protected area includes at least one of the following services: provision of contents, electronic trade (e-commerce), payment or settlement services and authorized services. 13. Method in accordance with claim 12, wherein with a payment service, the costs arising are automatically invoiced by means of the unique connection identifier of the second network. 14. Method in accordance with claim 1, characterized in that further data are automatically called up from the terminal and/or further procedural steps are initiated in the protected area using the unique connection identifier of the second network. 15. Method in accordance with claim 1, wherein further personalisation of the terminal takes place by entering a PIN. 16. Method for providing data for automatic identification of access rights to protected areas in networks, with the following procedural steps: provision of at least one unique identifier respectively from at least two different networks while a connection to both networks exists, whereby the connection to one of the networks happens by means of the other network; storage of a combination of the different identifiers in an authentication unit; authentication and/or issue exclusively of one of the unique identifiers when a corresponding enquiry is made regarding the other unique identifiers; deletion of the data from the authentication unit as soon as a connection with at least one of the two networks has ended. 17. Method in accordance with claim 16, wherein at least one of the identifiers is an IP number and/or a unique connection identifier of a terminal. 18. Method in accordance with claim 16, wherein it is checked whether the enquiry originates from an authorised place or from an authorised service. 19. Method in accordance with claim 16, wherein the combination stored in the current authentication unit contains further information in addition. 20. Method in accordance with claim 19, wherein the additional data have at least one of the following: a dial-in number into one of the networks, a user name (login) and a password. 21. Method in accordance with claim 16, wherein a call-up number block or a target number block is identified by means of the authentication unit. 22. Method in accordance with claim 1 or 16, wherein the first and second networks are based on different protocols. 23. Method in accordance with claim 1 or 16, wherein the first network is the internet, and the second network is a telephone network.
This invention relates to automatic terminal or user identification in networks, in particular in the interconnection of networks that constitutes the internet, and in particular to a method for automatically identifying an access right to protected areas of networks, in particular in the interconnection of networks that constitute the internet, whereby the term protected area includes any transactions which are not freely available. The handling of sensitive data or transactions, excluding unauthorised users from networks, in particular in the freely accessible internet, poses great security problems. On the one hand, access rights must first of all be guaranteed for the transactions, excluding unauthorised users, and on the other hand, a secure transfer of the data must then take place. This invention deals with the first of these problems, namely the checking of whether a terminal which carries out transactions excluding unauthorised users, also has access rights to the same. A conventional method for identifying a terminal or a user for the supply of a specific service, such as for example, access to protected areas on the internet, is to request a user name and a password. This type of method, whereby a user name and a password are requested, provides a relatively high level of security with regard to the identification of the user. With this method, however, it is necessary for the user to first of all be registered in some form, so as to use a desired area. The consequence of this for the user is that, if required, he must provide personal data for the registration even if he doesn't feel this is justified. Furthermore, users nowadays often write down user names and passwords because they have to administer too many passwords or pins, eg. for accessing their own computers, account card, credit card etc. However, it is well known that this writing down goes hand in hand with a security risk. For the corresponding service provider, this also means that correspondingly efficient customer data administration must be provided, which generally requires manual support. For the provider of a specific service, it is often not, however, necessary for the receiver of the service to be registered with them in any form. The customer is thus eg. anonymous to the network operator (provider) during open “call by call” or during open “internet by call”. The network operator only knows the call-up number, ie. a unique connection identifier of an otherwise anonymous customer, the target call-up number and the length of the call. For invoicing purposes, these data are general communicated to the collection point at the telephone company of the customer, for example Deutsche Telekom AG. Here, the customer can remain fully anonymous to the provider of a specific service, because other than the unique connection identifier, no further information about the customer is required. If the network operator or the service provider would like, however, to offer the respective customer transactions, excluding unauthorised third parties, for example to make available confidential date—such as a individual connection identification—or make possible access to other protected areas, this was previously only possible with a pre-registration so as to ensure that only authorised terminals could gain access to the respective data. The aim of this invention, therefore, is to make possible automatic identification of access rights to protected areas in networks, in particular on the internet. In accordance with the invention, this task is fulfilled with a method for automatic identification of an access right to protected areas in a first network using a unique connection identifier of a second network, in particular in the interconnection of networks that constitutes the internet, with the following procedural steps: dynamic or static assignment of a unique identifier of the first network for a terminal during or prior to the latter's connection to the first network, storage of a combination of at least the unique connection identifier of the second network and the unique identifier of the first network in an authentication unit, questioning of the authentication unit in order to establish the unique connection identifier of the second network using the unique identifier of the first network when the terminal wishes to gain access to the protected area, checking whether an access right exists for the protected area for the unique connection identifier of the second network. This method thus makes possible a secure, automatic identification of access rights to protected area in networks using the identifiers from two different networks. Pre-registration by means of a user name and password and the supply of personal information is not necessary. But even with access to areas which also require registration, such as for example commercial data bases, the method in accordance with the invention also makes it possible for the access to be only to specific network elements, in particular specific telephone connections (both mobile and fixed networks), and this excludes any misuse, even when user names and passwords are lost or knowingly passed on to others. In accordance with a preferred embodiment of the invention, the combination stored in the current authentication unit contains additional data, such as for example the dial-in number into the network, a user name (login) and/or a password. These data can make better identification of the terminal possible, whereby in particular, the user name and the password can be automatically produced by dialling into the network. With a particularly preferred embodiment of the invention, the authentication unit is only temporarily run so that it is essentially a dynamic unit. Preferably, the combination of data is deleted from the authentication unit as soon as the terminal ends its connection. In this way it is guaranteed that access to the protected area is only possible for as long as a connection from the unique connection identifier to the network exists. With one embodiment of the invention given as an example, the unique identifier of the second network is a call-up number. Preferably, the protected area includes the provision of an online individual connection identification so that the user of “call by call” or “internet by call” services can gain access to his connection identifications without having to register in advance. The individual connection identification is provided here automatically for the unique connection identifier of the terminal. With an alternative embodiment of the invention, before the release of a individual connection identification, an additional entry is required on the user's terminal so as to ensure that not every terminal which has access to a specific network element or a specific telephone connection can also call up the connection identifications for this connection. The additional entry comprises, for example, the entry of an invoice and/or customer number of the telephone company, and/or a PIN. In order to guarantee a high level of security with identification and to prevent misuse of the authentication unit, only authorised services have access to the authentication unit, and these must, if so required, register in advance with the authentication unit and identify themselves when so requested. With one embodiment of the invention, the protected area includes at least one of the following services: provision of data (commercial data bases), electronic trade (e-commerce) and payment. In the e-commerce area, in general the pre-registration of a customer can not be dispensed with, but the use of the e-commerce services can be made simpler because a terminal can be automatically identified using its connection identifier such as eg. its telephone connection. With the payment service, amounts of money can, for example, be invoiced by means of the customer's telephone bill, eg. the one-off invoicing of a small amount for reading a specific newspaper article on the internet. The costs arising from the payment service are preferably invoiced automatically by means of the unique connection identifier. Here, the method in accordance with the invention makes it possible to subsequently provide exact evidence of the connection established between two network elements, the contact, the order, and if required, the supply of the service provided, even without registration of the respective customer. With another embodiment of the invention, further data from the terminal are automatically called up and/or further procedural steps are initiated in the protected area using the unique connection identifier of the second network, such as eg. the connection number or SIM card address. The additional data can be provided, for example, from a pre-registration under the unique connection identifier. Such additional data are in particular practical in the e-commerce area where, if required, delivery and invoice addresses have to be given. As further procedural steps, eg. automatic processing of an order can take place. The method in accordance with the invention can also be used in combination with known authentication with user name and password so as to achieve even higher data security. The task which forms the basis of the invention is also fulfilled with a method for providing data for an automatic identification of access rights to protected areas in networks, in particular in the interconnection of networks that constitutes the internet, with the following procedural steps: provision of at least one respective unique identifier from at least two different networks while a connection to both networks exists, the storage of a combination of the different identifiers in a dynamic authentication unit, issue and/or authentication of one of the unique identifiers with a corresponding enquiry with regard to the other unique identifiers, deletion of the data from the dynamic authentication unit as soon as a connection with at least one of the two networks is ended. The method in accordance with the invention provides a dynamic authentication unit of the terminal currently located in the network which makes possible identification of a terminal using its unique identifier from both networks. The authentication unit here is run in real time so that the stored data are only kept for as long as the terminal is in the network. After the connection has ended, the data are immediately deleted so as to prevent any misuse. Preferably, at least one of the identifiers is an IP number and/or a unique connection identifier of a terminal. For increased data security, it is checked that the enquiry with regard to a specific IP number originates from an authorised service. In this way it is ensured that data located in the authentication unit is not improperly used. For increased data security, data additional to the aforementioned combination are stored in the current authentication unit. These can include, for example, the dial-in number, a user name (login) and a password. These additional data provide further improved identification security. With one embodiment of the invention, a call-up number block or a target number block can be identified by means of the authentication unit or the identifier issued. In the following this invention is described in greater detail using a preferred embodiment of the invention given as an example, and with reference to the drawing. In the drawing: FIG. 1 shows a schematic system overview for an open “internet by call” service of a telecommunications network operator. Using FIG. 1, the method in accordance with the invention with automatic identification of access rights is described in more detail using the example of an online individual connection identification (EVN) for “internet by call” customers. First of all, however, the general invoicing mode with an “internet by call” service is described. With an open “internet by call” service the customer, whose connection runs, for example, to Deutsche Telekom AG (DTAG), dials via the DTAG network into the network of a corresponding network operator, hereinafter referred to as the provider. DTAG connects the corresponding call in its network up to a defined hand-over point which is also called the “point of interconnect” (POI). At this POI, the call from DTAG is transferred to the provider of the “internet by call” service. If required, there is now a connection of the call in the network of the operator, and the call is timed on a modem bank of the provider. In so far as is required, the customer data, such as for example a user name and a password are checked and then the customer is allocated a (dynamic) IP address. The call is now further connected to its target destination (eg. the public internet) on the basis of the internet protocol (IP). The data relevant for invoicing the call are recorded by the provider, and passed on to the collection point at DTAG. The provider receives information from DTAG concerning which data sets were invoiced under which invoice number (invoice number, customer number and invoice date), without the customer's particulars being known to the provider. On their invoices, DTAG do not list the individual “internet by call” calls made by the customer, which the latter can, however, request online, as described below. The system described below with reference to FIG. 1 makes possible an automatic connection-based authentication of a customer so as to make possible access to an online individual connection identification of an “internet by call” provider. Block 1 in FIG. 1 represents the telecommunications network outside of the provider's network. In block 1, the dialling and the connection of the call as far as the POI of the “internet by call” provider takes place. The system of the network provider is shown by a box 2 outlined by a broken line in FIG. 1. Block 4 in FIG. 1 represents a switch in which the data relevant to invoicing the customer are produced. These customer data, which are called “call data records” (CDR) contain eg. the customer's unique connection identifier, the dial-in number into the provider's network, and the start and the end time of the call. These data are further conveyed in the provider's network to a calculation system in block 6 which calculates the costs for the respective call. The calculated costs are communicated to DTAG in block 8, giving the unique connection identifier. DTAG then invoices these costs to the customer of the respective connection of the unique connection identifier, and sends data relating to the invoice back to the calculation system in block 6. These data include, for example, the account number, the customer number and the invoice date. The customer's personal data are not included. From block 6, the calculated costs together with the CDR data are communicated to an internal network data base server in block 10. This communication can take place immediately or only after receipt of the invoice data by DTAG. If the data are communicated immediately, the invoice data sent back later by DTAG after receipt are communicated subsequently to the data base server 10, which then accumulates and controls these data. The switch in block 4 conveys a part of the CDR data, namely the unique connection identifier and the dial-in number onto a modem bank in block 12, where the call is timed. From the modem bank in block 12, the data are communicated to a server in block 14. Here, a current IP address for the call is allocated. The current IP address, the corresponding unique connection identifier and the dial-in number are then conveyed on to an authentication unit in block 16. When the call has ended, ie. the connection between the provider's network and the customer is broken, the switch in block 4 informs the modem bank in block 12 that the call has ended. The corresponding space on the modem bank is released, and the modem bank informs the server in block 14, giving the corresponding IP address, that the call has ended. The server in block 14 once again transfers this information immediately to the authentication unit in which the data from the IP address, the unique connection identifier and the dial-in number are immediately deleted. The authentication unit thus contains a dynamic data base in which respectively only current authentication data are stored, ie. data relating to a current connection between a customer connection (unique connection identifier) and a dial-in point of the network (dial-in number) and the dynamically assigned IP address. This specific combination of data is only stored for as long as an actual connection to a customer connection exists. If a customer would like to see his invoice data online, he will call up the corresponding internet page in the provider's network which has access to the data base server in block 10 via a web interface in block 20. By means of the web interface, the data base server 10 is informed of the currently assigned IP number of the customer, not, however, the unique connection identifier of the same. The data base server in block 10 therefore makes an enquiry to the authentication unit in block 16 so as to establish whether the customer's IP address used during the enquiry represents a current IP address, and furthermore, to which connection, ie. to which unique connection identifier the IP address is assigned. If it is a current IP address, the data combination is sent from the authentication unit to the data base server in block 10, and the data base server can now filter out the individual connection identifications corresponding to the unique connection identifier and release them for inspection. If required, additional information, such as for example a PIN and/or an invoice number and/or a DTAG customer number can also be requested so as also only to make the information relating to the individual connection identification available to the person or the terminal which actually has access to the DTAG invoice. The essential feature for secure, connection-based identification of a terminal is the provision of the dynamic authentication unit which only contains data for currently existing connections, and so offers a high level of security against misuse. Although this invention was described especially using an online individual connection identification, the connection-based authentication of access rights can, of course, also be extended to other areas. For example, any internal network or also external network service could access the authentication unit so as to establish whether and to which telephone connection (unique connection identifier) a specific IP address is currently assigned. The unique connection identifier permits a connection-based authentication by means of the respective service. Of course only specific registered services can gain access to the authentication unit, and they must also be respectively identified so as to prevent any misuse of the authentication unit. This type of service is, for example, payment services which invoice amounts by means of a corresponding collection system with DTAG's telephone bill. This type of invoicing takes place, for example, when reading specific newspaper articles on the internet where a fee is payable. Proof of the connection having been made, the order, the supply as well as the implementation of payment claims and supply obligations is thus possible using the above authentication method, even with “anonymous” end customers. Another possibility for the use of a connection-based authentication is identification by e-commerce providers. When placing orders with or making enquiries of e-commerce providers, these can automatically carry out a connection-based authentication, and so clearly allocate orders. This is particularly beneficial when buying virtual products (eg. digital books, sound and film recordings), because the delivery address here does not represent any control. Further authentication by means of user name and password can then be dispensed with, or used in addition, so as to offer a still higher level of security. Using connection-based authentication, the e-commerce provider can then call up further relevant customer data provided the customer is registered with the unique connection identifier. E-commerce providers, and also providers of other contents, can block different unique connection identifiers with the network operator so as to prevent further transactions being made from these connections. In this respect, connection-based authentication provides protection against misuse. Another example where connection-based authentication can be of particular use is registration with specific services by means of the unique connection identifier. The customer can, for example, clear his connection for specific services, and thereupon receives an automatically produced code which in the future he adds to the dial-in number in subsequent dialling processes. Using this code, a specific set of services can be assigned to the corresponding unique connection identifier which have been approved for this unique connection identifier (eg. only online tariff services, no XXX services). With an online authorisation process, the user or a terminal can also be securely identified so as to avoid misuse. In many cases, the connection-based identification can replace an electronic signature, and also makes possible the transfer of payment models known from the telephone networks to the data networks. Connection-based identification makes it possible in general to make available contents, excluding third parties, without any further authentication, and to block contents for unique connection identification. Using the connection technical information, it can also be checked whether a particular service is expedient for this connection. There is no sense in transferring a videostream to a GSM mobile, whereas this can be expedient for a UMTS terminal or a fixed net connection with terminal. This invention is not limited to the precise embodiment described and the above-specified examples. Rather in general it provides automatic authentication of a terminal in networks, in particular in the interconnection of networks that constitutes the internet, whereby at least two identifiers from at least two different networks are used. This authentication can be used for different purposes.
20060110
20120228
20060727
85308.0
H04M1500
0
DOAN, TRANG T
AUTOMATIC, CONNECTION-BASED TERMINAL OR USER AUTHENTICATION IN COMMUNICATION NETWORKS
UNDISCOUNTED
0
ACCEPTED
H04M
2,006
10,539,637
ACCEPTED
On-growth inhibiting compounds
An on-growth inhibiting agent, for the inhibition and/or prevention of on-growth of biological organisms on objects or living beings, includes at least one cyclotide, and a suitable carrier medium. A plant extract containing a mixture of cyclotides is also usable.
1. On-growth inhibiting agent, for the inhibition and/or prevention of on-growth of biological organisms on objects or living beings, said agent comprising at least one cyclotide, and a suitable carrier medium. 2. Agent according to claim 1, said cyclotide(s) having the general formula wherein C is cysteine; each of [X1 . . . Xa], [XI1 . . . XIb], [XII1 . . . XIIc], [XIII1 . . . XIIId], [XIV1 . . . XIVe] and [XV1 . . . XVf] represents one or more amino acid residues wherein each one or more amino acid residues within or between the sequence residues may be the same or different; and wherein a, b, c, d, e and f represent the number of amino acid residues in each respective sequence and each of a to f may be the same or different and range from 1 to about 20 (SEQ ID NO: 1); or an analogue of said sequence. 3. Agent according to claim 1, wherein each of a to f ranges from 1 to about 10 (SEQ ID NO: 2). 4. Agent according to claim 1, wherein a, b, c, d, e and f represent the number of amino acid residues in each respective sequence and wherein a is from about 3 to about 6, b is from about 3 to about 5, c is from about 2 to about 7, d is about 1 to about 3, e is about 3 to about 6, and f is from about 4 to about 9 (SEQ ID NO: 3). 5. Agent according to claim 1, wherein a, b, c, d, e and f represent the number of amino acid residues in each respective sequence and wherein a is about 3, b is about 4, c is from about 4 to about 7, d is about 1, e is about 4 or 5, and f is from about 4 to about 7 (SEQ ID NO: 4). 6. Agent according to claim 1, wherein a, b, c, d, e and f represent the number of amino acid residues in each respective sequence and wherein a is about 6, b is about 4, c is 3, d is about 1, e is about 5, and f is about 8 (SEQ ID NO: 5). 7. Agent according to claim 1, comprising any of the following cyclotides alone or in combination: vico A, vico B, hypa A, cycloviolacin O1, cyclopsychotride A, cycloviolacin O7, circulin D, circulin E, cycloviolin C, cycloviolacin O3, cycloviolacin O9, cycloviolacin O10, cycloviolacin H1, circulin C, cycloviolin A, cycloviolin D, circulin F, circulin A, circulin B, cycloviolacin O2, cycloviolacin O4, cycloviolacin O6, cycloviolacin O11, cycloviolacin O8, cycloviolacin O5, kalata B5, cycloviolin B, varv A, kalata S, kalata B1, kalata B4, varv E, cycloviolacin O12, varv D, varv C, varv B, varv G, varv H, kalata B2, kalata B3, kalata B6, varv F, kalata B7. 8. Agent according to claim 1, wherein the cyclotide is cycloviolacin 02. 9. A plant extract, comprising a fraction from an extraction process containing a mixture of cyclotides. 10. A plant extract as claimed in claim 9, obtained from Sweet Violet. 11. A method of preventing on-growth of biological organisms on objects or living beings, comprising applying an agent as claimed in claim 1 or on a surface of said object or living being. 12. A product, protected from on-growth of biological organisms by the application of an agent as claimed in claim 1 or on a surface thereof. 13. A method of preventing on-growth of biological organisms on objects or living beings, comprising applying an extract as claimed in claim 9 on a surface of said object or living being. 14. A product, protected from on-growth of biological organisms by the application an extract as claimed in claim 10 on a surface thereof.
The present invention relates to compounds, methods and agents, for preventing or inhibiting on-growth of living organisms on surfaces in general, e.g. on physical objects and/or living beings, such as barnacles on marine structures, micro-organisms forming bio-films on e.g. medical equipment, and on living animals, such as fish in fish cultures. BACKGROUND OF THE INVENTION AND PRIOR ART The solution of the severe technical and economical problem caused by marine fouling organisms, e.g. barnacles, blue mussels, algae and hydroids, for the shipping industry and in aquaculture has been the use of TBTO (tri-n-butyl tin oxide), copper oxide and herbicides in marine coatings. However, several of these have been recognised to be toxic against non-fouling marine organisms. For example, TBTO has been ascribed effects such as reproduction failure and decrease in adult growth in oysters and the development of imposex in gastropodes such as the dog whelk. Because of these unwanted side effects, the use of TBTO will be stopped by future bans; the International Marine Organisation will recommend a global ban from the year 2005. Therefore it is urgent to find new non-toxic alternatives which exert a specific action on target organisms and which also are biodegradable. Craik et al in WO 01/27147 discloses a novel cyclic molecular framework comprising i.a. so called cyclotides, i.e. cyclic peptides. These compounds are claimed to be usable for treatment or prophylaxis of disease conditions in animals, mammals and plants. WO 00/68265 (Ouelette et al) discloses pharmaceutical compounds based on cyclic peptides. WO 99/21879 (Chang et al) discloses cyclic peptides having antimicrobial and antibacterial activity. SUMMARY OF THE INVENTION I.a. in view of the toxicity of the presently used compounds for preventing on-growth on i.a. marine structures, it would be desirable to have access to nontoxic substances, which do not accumulate in the environment, and which do not intervene irreversibly in the natural biological/ecological systems. One promising approach to find new non-toxic antifouling agents has been to explore natural compounds occurring in the marine environment, especially those produced by marine organisms free from fouling. The present inventors have shown that this search among biologically active natural products may be expanded to terrestrial ones as well, by the potent, antifouling effect against barnacles (Balanus amphitrite, Darwin) of the plant peptide cycloviolacin O2, isolated from the Sweet violet, Viola odorata L. (Violaceae). This peptide is one member of the family of cyclotides, which today consist of almost 50 members. Their main character is their cyclic cystine knot; their amino acid backbone is circular and thus they lack both N- and C-terminals, and they all contain six cysteine residues involved in three disulfide bridges in a knotted arrangement. In combination with their size, ranging from 28-37 amino acid residues, these structural features renders the cyclotide peptides an extreme stability. This structural scaffold, unique for the cyclotides, has previously been shown able to mediate a variety of biological activities, such as antimicrobial and insecticidal effects. The inventors have now surprisingly discovered that the antifouling effect against barnacles of cyclotides, and in particular cycloviolacin O2 is, in contrast to the existing antifouling agents on the market today, is non-toxic and reversible. Thus, the present invention in its broadest aspect, which provides a novel on-growth inhibiting agent comprising a class of compounds having an on-growth inhibiting and preventing effect, is defined in claim 1. In a further aspect of the invention, an extract from a member of the Violaceae family of plants having on-growth inhibiting and preventing properties, is defined in claim 9. In a still further aspect there is provided a method of preventing on-growth of organisms in general, including larvae, bacteria, viruses, and fungi on physical objects or on living beings, said method being defined in claim 11. BRIEF DESCRIPTION OF THE DRAWINGS The invention will now be further illustrated with reference to the attached drawings wherein FIG. 1 illustrates the isolation by ion exchange chromatography. Cyclotides with a basic net charge was effectively captured by strong cation exchange chromatography. After elution of non charged substances, the bound peptides, here marked *, were eluted in a NaCl gradient (0-1 M). A solvent composition of 25% AcN, 0.1% TFA in water was used; the addition of AcN was shown to promote ionic interactions. FIG. 2 shows the antifouling effect of cycloviolacin O2. The settlement was inhibited in a dose-dependent manner. At 0.25 μM cycloviolacin O2 there was a complete inhibition of settlement. No one of the tested concentrations showed an increase in mortality compared to the control (saltwater only). All concentrations were tested in quadruplicates. FIG. 3 demonstrates the reversibility test. Compared to the control, a lower percentage of settlement was seen of cypris transferred from 2.5 μM cycloviolacin O2. This is however a normal behaviour after long incubation times, in this case 3+5 days, and may be explained by exhaustion. No increase in mortality was observed. All concentrations were tested in quadruplicates. FIG. 4 illustrates effect on settlement of Fraction P from an extraction process performed on Sweet Violet. FIG. 5 illustrates effect on settlement of Fraction I from Sweet Violet. DETAILED DESCRIPTION OF THE INVENTION The invention is based on the discovery that a cyclopeptide designated cycloviolacin 02, extracted from the Sweet Violet, Viola odorata L., has an anti-fouling effect against larvae from barnacles, i.e. on-growth of barnacles on e.g. boat hulls is inhibited and even prevented, this effect being reversible. The mechanism of action is unknown at this stage. However, without wishing to be bound by theory, it is believed that the effect may be due to a inhibition at the early stage of folding, that is prevention of the formation of a biofilm of microorganisms that preceeds settling of macroorgansims (such as barnacles). This possibility is supported by earlier observations of the antifungal and antimicrobial effect of cyclotides. Hence, it is reasonable to expand the field of the invention to areas outside the marine environmont, such as an ingredient in house paints, to prevent growth in filters and on medical equipment. The same is valid even if the mechanism is more specific, i.e. if the cyclotides act by direct binding to a molecular target (i.e. a receptor or an enzyme) which in turn repells the settling organsim(s). The latter theory is in part supported by the their reported insecticidal activity, that is that they inhibit growth of Helicouerpa caterpillars. In its most general form, the invention comprises on-growth inhibiting agents comprising one or more compounds selected from the class of compounds designated as cyclotides, for the inhibition and/or prevention of on-growth of biological organisms on objects or living beings, said agent further comprising a suitable carrier medium. An embodiment of the invention comprises an extract from plants, preferably from Sweet Violet, comprising a mixture of cyclotides. In a particular embodiment, the cyclotide cycloviolacin O2 is used as the active agent. Products, in a general sense, comprising physical objects as well as living beings, such as fish, protected by the novel agent is also an aspect of the invention. Also, the method of protecting such products by applying an agent comprising the cyclotide(s), in any of the forms discussed, is part of the inventive concept. As already discussed above, a cyclotide is a cyclic peptide which is characterized by being fairly small (the known naturally occurring cyclotides have 28-37 amino acids, although the compounds according to the invention shall not be considered limited to any particular number of amino acids), and by containing six cysteine residues forming three disulphide bridges in a knotted arrangement. A schematic representation of a general cyclotide is given in Formula I: wherein C is cysteine; each of [X1 . . . Xa], [XI1 . . . XIb], [XII1 . . . XIIc], [XIII1 . . . XIIc], [XIV1 . . . XIVe], and [XV1 . . . Xvf] represents one or more amino acid residues wherein each one or more amino acid residues within or between the sequence residues may be the same or different; and wherein a, b, c, d, e and f represent the number of amino acid residues in each respective sequence and each of a to f may be the same or different and range from 1 to about 20; or an analogue of said sequence. Preferably each of a to f ranges from 1 to about 10. In a further embodiment a, b, c, d, e and f represent the number of amino acid residues in each respective sequence and wherein a is from about 3 to about 6, b is from about 3 to about 5, c is from about 2 to about 7, d is about 1 to about 3, e is about 3 to about 6, and f is from about 4 to about 9. In a still further embodiment a, b, c, d, e and f represent the number of amino acid residues in each respective sequence and wherein a is about 3, b is about 4, c is from about 4 to about 7, d is about 1, e is about 4 or 5, and f is from about 4 to about 7. Another embodiment is provided wherein a, b, c, d, e and f represent the number of amino acid residues in each respective sequence and wherein a is about 6, b is about 4, c is 3, d is about 1, e is about 5, and f is about 8. As examples of cyclotides usable according to the invention, the following non-exhaustive and non-limiting listing of a number of known cyclotides is given. Thus, any of vico A, vico B, hypa A, cycloviolacin O1, cyclopsychotride A, cycloviolacin O7, circulin D, circulin E, cycloviolin C, cycloviolacin O3, cycloviolacin O9, cycloviolacin O10, cycloviolacin H1, circulin C, cycloviolin A, cycloviolin D, circulin F, circulin A, circulin B, cycloviolacin O2, cycloviolacin O4, cycloviolacin O6, cycloviolacin O11, cycloviolacin O8, cycloviolacin O5, kalata B5, cycloviolin B, varv A, kalata S, kalata B1, kalata B4, varv E, cycloviolacin O12, varv D, varv C, varv B, varv G, varv H, kalata B2, kalata B3, kalata B6, varv F, kalata B7, alone or in combination can be used in the on-growth inhibiting agent according to the invention. The actual amino acid sequence for these compounds can be found in Table 4, in the doctoral thesis by Ulf Göransson, “Macrocylic Polypeptides from Plants” (ACTA UNIVERSITATIS UPSALIENSIS UPPSALA 2002), page 36. The particular peptide tested in the Examples below, cycloviolacin O2, belongs to the family of cyclic plant peptides recently named cyclotides. It was isolated from the dried aerial part of the plant Viola odorata through already established techniques for cyclotide isolation in combination with strong cation exchange chromatography. The latter was shown to be an efficient complementary method for capture of cyclotides containing a positive net charge (FIG. 1). The rapidly growing family today consists of about 50 different peptides, mainly isolated from the Violaceae and Rubiaceae plant families. The number of cyclotides known to occur in the family of Violaceae, and their high degree of sequence homology, made molecular weight alone insufficient for absolute identification after isolation of the peptide. Hence, it was modified by introduction of charged cleavage sites on the cysteines, followed by enzymatic digestion to produce peptide fragments suitable for sequencing by MS. After aminopropylation and tryptic cleavage the major part of the sequence was obtained. For full coverage, possible cleavage sites were constrained to modified cysteines only: trypsin was exchanged for endoproteinase LysC to prevent cleavage after the arginine residue, native lysine cleavage sites were protected by acetylation, and finally, cysteines were aminoethylated instead of aminopropylated to better suit the chosen enzyme. After this, the full sequence could be determined to cyclo-(VWIPCISSAIGCSCKSKVCYRNGIPCGESC), unambiguously identifying the peptide as the previously reported cycloviolacin O2. A vide variety of effects has previously been ascribed to the cyclotides, including antimicrobial, HIV-inhibitory, trypsin inhibitory and cytotoxic ones. Their function within the plant however, have not yet been fully elucidated, but probably they are involved in the host defence system. This conjecture was recently supported by Jennings and coworkers, that showed potent insecticidal activities of the cyclotide kalata B1; growth and development of the insect larvae (from Helicoverpa punctigera) was shown to be greatly affected in a feeding trial. While this activity seems intriguingly similar in aspect to cycloviolacin O2:s ability to inhibit cyprides from fouling; the insect larvae also showed an increase in mortality over time. Though, it may be hypothesized that there might be a common mechanism behind the two findings, and that the difference instead lies in the surrounding environment and its influence to the test organisms ability to give off the peptide; the marine milieu simulated in the antifouling bioassay, is ideally suited to maintain equilibriums of water soluble compounds such as peptides. Indeed, the fact that the antifouling effect is reversible show that such an equilibrium does exist in our system. Hence, the reason that the peptide can be solubilised in the surrounding water may be the simple explanation to the difference in toxicity between these two seemingly related activities. All of the members of the cyclotide family contain around 30 amino acid residues, organised in the characteristic cyclic cystine knot motif; a head-to-tail cyclised amide backbone further stabilised by three intramolecular disulfide bridges. Through slight variations in the sequences between cysteines—the loops—the plant provide itself with a library of different peptides. This variety of cyclotides may be used to further explore the antifouling effect reported here, as it enables detailed structure activity studies. Such studies may be further expanded by the use of synthetic chemistry developed for cyclotides, to identify which parts or regions of the peptide that is important for activity. Likewise, a similar approach may be used to optimise the sequence to suit a specific formulation or use, for example to covalently bind the cyclotide directly to a surface or into an antifouling paint. To our knowledge, this is the first disclosure of an evaluation of a natural product from a terrestrial source against fouling barnacles. Moreover, the tested substance represents a class and size of molecules—peptides—that generally are considered non-attractive due to their instability. However, we have isolated a peptide belonging to the cyclotide family, recognised as one of the most stable peptide structures known, with a potency in the same range as TBTO. A complete inhibition of fouling was observed at a concentration of 0.25 μM [EC50 values for TBTO, 0.09 μg ml−1 or 0.15 μM]. In addition, cycloviolacin O2 showed a distinct advantage compared to both TBTO and any other commercially used antifouling agent of today; the effect is non toxic and reversible. To conclude, we have shown that the search for antifouling agents may be expanded to natural products from terrestrial sources, exemplified here by the potent activity of the cyclic peptide cycloviolacin O2. Anti-Fouling Products Containing the Class of Inventive Compounds The novel class of compounds according to the invention can suitably be used in anti-fouling products for underwater use and such products can be prepared by conventional methods. Cyclotides as defined in the claims can for example be mixed with a binding agent such as an organopolysiloxane, e.g. a low molecular mass alkoxy-functional silicone resin, a silicone rubber or an organosilicon copolymer. An anti-fouling composition comprising cyclotides according to the invention and an organopolysiloxane can additionally comprise inorganic pigments, organic pigments, dyes (which are preferably insoluble in salt water) and/or conventional auxiliaries such as fillers, solvents, plasticizers, catalysts, inhibitors, tackifiers, coating additives and/or common dispersion auxiliaries. Other examples of anti-fouling compositions that are meant for use under water and that can be used with anti-fouling agents according to the present invention, are disclosed in U.S. Pat. No. 6,245,784-B1, U.S. Pat. No. 6,217,642-B1, U.S. Pat. No. 6,291,549-B1, U.S. Pat. No. 6,211,172-B1 and U.S. Pat. No. 6,172,132-B1. The final anti-fouling products could be used for underwater structures, e.g. in plumbing ports of nuclear power stations, at ocean facilities such as bayshore roads, undersea tunnels, port facilities, and in canals or channels, machinery operated by the power of sea motion (waves), such as power plants. The agents according to the invention could also be used for coating marine vessels, fishing gear (rope, fishing net or the like). The anti-fouling coating compositions can be applied either directly to the surface of vessel hulls and underwater structures or applied to the surface of vessel hulls and underwater structures pre-coated with undercoating material such as rust preventive and a primer. The anti-fouling coating compositions may also be used to repair surfaces of vessel hulls and underwater structures previously coated with a conventional anti-fouling paint or anti-fouling coating composition. Other structures and devices that can be protected by the novel agents are exemplified by membranes, pumps, filters etc employed in the biotechnology process industry. Further fields of use that are possible are the protection of medical equipment from the on-growth of bio film, i.e. bacterial and/or microbial adhesion on the surface of devices such as surgical instruments, tubing in contact with body fluids etc. It is also conceivable to protect fish in fish breeding plants form on-growth of unwanted species, e.g. bacteria and/or other organisms having a pathogenic effect on the fish, by the application of an agent according to the invention, either directly to the body of the animal, or by administration in the water or with the fodder. Possibly, also other animals such as cattle could be protected from infestation or attacks by vermins. The present invention will now be described by way of examples, based on extraction of active compounds from Sweet Violet, Viola odorata L. EXAMPLES General Procedures. HPLC (cation exchange and RP) was done on a Akta Basic system (Amersham Biosciences, Uppsala, Sweden). Mass spectrometry was done by nanospray-ion trap MS [Protana's NanoES source (MDS Protana A/S, Odense, Denmark) mounted on a LCQ (Thermo Finningan, San Jose, USA)] operated in the positive ion mode. Samples were sprayed using a 60% MeOH, 1% HOAc in water; the capillary temperature was set at 150° C. and the spray voltage at 0.5 kV. For MS/MS sequencing the relative CID was typically set at 35%. Unless otherwise stated, average masses were used and given as [M]. Isolation of Cycloviolacin O2. Dried and grinded plant material (Viola odorata L., obtained from Galke, Gittelde, Germany) was defatted with dichloromethane before the main extraction was carried out using 50% aqueous ethanol. This extract was concentrated in vacuo (i.e. all EtOH was removed) then the acidified extract was filtered through polyamide to remove tannins. This is referred to as Fraction P. Subsequently this extract was partitioned between H2O and n-BuOH. So far, the isolation procedure was carried out according to Claeson et al in “Fractionation protocol for the isolation of polypeptides from plant biomass”, J. Nat. Prod. 61, 77-81, and Broussalis et al in “First cyclotide from Hybanthus (Violaceae)”, Phytochemistry 58, 47-51. The BuOH fraction was then evaporated, and redissolved in 25% acetonitrile, 0.1% trifluoroacetic acid in water before pumped through a Vydac sulfonic acid polymeric strong cation exchange column (400VHP575, 5 μm, 7.5 mm ID×50 mm) at a flow rate of 1 ml/min, until the binding sites of the gel were saturated. Bound substances were then eluted with a salt gradient, ranging from 0 to 1M NaCl. The peak (referred to as Fraction I) eluting in the salt gradient was collected (FIG. 1), and analysed by RP-HPLC and MS, and was found to contain a mixture of peptides. The major peptide was then isolated by means of RP-HPLC in an analogous way as described in the article by Broussalis et al and in Göransson et al, “Seven novel macrocyclic polypeptides from Viola arvensis”, J. Nat. Prod. 62, 283-6. LC/MS Analysis of Fraction P of Viola odorata. The fraction contains a mixture of cyclotides, one of the major components is cycloviolacin O2 which was tested as a pure compound. However, results from testing the fraction itself reveals that a similar activity may be found for other members of the cyclotide family. An LC/MS analysis was performed on this extract, and is shown in FIG. 6. Some of the identified cyclotides are marked in the chromatogram as folloes: cycloviolacin O2 (marked as 1). These are kalataS/varv peptide A (2); varv peptide D (3); varv peptide E (4); cycloviolacin O9 (5); cycloviolacin O3 (6); cycloviolacin O7 (7), which represent a wide variety of cyclotide sequences. Aminopropylation/aminoethylation. Peptide (1-5 nmol) was reduced with dithioerythritol (DTE, 390 nmol) in 0.25 M Tris-HCl containing 1 mM EDTA and 6 M guanidine-HCl (pH 8.5; 24° C.; 1 h). Reduced peptide was then alkylated by the addition of 25 times the amount bromopropylamine/bromoethylamine versus DTE (9.75 μmol) dissolved in 10 ul of the Tris-HCl buffert. The reaction was then incubated overnight (37° C.), after which it was terminated by injection on RP-HPLC. Acetylation of Lysines. Dry peptide (1 nmol) was dissolved in 20 μl 50 mM NH4HCO3. To this, 50 μl of acetic anhydride in methanol (⅓) was added. After 1 hour incubation at room temperature, the mixture was lyophilized to dryness. Larval Bioassay. The brood stock of adult barnacles (B. improvisus, Darwin 1854) were allowed to settle on Plexi glass® panels in the sea on a raft outside Tjärnö Marine Biological Laboratory (58°53′N, 11°8′E). Cleaned from epiphytes they were brought to the laboratory and immediately placed in trays with running seawater (salinity 32±1%). When regularly fed, with nauplii of Artemia salina, B. improvisus will spawn throughout the year. For larval rearing we used the method according to Berntsson et al., described in “Reduction of barnacle recruitment on micro-textured surfaces: Analysis of effective topographic characteristics and evaluation of skin friction”, Biofouling 16, 245-261. The experiment for the evaluation of the effect on settlement and mortality was performed using polystyrene Petri dishes (ø 48 mm) to which 10 ml of the peptide dissolved to different concentrations in filtered seawater (0.2 μm, 32±1‰) was added. Competent cyprids (20±2 ind.) were added to each dish in four replicates and dishes with filtered seawater served as controls. Dishes were maintained for 3-4 days in room temperature after which they were examined under a stereo microscope for attached and metamorphosed individuals and also, for dead cyprids. Reversibility Test. Half of the number of cyprids in each petri dish incubated at the highest tested concentration, 2.5 μM, were moved to a petri dish containing 10 ml of fresh seawater. These petridishes, as well as the original ones incubated at this concentration were examined as described above after five days of incubation. Statistical Method Results are reported as means±standard error and using 1-factor analysis of variance (ANOVA). Example 1 Isolation and identification of cycloviolacin O2. Extraction of plant material and isolation of cycloviolacin O2 was carried out as previously described, with the exception of the use of strong cation exchange chromatography, which effectively captured positively charged cyclotides (FIG. 1). The peak eluting in the salt gradient was collected, and analysed by RP-HPLC and MS, and was found to contain a mixture of peptides. The major peptide was then isolated by means of RP-HPLC, in analogy with previous isolations of cyclotides. The molecular weight of the isolated peptide was determined to 3140.4 Da, congruent with the molecular weight of the earlier reported cycloviolacin O2 (calculated 3140.8). To unambiguously establish its identity, the peptide was digested with trypsin after converting the cysteines of the reduced peptide into its aminopropylated and its acetylated and aminoethylated derivatives. Obtained fragments were then sequenced by MS/MS. After aminopropylation and tryptic cleavage, the sequence of 26 out of 31 amino acids in four identified fragments were successfully determined (sorted after masses, all cysteines converted to their aminopropylated derivatives): VCYR [597.5 (MH+)] VWIPC [674.4 (MH+)]; ISSAIGC [707.5 (MH+)] and NGIPCGESC [994.5 (MH+)]. The remaining five residues were identified first after acetylation, to protect this particular fragment from internal cleavage, followed by aminoethylation and tryptic cleavage to KSKVC [691.3, (MH+)]. Together, these MS data gave the following sequence: cyclo-(VWIPCISSAIGCSCKSKVCYRNGIPCGESC). Example 2 On-Growth Inhibiting (“Antifouling”) Effect of Cycloviolacin O2. The effect of cycloviolacin O2 on settlement and mortality of B. improvisus is shown in FIG. 2. The settlement was inhibited in a dose-dependent manner; at the lowest tested concentration (0.0025 μM), the degree of settlement was the same as in the control (saltwater only) with 68±3% and 67±3% settlement respectively; at 0.025 μM only 21±0.5% of the cyprids settled; and at 0.25 μM cycloviolacin O2 there was a complete inhibition of settlement. The antifouling effect is non-toxic and reversible. No increase in mortality could be detected even at the highest tested concentration (2.5 μM), compared to the control (FIG. 2). Cyprids incubated at this concentration were then moved into petri dishes containing fresh sea water (without cycloviolacin O2), where they regained their normal behaviour, that is to settle, as shown in FIG. 3. After five days of incubation in this solution, 27% of the transferred cyprids had settled. No increase in mortality was observed. Example 3 On-Growth Inhibiting (“Antifouling”) Effects of Viola odorata Extracts Extraction and fractionation of plant material was carried out as previously described (Claeson et al., 1998; Göransson et al., 1999; Broussalis et al.,. 2001). The peptide enriched crude extract obtained following the established fractionation protocol (i.e. Fraction P) was subjected to cation exchange chromatography, to capture the positively charged cyclotides (Fraction I). Both Fraction P and I were tested for antifouling effect (settling and mortality) of Balanus improvisous (FIGS. 4 and 5, respectively). When testing Fraction P, settlement was inhibited in a dose-dependent manner; at lowest concentration (0.001 mg/ml), the degree of settlement was the same as in the control (saltwater only); and at 0.1 mg/ml there was a complete inhibition of settlement. Fraction I also inhibited settlement, but only at 0.1 mg/ml. Fraction I was further purified by means of RP-HPLC and the major cyclotide was isolated (i.e. cycloviolacin O2). The inhibition on settlement of cycloviolacin O2 is dose-dependent and at 0.25 μM there was a complete inhibition. Example 4 A Field Test was Performed as Follows: Fraction P of V. odorata was dissolved in a marine paint (SPF, Loutrec, Lidingö, Sweden) in two different concentrations, 1% and 0.1% (w/w). Plexiglass plates (PMMA, polymethylmetacrylate) of 11×11 cm were then coated with 2 ml in a single layer of respective paint. A set of plates were painted with paint only and served as controls, and all experiments were done in quadruplicates. After drying, the plates were randomly fixed to ropes, attached in one end to a buoy and in the other to a weight, which were deployed in the sea in a bay outside Tjärnö Marine Biological Laboratory (58°53′N, 11°8′E) in August 2003. A set of 4 plates (of each concentration and control) were brought to the lab after 4 and 8 weeks, respectively, and examined for settled barnacles. No settling could be observed for the dishes coated with paint containing Fraction P.
<SOH> BACKGROUND OF THE INVENTION AND PRIOR ART <EOH>The solution of the severe technical and economical problem caused by marine fouling organisms, e.g. barnacles, blue mussels, algae and hydroids, for the shipping industry and in aquaculture has been the use of TBTO (tri-n-butyl tin oxide), copper oxide and herbicides in marine coatings. However, several of these have been recognised to be toxic against non-fouling marine organisms. For example, TBTO has been ascribed effects such as reproduction failure and decrease in adult growth in oysters and the development of imposex in gastropodes such as the dog whelk. Because of these unwanted side effects, the use of TBTO will be stopped by future bans; the International Marine Organisation will recommend a global ban from the year 2005. Therefore it is urgent to find new non-toxic alternatives which exert a specific action on target organisms and which also are biodegradable. Craik et al in WO 01/27147 discloses a novel cyclic molecular framework comprising i.a. so called cyclotides, i.e. cyclic peptides. These compounds are claimed to be usable for treatment or prophylaxis of disease conditions in animals, mammals and plants. WO 00/68265 (Ouelette et al) discloses pharmaceutical compounds based on cyclic peptides. WO 99/21879 (Chang et al) discloses cyclic peptides having antimicrobial and antibacterial activity.
<SOH> SUMMARY OF THE INVENTION <EOH>I.a. in view of the toxicity of the presently used compounds for preventing on-growth on i.a. marine structures, it would be desirable to have access to nontoxic substances, which do not accumulate in the environment, and which do not intervene irreversibly in the natural biological/ecological systems. One promising approach to find new non-toxic antifouling agents has been to explore natural compounds occurring in the marine environment, especially those produced by marine organisms free from fouling. The present inventors have shown that this search among biologically active natural products may be expanded to terrestrial ones as well, by the potent, antifouling effect against barnacles ( Balanus amphitrite , Darwin) of the plant peptide cycloviolacin O2, isolated from the Sweet violet, Viola odorata L. (Violaceae). This peptide is one member of the family of cyclotides, which today consist of almost 50 members. Their main character is their cyclic cystine knot; their amino acid backbone is circular and thus they lack both N- and C-terminals, and they all contain six cysteine residues involved in three disulfide bridges in a knotted arrangement. In combination with their size, ranging from 28-37 amino acid residues, these structural features renders the cyclotide peptides an extreme stability. This structural scaffold, unique for the cyclotides, has previously been shown able to mediate a variety of biological activities, such as antimicrobial and insecticidal effects. The inventors have now surprisingly discovered that the antifouling effect against barnacles of cyclotides, and in particular cycloviolacin O2 is, in contrast to the existing antifouling agents on the market today, is non-toxic and reversible. Thus, the present invention in its broadest aspect, which provides a novel on-growth inhibiting agent comprising a class of compounds having an on-growth inhibiting and preventing effect, is defined in claim 1 . In a further aspect of the invention, an extract from a member of the Violaceae family of plants having on-growth inhibiting and preventing properties, is defined in claim 9 . In a still further aspect there is provided a method of preventing on-growth of organisms in general, including larvae, bacteria, viruses, and fungi on physical objects or on living beings, said method being defined in claim 11 .
20060425
20081209
20070125
64611.0
A61K3812
0
HA, JULIE
ON-GROWTH INHIBITING COMPOUNDS
SMALL
0
ACCEPTED
A61K
2,006
10,539,722
ACCEPTED
Aluminum alloy tube and fin assembly for heat exchangers having improved corrosion resistance after brazing
The present invention provides extruded tubes for heat exchangers having improved corrosion resistance when used alone and when part of a brazed heat exchanger assembly with compatible finstock. The tubes are formed from a first aluminum alloy containing 0.4 to 1.1% by weight manganese, up to 0.01% by weight copper, up to 0.05% by weight zinc, up to 0.2% by weight iron, up to 0.2% by weight silicon, up to 0.01% by weight nickel, up to 0.05% by weight titanium and the balance aluminum and incidental impurities. The fins are formed from a second aluminum alloy containing 0.9 to 1.5% by weight manganese or an alloy of the AA3003 type, this second aluminum alloy further containing at least 0.5% by weight zinc.
1. An aluminum alloy for heat exchanger tubing comprising: 0.4 to 1.1% by weight manganese; up to 0.01% by weight copper; up to 0.05% by weight zinc; up to 0.2% by weight iron; up to 0.2% by weight silicon; up to 0.01% by weight nickel; up to 0.05% by weight titanium; and a balance of aluminum and incidental impurities, wherein said alloy is homogenized at a temperature of between 580 and 620° C. and extruded into tubing and brazed. 2. Brazed extruded heat exchanger tubing formed from an aluminum alloy comprising 0.4 to 1.1% by weight manganese, up to 0.01% by weight copper, up to 0.05% by weight zinc, up to 0.2% by weight iron, up to 0.2% by weight silicon, up to 0.01% by weight nickel, up to 0.05% by weight titanium and the balance aluminum and incidental impurities. 3. A brazed heat exchanger assembly comprising: joined extruded heat exchanger tubes comprising a first aluminum alloy comprising 0.4 to 1.1% percent by weight manganese, up to 0.01% by weight copper, up to 0.05% by weight zinc, up to 0.2% by weight iron, up to 0.2% by weight silicon, up to 0.01% by weight nickel and a balance of aluminum and incidental impurities; and heat exchange fins, comprising a second aluminum alloy comprising 0.9 to 1.5% by weight manganese, an alloy of the AA3003 type, and at least 0.5% by weight zinc, wherein the brazed tubes exhibit good self corrosion protection and the fins are galvanically sacrificial relative to the tubes. 4. A brazed heat exchanger assembly according to claim 3, wherein the manganese weight percent of the first aluminum alloy is related to the manganese weight percent of the second aluminum alloy by the formula Mntube(wt %)>Mnfin (wt %)−0.8 wt % where Mntube is the manganese weight percent of the first aluminum alloy and Mnfin is the manganese weight percent of the second aluminum alloy. 5. A brazed heat exchanger assembly according to claim 3, wherein the second aluminum alloy further comprises less than 0.05% by weight copper. 6. A brazed heat exchanger assembly according to claim 3, where a galvanic current from fin to tube is greater than +0.05 microamps per square centimeter. 7. A brazed heat exchanger assembly according to claims 3, wherein the manganese weight percent of the first aluminum alloy is between 0.6 and 1.19%. 8. A brazed heat exchanger assembly according to claim 7 where the manganese weight percent of the first aluminum alloy is between 0.9 and 1.1%.
TECHNICAL FIELD This invention relates to extruded aluminum alloy products of improved corrosion resistance. It particularly relates to extruded tubes for heat exchangers having improved corrosion resistance after brazing when paired with a compatible finstock. BACKGROUND ART Commercially produced aluminum microport tubing for use in brazed applications is generally produced in the following manner. The extrusion ingot is cast and optionally homogenized by heating the metal to an elevated temperature and then cooling in a controlled manner. The ingot is then reheated and extruded into microport tubing. This is generally thermally sprayed with zinc before quenching, drying and coiling. The coils are then unwound, straightened and cut to length. The tubes obtained are then stacked with corrugated fins clad with filler metal between each tube and the ends are then inserted into headers. The assemblies are then banded, fluxed and dried. The assemblies can be exposed to a braze cycle in batch or tunnel furnaces. Generally, most condensers are produced in tunnel furnaces. The assemblies are placed on conveyor belts or in trays that progress through the various sections of the furnace until they reach the brazing zone. Brazing is carried out in a nitrogen atmosphere. The heating rate of the assemblies depends on the size and mass of the unit but the heating rate is usually close to 20° C./min. The time and temperature of the brazing cycle depends on the part configuration but is usually carried out between 595 and 610° C. for 1 to 30 minutes. A difficulty with the use of aluminum alloy products in corrosive environments, such as automotive heat exchanger tubing, is pitting corrosion. Once small pits start to form, corrosion actively concentrates in the region of the pits, so that perforation and failure of the alloy occurs much more rapidly than it would if the corrosion were more general. With such a large cathode/anode area ratio, the dissolution rate at the active sites is very rapid and tubes manufactured from conventional alloys can perforate rapidly, for example in 2-6 days in the SWAAT test. Zinc coating applied to the tube after extrusion acts to inhibit corrosion of the tube itself. However during the braze cycle, the Zn layer on the extruded tube starts to melt at around 450° C. and once molten, is drawn into the fillet/tube joint through capillary action. This occurs before the Al—Si cladding (fin material) melts at approximately 570° C. and as result the tube-to-fin fillet becomes enriched with Zn, rendering it electrochemically sacrificial to the surrounding fin and tube material. A problem with thermally spraying with zinc before brazing is therefore that the braze fillets become zinc enriched and tend to be the first parts of the units to corrode. As a result, the fins become detached from the tubes, reducing the thermal efficiency of the heat exchanger. In addition to these physical effects, any enrichment of the fillet region with Zn has the effect of reducing the thermal conductivity of the prime heat transfer interface between the tube/fin. There is also a desire to move away from the use of zinc for cost savings and for workplace environment reasons. In an assembly of brazed tubes and fins, it has been found to be advantageous to have the fins corrode first and thereby galvanically protect the tubes. Most fin alloys used with extruded tubes are clad alloys where the core alloys are either 3XXX or 7XXX series alloy based and contain some zinc to make them electronegative, and thereby provide this type of protection. By making the fin sufficiently electronegative, the tubes to which the fins are brazed can be protected, in this way, if the zinc content of the fin is raised sufficiently. However, this has a negative impact on the thermal conductivity of the fin and on the ultimate recyclability of the unit. Furthermore, if the fin material is too electronegative it can corrode too fast and thereby compromises the thermal performance of the entire heat exchanger. Corrosion potential and the difference between corrosion potential of tube and fin have been frequently used to select tube and fin alloys to be galvanically compatible (so that the fin corrodes before the tube). This technique serves to give an approximate galvanic ranking. In order to obtain a true determination of the performance of such combinations it has been found that a measurement of the direction and magnitude of the galvanic current permits a better determination of ultimate performance. Little attempt has been made to optimize the tube-fin combination in heat exchangers based on extruded tubes through the use of appropriate alloys alone, the use of zinc cladding being widely used instead. One constraint on such optimization is that it still also must be possible to extrude the tubes without difficulty. Anthony et al., U.S. Pat. No. 3,878,871, issued Apr. 22, 1975, describes a corrosion resistant aluminum alloy composite material comprising an aluminum alloy core containing from 0.1 to 0.8% manganese and from 0.05 to 0.5% silicon, and a layer of cladding material which is an aluminum alloy containing 0.8 to 1.2% manganese and 0.1 to 0.4% zinc. Sircar, U.S. Pat. No. 5,785,776, issued Jul. 28, 1998, describes a corrosion resistant AA3000 series aluminum alloy containing controlled amounts of copper, zinc and titanium. It has a titanium content of 0.03 to 0.30%, but this level of titanium raises the pressures required for extrusion, which will ultimately lower productivity. In Jeffrey et al., U.S. Pat. No. 6,284,386, issued Sep. 4, 2001, extruded aluminum alloy products having a high resistance to pitting corrosion are described in which the alloy contains about 0.001 to 0.3% zinc and about 0.001 to 0.03% titanium. The alloys preferably also contain about 0.001 to 0.5% manganese and about 0.03 to 0.4% silicon. These extruded products are particularly useful in the form of extruded tubes for mechanically assembled heat exchangers. It is an object of the present invention to provide brazed extruded aluminum alloy tubing for heat exchangers having adequate corrosion resistance without special treatments, such as thermal spraying of the surface with zinc, and also being galvanically compatible with fins joined thereto. It is a further object of the present invention to provide a brazed heat exchanger assembly consisting of extruded tubing and fins in which the tubing alloy is optimized to minimize self corrosion and so that the heat exchanger is protected from overall corrosion by a slow corrosion of the fins. DISCLOSURE OF THE INVENTION The present invention in one embodiment relates to an aluminum alloy for an extruded heat exchanger tube comprising 0.4 to 1.1% by weight manganese, preferably 0.6 to 1.1% by weight manganese, up to 0.01% by weight copper, up to 0.05% by weight zinc, up to 0.2% by weight iron, up to 0.2% by weight silicon, up to 0.01% by weight nickel, up to 0.05% by weight titanium and the balance aluminum and incidental impurities. Further embodiments comprise an extruded tube made from the above alloy and such a tube when brazed. In a yet further embodiment, the invention relates to a brazed heat exchanger comprising joined heat exchanger tubes and heat exchanger fins, where the tubes are extruded tubes made from a first alloy comprising the aluminum alloy described above and the fins are formed from a second alloy comprising an aluminum alloy containing about 0.9 to 1.5% by weight Mn and at least 0.5% by weight Zn, or an aluminum alloy of the AA3003 type, with this second alloy further containing at least 0.5% by weight zinc. Fin alloys of this type have sufficient mechanical properties to meet the heat exchanger construction requirements. It appears that the above unique combination of alloying elements for the tubes gives unexpectedly good self anti-corrosion results for the tubes without the need for any coating of zinc. Also by keeping the manganese content of the tube alloy within 0.8% by weight of that of the fin or greater than or equal to the manganese content in the fin, the fin remains sacrificial, thus protecting the tube and the galvanic corrosion current remains relatively low so that the fin is not corroded so rapidly in service that the thermal performance of the assembly is compromised. The above combination of aluminum alloy fins and extruded tubes when assembled and furnace brazed exhibit a very slow and uniform corrosion of exposed fin surfaces, rather than localized pitting of the tube. The invention is particularly useful when the tubes are microport tubes and the assembly has been furnace brazed in an inert atmosphere. When a brazed heat exchanger is manufactured with these alloy limitations, the heat exchanger tubes can be used without a zincating treatment. The heat exchanger tube does not show self-corrosion in areas remote from the fins (e.g. in between the header and fin pack), and the fins corrode before the tubing but at a rate sufficiently slow to ensure performance of the heat exchanger is maintained for extended periods of time. BRIEF DESCRIPTION OF THE DRAWINGS The present invention will be described in conjunction with the following figures: FIG. 1 is a micrograph of a section of a brazed fin and tube assembly of a fin and tube combination outside the scope of this invention. FIG. 2 is a micrograph of a section of a brazed fin and tube assembly of a further fin and tube combination outside the scope of this invention. FIG. 3 is a micrograph of a section of a brazed fin and tube assembly of a fin and tube combination within the scope of this invention. FIG. 4 is a graph of corrosion potential as a function of manganese content of various extruded tubes and fin materials showing the relationship between manganese content and corrosion behaviour. BEST MODES FOR CARRYING OUT THE INVENTION According to a preferred feature, the fin alloy has less than about 0.05% by weight of copper to make it galvanically compatible with the amount of copper in the extruded tube. Manganese in the tube alloy in the amount specified provides for good self-corrosion protection, along with adequate mechanical strength yet still permits the tubing to be easily extruded. If the manganese is less than 0.4% by weight the tube itself can corrode when coupled with the fin, and if greater than 1.1% by weight the extrudability of the material is adversely affected. When the manganese levels in the tube alloy is less than the manganese in the fin alloy by less than 0.8% by weight (and preferably by less than 0.6% by weight), or is greater than the manganese in the fin alloy, then the fin remains sacrificial to the tube, the corrosion current remains low and therefore the rate of fin corrosion is acceptable. To meet compatibility requirements under a broad range of conditions, it is preferred that the manganese level in the tube therefore be greater than 0.6% by weight. The conditions on manganese can be expressed as a formula, Mntube>Mnfin−0.8, provided that Mntube is in the range 0.4 to 1.1 wt % or more preferably Mntube>Mnfin−0.6, provided that Mntube is in the range 0.4 to 1.1 wt % A particularly preferred tube alloy composition contains 0.9 to 1.1% by weight of manganese, since this represents an alloy that can be extruded into the desired tubes whilst minimizing the manganese concentration differences between tube and fin. The fin also remains sacrificial to the tube if the manganese content is greater than or equal to that of the tube, but because many commercial fin alloys have Mn levels of about 1%, tube alloys having manganese greater than 1% are less generally useful in the present invention because of increased difficulty in extrudability. The relative manganese content of the fin and tube alloys can also be expressed by the measured galvanic corrosion current. The measured galvanic corrosion current from the fin to the tube must preferably exceed +0.05 microamps per square centimeter when measured via ASTM G71-81. The zinc content of the tube must be maintained at a low level to ensure that the fin remains sacrificial to the tube. Even relatively low levels of zinc can alter the galvanic corrosion current and thereby alter this sacrificial relationship. The zinc must therefore be kept at less than 0.05% by weight, more preferably at less than 0.03% by weight. Iron, silicon, copper and nickel all contribute to self-corrosion of the tube and therefore must be below the stated levels. In addition, iron above 0.2% by weight results in poor extrusion surface quality. Titanium additions to the alloy make it difficult to extrude and therefore the titanium should be less than 0.05% by weight. The alloy billets are preferably homogenized between 580 and 620° C. before extrusion into tubes. Example 1 Tests were conducted using the alloys listed in Table 1 below: TABLE 1 Alloy Cu Fe Mg Mn Ni Si Ti Zn A <.001 0.09 <.001 0.22 <.001 0.058 0.017 0.004 B 0.014 0.07 <.001 0.23 <.001 0.07 0.008 0.17 C 0.015 0.51 0.021 0.33 0.001 0.32 0.014 0.007 D 0.001 0.08 <.001 0.98 0.002 0.064 0.014 0.18 E 0.015 0.09 <.001 1.00 <.001 0.07 0.007 0.18 F <.001 0.08 <.001 0.98 0.001 0.071 0.008 0.005 G 0.006 0.11 0.001 0.42 0.001 0.078 0.023 0.027 H 0.006 0.10 0.002 0.63 0.001 0.079 0.021 0.029 I 0.001 0.09 <0.001 0.61 0.002 0.08 0.016 0.002 J 0.0035 0.11 <0.001 0.62 0.002 0.09 0.016 0.002 K 0.08 0.59 <0.001 1.05 <0.001 0.23 0.01 0.01 These alloys were cast into 152 mm diameter billets. Alloy C was a commercial 3102 alloy and Alloy K a commercial 3003 alloy. The billets were further machined down to 97 mm in diameter and homogenized between 580 and 620° C. They were then extruded into tubes. Samples of the tubing were subjected to a simulated brazing process and then subjected to a SWAAT test using ASTM standard G85 Annex 3 and galvanic corrosion currents were measured against a standard finstock material manufactured from AA3003 alloy containing 1.5% by weight added zinc and clad with AA4043 alloy that had also been given a simulated braze cycle, in accordance with ASTM G71-81. The results are shown in Table 2 below: TABLE 2 SWAAT life Galvanic corrosion current Alloy (days) (μA/cm2)* A 56 −3.2 B <20 D 56 −2.4 E <20 F 56 0.2 G 55 3.1 H 55 5 I 55 J 55 F unhomogenized 21 C zincated 56 −26.9 K <5 *+ve corrosion current = current flow from fin to tube −ve corrosion current = current flow from tube to fin The results of a test carried out on a zincated 3102 tube (e.g. Alloy C, Extruded and zincated) are shown for comparison. In Table 2, a SWAAT life of 55 to 56 days indicated no perforation of the tube by self-corrosion and a positive galvanic corrosion current indicates that the fin corrodes preferentially. A small value indicates a low rate of corrosion. A sample of alloy F was also extruded without homogenization and subjected to a SWAAT test. Alloys A, D have compositions outside the claimed range. They nevertheless show excellent SWAAT performance indicating that for self-corrosion these alloys would be also be acceptable even when the Mn is less than the range of this invention. It is believed that this is a result of the low Cu, Fe and Ni in these alloys. The amount of Mn present has no significant effect on the self-corrosion behaviour. However, the galvanic corrosion current is unacceptable for these compositions. This is believed to be due to manganese levels that are too low in one case and zinc levels that are too high in the other. Both these elements are important in ensuring acceptable performance of the fin-tube galvanic couple. Samples of extruded heat exchanger tubing made from alloys A, D and F were brazed into heat exchanger assemblies using fins manufactured from AA3003 with 1.5% Zn. The AA3003 composition had 1.1% by weight Mn. The assemblies were then exposed to SWAAT testing and examined metallographically. The results are shown in FIGS. 1 to 3. FIGS. 1 and 2, correspond to alloys A and D tubing incorporated into a heat exchanger after 8 and 7 days exposure respectively to the SWAAT test. Substantial pitting corrosion of the tubes near the fin is observed, although in tests of the tube alone, no pitting occurred after long exposure. Figure shows a combination of tubing of Alloy F with the same fin stock (i.e. a combination within the scope of this invention), in which there was no through-thickness pitting until after 20 days SWAAT exposure (compared to 7 or 8 days for the combinations outside the scope of the invention). A 20 day life is considered under this test to be adequate performance. Alloys B, E and K have copper outside the desired range and show poor SWAAT results, indicating that alloys with such a copper level would suffer from excessive self-corrosion, whether or not the manganese composition met the requirements. Alloy D has a zinc level that exceeds the desired range and shows that although the manganese level is within the desired range, the fin-tube galvanic corrosion current is negative and the tube would therefore corrode first. The self-corrosion performance (SWAAT test) is acceptable, but because of the fin-tube galvanic corrosion, the overall assembly would fail. Alloy K also has Fe and Si above the required amounts. Alloys F, G, I and J lie within the claimed range. Alloys F, G and H exhibits acceptable performance on both the SWAAT tests on the tubing and the galvanic corrosion behaviour. Alloys I and J show good SWAAT behaviour, and lack any significant-levels of elements that would give poor galvanic current performance. Alloy F in un-homogenized condition however, shows unacceptable SWAAT performance indicating that homogenization of the product is a preferred process step to achieve good performance. Finally Alloy C was a standard tube alloy and was tested in zinc-coated form. As expected this gave good SWAAT performance, since the zinc layer is sacrificial to the entire tube and so overcomes the negative effects of elements such as copper. The negative galvanic corrosion current in this case indicates that the zinc surface layer is sacrificial as noted above. Alloy C had manganese less than the desired range and only performs because of the presence of the zinc coating. However, as noted above, zinc has a number of negative features that mean it is not used in the present invention. Example 2 In order to show the effect of changes in fin Mn composition, the corrosion potential of the various tube alloys of Example 1 were compared to the corrosion potential of various fin alloys. A necessary condition for the fin to be sacrificial with respect to the tube is that the tube corrosion potential be clearly less negative than the fin corrosion potential. The corrosion potential of the tube alloys of Example 1 were determined and plotted on a graph in FIG. 4 showing the variation with manganese content. Curves are shown for the tube alloys in the as-cast condition as well as following homogenization at 580 or 620° C. Various fin alloys (identified as samples 1 to 3) based on the commercial AA3003 with 1.5% Zn composition, but having different Mn compositions within the preferred Mn range of the present invention, were prepared by book mould casting, processed to finstock gauge by hot and cold rolling. They were then subjected to a simulated braze cycle and the corrosion potential measured. The compositions and measured corrosion potentials are given in Table 3. TABLE 3 Sam- ple Ecorr No Cu Fe Mg Mn Ni Si Ti Zn (mV) 1 0.12 0.53 0.010 1.08 0.004 0.29 0.011 1.50 −790 2 0.133 0.55 0.0003 0.9 0.002 0.34 0.007 1.61 −797 3 0.13 0.55 0.0004 1.24 0.002 0.33 0.006 1.63 −786 The corrosion potentials for samples 1 to 3 are shown as horizontal dashed lines on FIG. 4. In order that the fin material be sacrificial compared to the tube alloy the fin corrosion potential must be more negative that the tube alloy corrosion potential. For practical reasons and to account for inevitable variation in materials, only tube alloy compositions that have corrosion potentials that exceed (are less negative than) those of the fin by 25 mV are selected. From FIG. 4, therefore, the minimum tube manganese level compatible with each of the three fin manganese compositions is determined. These are given in Table 4, along with the corresponding tube manganese composition and the minimum acceptable tube manganese in accordance with the formula: Mntube>Mnfin−0.8 wt % except 0.4<=Mntube<=1.1 wt % TABLE 4 Measured Calculated minimum minimum acceptable Mn acceptable Mn Fin sample Mn in fin in tube in tube 1 1.08 0.43 0.40 2 0.9 0.40 0.40 3 1.24 0.48 0.44
<SOH> BACKGROUND ART <EOH>Commercially produced aluminum microport tubing for use in brazed applications is generally produced in the following manner. The extrusion ingot is cast and optionally homogenized by heating the metal to an elevated temperature and then cooling in a controlled manner. The ingot is then reheated and extruded into microport tubing. This is generally thermally sprayed with zinc before quenching, drying and coiling. The coils are then unwound, straightened and cut to length. The tubes obtained are then stacked with corrugated fins clad with filler metal between each tube and the ends are then inserted into headers. The assemblies are then banded, fluxed and dried. The assemblies can be exposed to a braze cycle in batch or tunnel furnaces. Generally, most condensers are produced in tunnel furnaces. The assemblies are placed on conveyor belts or in trays that progress through the various sections of the furnace until they reach the brazing zone. Brazing is carried out in a nitrogen atmosphere. The heating rate of the assemblies depends on the size and mass of the unit but the heating rate is usually close to 20° C./min. The time and temperature of the brazing cycle depends on the part configuration but is usually carried out between 595 and 610° C. for 1 to 30 minutes. A difficulty with the use of aluminum alloy products in corrosive environments, such as automotive heat exchanger tubing, is pitting corrosion. Once small pits start to form, corrosion actively concentrates in the region of the pits, so that perforation and failure of the alloy occurs much more rapidly than it would if the corrosion were more general. With such a large cathode/anode area ratio, the dissolution rate at the active sites is very rapid and tubes manufactured from conventional alloys can perforate rapidly, for example in 2-6 days in the SWAAT test. Zinc coating applied to the tube after extrusion acts to inhibit corrosion of the tube itself. However during the braze cycle, the Zn layer on the extruded tube starts to melt at around 450° C. and once molten, is drawn into the fillet/tube joint through capillary action. This occurs before the Al—Si cladding (fin material) melts at approximately 570° C. and as result the tube-to-fin fillet becomes enriched with Zn, rendering it electrochemically sacrificial to the surrounding fin and tube material. A problem with thermally spraying with zinc before brazing is therefore that the braze fillets become zinc enriched and tend to be the first parts of the units to corrode. As a result, the fins become detached from the tubes, reducing the thermal efficiency of the heat exchanger. In addition to these physical effects, any enrichment of the fillet region with Zn has the effect of reducing the thermal conductivity of the prime heat transfer interface between the tube/fin. There is also a desire to move away from the use of zinc for cost savings and for workplace environment reasons. In an assembly of brazed tubes and fins, it has been found to be advantageous to have the fins corrode first and thereby galvanically protect the tubes. Most fin alloys used with extruded tubes are clad alloys where the core alloys are either 3XXX or 7XXX series alloy based and contain some zinc to make them electronegative, and thereby provide this type of protection. By making the fin sufficiently electronegative, the tubes to which the fins are brazed can be protected, in this way, if the zinc content of the fin is raised sufficiently. However, this has a negative impact on the thermal conductivity of the fin and on the ultimate recyclability of the unit. Furthermore, if the fin material is too electronegative it can corrode too fast and thereby compromises the thermal performance of the entire heat exchanger. Corrosion potential and the difference between corrosion potential of tube and fin have been frequently used to select tube and fin alloys to be galvanically compatible (so that the fin corrodes before the tube). This technique serves to give an approximate galvanic ranking. In order to obtain a true determination of the performance of such combinations it has been found that a measurement of the direction and magnitude of the galvanic current permits a better determination of ultimate performance. Little attempt has been made to optimize the tube-fin combination in heat exchangers based on extruded tubes through the use of appropriate alloys alone, the use of zinc cladding being widely used instead. One constraint on such optimization is that it still also must be possible to extrude the tubes without difficulty. Anthony et al., U.S. Pat. No. 3,878,871, issued Apr. 22, 1975, describes a corrosion resistant aluminum alloy composite material comprising an aluminum alloy core containing from 0.1 to 0.8% manganese and from 0.05 to 0.5% silicon, and a layer of cladding material which is an aluminum alloy containing 0.8 to 1.2% manganese and 0.1 to 0.4% zinc. Sircar, U.S. Pat. No. 5,785,776, issued Jul. 28, 1998, describes a corrosion resistant AA3000 series aluminum alloy containing controlled amounts of copper, zinc and titanium. It has a titanium content of 0.03 to 0.30%, but this level of titanium raises the pressures required for extrusion, which will ultimately lower productivity. In Jeffrey et al., U.S. Pat. No. 6,284,386, issued Sep. 4, 2001, extruded aluminum alloy products having a high resistance to pitting corrosion are described in which the alloy contains about 0.001 to 0.3% zinc and about 0.001 to 0.03% titanium. The alloys preferably also contain about 0.001 to 0.5% manganese and about 0.03 to 0.4% silicon. These extruded products are particularly useful in the form of extruded tubes for mechanically assembled heat exchangers. It is an object of the present invention to provide brazed extruded aluminum alloy tubing for heat exchangers having adequate corrosion resistance without special treatments, such as thermal spraying of the surface with zinc, and also being galvanically compatible with fins joined thereto. It is a further object of the present invention to provide a brazed heat exchanger assembly consisting of extruded tubing and fins in which the tubing alloy is optimized to minimize self corrosion and so that the heat exchanger is protected from overall corrosion by a slow corrosion of the fins.
<SOH> BRIEF DESCRIPTION OF THE DRAWINGS <EOH>The present invention will be described in conjunction with the following figures: FIG. 1 is a micrograph of a section of a brazed fin and tube assembly of a fin and tube combination outside the scope of this invention. FIG. 2 is a micrograph of a section of a brazed fin and tube assembly of a further fin and tube combination outside the scope of this invention. FIG. 3 is a micrograph of a section of a brazed fin and tube assembly of a fin and tube combination within the scope of this invention. FIG. 4 is a graph of corrosion potential as a function of manganese content of various extruded tubes and fin materials showing the relationship between manganese content and corrosion behaviour. detailed-description description="Detailed Description" end="lead"?
20060413
20100824
20061019
88181.0
C22C2100
1
AUSTIN, AARON
ALUMINUM ALLOY TUBE AND FIN ASSEMBLY FOR HEAT EXCHANGERS HAVING IMPROVED CORROSION RESISTANCE AFTER BRAZING
UNDISCOUNTED
0
ACCEPTED
C22C
2,006
10,539,918
ACCEPTED
Method for the production of crystalline forms and crystalline forms of optical enantiomers of modafinil
The invention relates to a process for the preparation of crystalline forms of the optical enantiomers of modafinil, comprising stages comprising: i) dissolving one of the optical enantiomers of modafinil in a solvent other than ethanol, ii) crystallising the modafinil enantiomer, iii) recovering the crystalline form of the modafinil enantiomer so obtained. The invention also relates to a process for the preparation of the optical enantiomers of modafinil.
1. Process for preparation of crystalline forms of the optical enantiomers of modafinil, comprising the following stages: i) dissolving one of the optical enantiomers of modafinil in a solvent other than ethanol, ii) crystallising the enantiomer of modafinil, iii) recovering the crystalline form of the enantiomer of modafinil so obtained. 2. Process according to claim 1, in which the modafinil enantiomer is the laevorotatory enantiomer. 3. Process according to claim 1, in which the modafinil enantiomer is the dextrorotatory enantiomer. 4. Process according to claim 1, in which the crystalline form obtained is a polymorphic form. 5. Process according to claim 1, in which crystallisation is performed under kinetic or thermodynamic conditions. 6. Preparation process according to claim 5, in which crystallisation is performed by precipitation, possibly in the presence of seeds of crystals of the desired crystalline form. 7. Preparation process according to claim 5, in which crystallisation consists of cooling the solution obtained in stage i). 8. Process according to claim 7, in which cooling is slow. 9. Process according to claim 7, in which cooling is fast. 10. Process according to claim 8, in which the solvent used in stage i) is selected from acetone, 1-4 dioxan, ethyl acetate, ortho, meta or para xylene, or a mixture of ortho, meta and/or para xylene, and the polymorphic form so obtained is then described as Form I. 11. Process according to claim 9, in which the solvent used in stage i) is selected from methanol, water and alcohol/water mixtures, the crystalline form then obtained being described as Form I. 12-30. (canceled) 31. Process for the preparation of optically active modafinil from modafinil acid, comprising the following stages: i) separating the two optical enantiomers of (±)-modafinil acid and recovering at least one of the enantiomers, ii) placing one of the two enantiomers obtained in contact with a lower alkyl haloformate in the presence of alcohol or an organic base, iii) recovering the product obtained, iv) converting the ester obtained into an amide, v) recovering the product obtained in stage iv). 32. Process according to claim 31, in which the haloformate is a lower alkyl chloroformate. 33. Process according to claim 32, in which the lower alkyl chloroformate is methyl chloroformate. 34. Process according to any claim 31, in which the base used in stage ii) is selected from triethylamine, diisopropylamine, diethylmethylamine, DBU. 35. Process according to claim 31, in which the alcohol is methanol. 36. Process according to claim 31, in which stage iv) is carried out in the presence of a lower aliphatic alcohol. 37. Process according to claim 31, in which resolution of the optical enantiomers of (±)-modafinil acid in stage i) is carried out through a preferential crystallisation process. 38. Process according to claim 37, in which the process of resolving the two optical enantiomers of (±) modafinil acid or the salts of the same is a seeded process, the said process comprising the following stages: a) homogenising at a temperature TD a combination comprising the racemic mixture of crystals of the first enantiomer of modafinil acid and solvent in the form of conglomerate, for which the defining point E defined by the concentration and temperature variables TD lies in the monophase domain of the dilute solution, b) rapidly cooling the solution prepared in stage a) initially at the temperature TD down to temperature TF, c) seeding the solution in stage b) during or at the end of cooling (TF) with very pure seeds of the first enantiomer, d) harvesting the crystals of the first enantiomer, e) adding the racemic mixture of crystals in the form of conglomerate to the mother liquors resulting from the harvest performed in stage d) and homogenising the new combination by heating to a temperature TD, in such a way that the defining point E′ is symmetrical for E with respect to the plane of the racemic mixture of the solvent, (−)-antipode, (+)-antipode system, the said point E′ being located in the monophase domain of the dilute solution, f) rapidly cooling the solution obtained in stage e), initially at the temperature TD, down to the temperature TF, g) seeding the solution obtained in stage f) using very pure seeds of the second enantiomer, h) harvesting crystals of the second enantiomer, i) adding the racemic mixture in the form of a conglomerate of crystals to the mother liquors resulting from the crystal harvests performed in stage h) and homogenising the new combination heating to a temperature TD to obtain a composition which is identical to that of the combination having the initial defining point E, j) repeating stages a), b), c), d), e), f), h) and j) in order to obtain the first and then the second of the two enantiomers in succession. 39. Process according to claim 37, in which the process of separation of the two optical enantiomers of (±)-modafinil acid or salts of the same by preferential crystallisation is a self-seeded AS3PC process, the said process comprising the following stages: a) creating a combination comprising the racemic mixture of crystals of the first enantiomer of modafinil acid and solvent, in the form of conglomerate, for which the defining point E defined by the concentration and temperature variables TB is located in the two-phase domain of the enantiomer in excess and is in equilibrium with its saturated solution, b) applying a function for programming cooling from the temperature of the two-phase mixture prepared in stage a), the said programming function being such that the mother liquors remain slightly supersaturated encouraging growth of the enantiomer present in the form of crystals while preventing spontaneous nucleation, of the second enantiomer present in the solution, c) adopting a stirring speed which increases slightly over time throughout the period of crystal growth in stage b) in such a way that the stirring speed is at all times sufficiently slow to encourage growth of the first enantiomer while preventing the generation of excessively large shear forces giving rise to uncontrolled nucleation and sufficiently fast to produce a homogeneous suspension and rapid renewal of the mother liquor about each crystallite of the first enantiomer, d) harvesting crystals of the first enantiomer, e) adding the racemic mixture of crystals in the form of conglomerate to the mother liquors resulting from the harvest performed in stage d) and bringing the new combination to a temperature plateau TB for the time necessary to achieve thermodynamic equilibrium so that the defining point E′ is symmetrical for E with respect to the plane of the racemic mixtures of the solvent, (−)-antipode, (+)-antipode system, the said point E′ being located within the two-phase domain of the second enantiomer in excess and in equilibrium with its saturated solution, f) applying the same cooling programming function as in stage b) to the two-phase mixture prepared in stage e) containing the second enantiomer in such a way that the mother liquors remain slightly supersaturated during crystallisation so as to encourage growth of the enantiomer present in the form of crystals while preventing spontaneous nucleation of the first enantiomer present in the solution, g) adopting a stirring speed which increases slightly over time throughout the period of crystalline growth in stage f) in such a way that at all times it is sufficiently slow to encourage growth of the second enantiomer while avoiding generating excessively large shear forces bringing about uncontrolled nucleation, and sufficiently fast to achieve a homogeneous suspension and rapid renewal of the mother liquor around each crystallite of the second enantiomer, h) harvesting crystals of the second enantiomer, i) adding the racemic mixture of crystals in the form of conglomerate to the mother liquors resulting from the crystal harvest performed in stage g) in order to obtain a combination whose composition is identical to that of the initial combination E, j) repeating stages a), b), c), d), e), f) g), h) and i) to obtain the first and then the second of the two enantiomers in succession. 40. Process according to claim 39, characterised in that in stage a) choice of the solvent or solvents and the working temperature range are defined in such a way as to have simultaneously: antipodes forming a conglomerate and of which any racemate is metastable within the working temperature range, liquors which are sufficiently concentrated but of low viscosity and low vapour pressure, the absence of solvolysis and racemisation, stability of the solvates if these are present at equilibrium and they are in the form of separable enantiomers. 41. Process according to claim 39, characterised in that in stages (a) and (e) temperature TB is higher than temperature TL for homogenisation of the quantity of racemic mixture present in the initial suspension, and in that from the curve for the variation of THOMO in relation to the enantiomer excess and for a constant concentration of racemic mixture XL the said temperature TB is defined in such a way that the mass of fine crystals of the first enantiomer in stages (a) and (i) and the second enantiomer in stage (e) in equilibrium with their saturated solutions represents at most 50% and preferably between approximately 25% and 40% of the expected harvest. 42. Process according to claim 39, characterised in that in stages (b) and (f) the programming function for cooling the temperature TB to TF appropriate for the experimental assemblage is defined in such a way as to: achieve slight supersaturation throughout the period for crystallisation of the enantiomer present in the form of crystals at the start of each cycle, this slight supersaturation bringing about gentle growth and secondary nucleation, achieve maximum supersaturation of the other enantiomer at TF without primary nucleation, obtaining a harvest of crystals in stages (d) and (h) which after addition of the racemic mixture and making-up in stages (e) and (i), makes it possible for the operations to be cyclical. 43. Process according to claim 42, characterised in that the cooling programming function is determined for its part from TL to TF by cooling of the solution of concentration XL from TL+1° C. to TF, TF being below TL−(THOMO−TL), in order to obtain a stable saturated solution without primary nucleation while allowing a double harvest of the initial enantiomer excess and in that the said cooling programming function is determined for its part from TB to TL by extrapolation of the same function as determined from TL+1° C. to TF. 44. Process according to claim 39, characterised in that in the two stages (b) and (f) the heat release accompanying deposition of the first enantiomer and the second enantiomer is incorporated into the cooling programming function. 45. Process according to claim 39, characterised in that in stages (e) and (i) shortages of solvent are made up. 46. Process according to claim 39, characterised in that in stages (a), (e) and (i) the fine crystals of racemic mixture in the form of conglomerate, which are added, were before being introduced subjected to prior treatment accelerating the dissolution stage, such as grinding and sieving, treatment with ultrasound waves or partial lyophilisation. 47. Process according to claim 39, characterised in that in stages (a), (e) and (i), the stirring speed is increased. 48. Process according to claim 38 or 39, in which the solvent used in stage a) is ethanol, 2-methoxyethanol or methanol. 49. Process according to claim 48, in which the temperature TF lies between 0 and 40° C. 50. Process according to claim 48, in which the concentration of the racemic mixture in stage a) lies between 2 and 50% by mass. 51. Process according to claim 48, in which the enantiomer excess in stage a) lies between 1 and 50% by mass. 52. Process according to claim 51, in which the temperature TB lies between 25° C. and 50° C. 53. Process according to claim 48, in which duration of the temperature plateau TB lies between 15 and 60 min. 54. Process for preparation of one of the enantiomers of modafinil comprising the following stages: a) separating the two optical enantiomers of (±)-modafinil acid or salts of the same through a preferential crystallisation process as defined in claim 35, b) converting the said enantiomer to an amide, c) recovering the modafinil enantiomer obtained. 55. Process according to claim 54, in which stage b) is carried out in two stages: b1) conversion of the said enantiomer into a lower alkyl ester, b2) converting the product obtained in stage b1) to an amide. 56-63. (canceled) 64. Polymorphic form of the laevorotatory enantiomer of modafinil, characterized in that it produces an X-ray diffraction pattern comprising intensity peaks at the interplanar spacings: 8.54, 4.44, 4.27, 4.02, 3.98 (Å). 65. Polymorphic form according to claim 64, characterised in that it produces an X-ray diffraction spectrum comprising intensity peaks at the interplanar spacings: 13.40, 8.54, 6.34, 5.01, 4.68, 4.62, 4.44, 4.27, 4.20, 4.15, 4.02, 3.98, 3.90, 3.80, 3.43 (Å). 66. A pharmaceutical composition comprising a polymorphic form of the laevorotatory enantiomer of modafinil of claim 64. 67. A pharmaceutical composition comprising a polymorphic form of the laevorotatory enantiomer of modafinil of claim 64 in association with a pharmaceutically acceptable carrier. 68. A pharmaceutical composition comprising a polymorphic form of the laevorotatory enantiomer of modafinil of claim 65. 69. A pharmaceutical composition comprising a polymorphic form of the laevorotatory enantiomer of modafinil of claim 65 in association with a pharmaceutically acceptable carrier. 70. A method for prevention or treatment of a disease selected from hypersomnia; idiopathic hypersomnia; hypersomnia in patients affected by a cancer treated with morphine analgesics to relieve pain; sleep apnoeas; excessive somnolence associated with a disease; obstructive sleep apnoeas; narcolepsy; somnolence; excessive somnolence; excessive somnolence associated with narcolepsy; disturbances of the central nervous system; Parkinson's disease; cerebral ischaemia; alertness disturbances; alertness disturbances associated with Steinert's disease; attention disturbances; attention deficit hyperactivity disorder (ADHD); fatigue associated with multiple sclerosis and other degenerative diseases; depression; the depressive condition associated with low exposure to sunlight; schizophrenia; rotating shift work and time shift disorders; eating disturbances in which modafinil acts as an appetite stimulant, said method comprising administering to said patient a polymorphic form of the laevorotatory enantiomer of modafinil of claim 64. 71. A method for prevention or treatment of a disease selected from hypersomnia; idiopathic hypersomnia; hypersomnia in patients affected by a cancer treated with morphine analgesics to relieve pain; sleep apnoeas; excessive somnolence associated with a disease; obstructive sleep apnoeas; narcolepsy; somnolence; excessive somnolence; excessive somnolence associated with narcolepsy; disturbances of the central nervous system; Parkinson's disease; cerebral ischaemia; alertness disturbances; alertness disturbances associated with Steinert's disease; attention disturbances; attention deficit hyperactivity disorder (ADHD); fatigue associated with multiple sclerosis and other degenerative diseases; depression; the depressive condition associated with low exposure to sunlight; schizophrenia; rotating shift work and time shift disorders; eating disturbances in which modafinil acts as an appetite stimulant, said method comprising administering to said patient a polymorphic form of the laevorotatory enantiomer of modafinil of claim 65. 72. A method of stimulating cognitive function in a patient comprising administering to said patient a polymorphic form of the laevorotatory enantiomer of modafinil of claim 64. 73. A method of stimulating cognitive function in a patient comprising administering to said patient a polymorphic form of the laevorotatory enantiomer of modafinil of claim 65. 74. A composition comprising a laevorotatory enantiomer of modafinil that produces an X-ray diffraction pattern comprising intensity peaks at the interplanar spacings: 8.54, 4.44, 4.27, 4.02, 3.98 (Å). 75. A composition of claim 74, wherein the laevorotatory enantiomer of modafinil produces an X-ray diffraction spectrum comprising intensity peaks at the interplanar spacings: 13.40, 8.54, 6.34, 5.01, 4.68, 4.62, 4.44, 4.27, 4.20, 4.15, 4.02, 3.98, 3.90, 3.80, 3.43 (Å). 76. A composition of claim 74, further comprising a pharmaceutically acceptable carrier. 77. A composition of claim 75, further comprising a pharmaceutically acceptable carrier.
The invention relates to a process for obtaining crystalline forms of the enantiomers of modafinil, and the crystalline forms which it is possible to obtain according to this process. The invention also relates to a new process for the preparation of optical enantiomers of modafinil from (±) modafinil acid. U.S. Pat. No. 4,177,290 describes modafinil in racemic form, also known as (±) 2-(benzhydrylsulphinyl)acetamide or (±) 2-[(di-phenylmethyl)sulphinyl] acetamide, as a compound having properties of stimulating the central nervous system. U.S. Pat. No. 4,927,855 describes the two optical enantiomers of modafinil. More particularly it describes the laevorotatory enantiomer and its use as an antidepressant or stimulant agent in the treatment of hypersomnia and disorders associated with Alzheimer's disease. The process for the preparation of the two optical enantiomers of modafinil from (±) modafinil acid or (±)-benzhydrylsulphinylacetic acid described in this document is illustrated in the following synthesis diagram: This process comprises carrying out resolution of the optical enantiomers of (±) modafinil acid in a first stage via the formation of diastereoisomers with the optically active agent α-methylbenzylamine. The (−)-α-methylbenzylamine-(−)-benzhydrylsulphinyl acetate is then converted to (−)-benzhydrylsulphinylacetic acid by acid hydrolysis. The latter is esterified in the presence of dimethyl sulphate and then converted to amide in the presence of ammonia (gas). The (−) or I (laevorotatory) enantiomer of modafinil is obtained through this process with an overall yield of 5.7% in relation to the (±) modafinil acid, calculated on the basis of the yields corresponding to each stage. The term “enantiomer” refers to stereoisomer molecules which are non-superimposable mirror images of each other. Enantiomers are typically designated using either (+) and (−) or (d) and (I), which indicates optical rotating power in the chiral centre. Stereoisomerism may also be denoted by either (D) or (L) or by (R) and (S), these being descriptive of the absolute configuration. In what follows the laevorotatory enantiomer of modafinil will be referred to without distinction as the I or (−) enantiomer, and the dextrorotatory enantiomer will for its part be referred to as the d or (+) enantiomer. A process through which different crystalline forms of the optical enantiomers of modafinil can be obtained has now been discovered. More specifically the inventors have shown that the crystalline form obtained mainly depends on the nature of the crystallisation solvent used. For the purposes of this description the term “crystalline form” refers to either a polymorphic form or a solvate, without distinction. By “polymorphic form” is meant an organised structure involving only molecules of the solute, having a characteristic crystalline signature. The term “solvate” relates to an organised structure having a characteristic crystalline signature which involves both molecules of solute and molecules of solvent. Solvates having one molecule of solute for one molecule of solvent are called true solvates. Furthermore the inventors have shown that l-modafinil and d-modafinil prepared according to the conditions described in U.S. Pat. No. 4,177,290 are obtained in the form of one polymorphic form described as form I, which corresponds to the thermodynamically most stable polymorphic form under normal temperature and pressure conditions. Form I has the X-ray diffraction spectrum below in which d represents the interplanar spacing and the ratio (I/Io) the relative intensity. CRL 40982 FORM I 2 Theta (degrees) d (Å) I/Io (%) 9.8 13.40 32 15.4 8.54 87 20.8 6.34 24 26.4 5.01 14 28.3 4.68 19 28.7 4.62 16 29.9 4.44 45 31.1 4.27 100 31.6 4.20 23 32 4.15 14 33.1 4.02 78 33.4 3.98 84 34.1 3.90 16 35.1 3.80 15 39 3.43 22 Diffractometer: Miniflex Rigaku (Elexience) The crystalline forms of a given compound generally have physical, pharmaceutical, physiological and biological properties which differ from each other very sharply. In this respect the crystalline forms of optically active modafinil, in particular the polymorphic forms, are of interest in that they have different and advantageous properties in comparison with form I. According to another aspect, a new process for the preparation of the optical enantiomers of modafinil from (±)-modafinil acid has now been discovered, and this process can be used to isolate each enantiomer in yields and with an optical purity which are markedly superior to those described in U.S. Pat. No. 4,927,855. In a particularly advantageous fashion a process for resolution of the two optical enantiomers of (±)-modafinil acid by preferential crystallisation, which is advantageously applicable to the preparation scale, has now been developed. This process for the resolution of (±)-modafinil acid has many advantages: it avoids the use of a costly chiral intermediate whose further preparation involves losses which are rarely less than 10% (De Min., M., Levy, G. and Michwater J.-C., 1988, J. Chem. Phys. 85, 603-19), the two enantiomers are obtained directly, contrary to the method which makes use of conventional resolution through the formation of diastereoisomer salts, the yield is theoretically quantitative as a result of successive recycling of the mother liquors, Purification of the crude enantiomer crystals is easy. The invention therefore aims to provide a process of preparation for crystalline forms of the enantiomers of modafinil. The invention also aims to provide a new process for preparation of the optical enantiomers of modafinil, and in particular the laevorotatory enantiomer of modafinil. Process for the Preparation of 1-Modafinil Polymorphs These objects and others are accomplished by this invention which relates more particularly, in a first aspect, to a process for the preparation of crystalline forms of the optical enantiomers of modafinil, comprising the following stages: i) dissolving one of the optical enantiomers of modafinil in a solvent other than ethanol, ii) crystallising the said enantiomer of modafinil, and iii) recovering the crystalline form of the said enantiomer of modafinil so obtained. For the purposes of this invention, the solvent used in stage i) of the process, also referred to as the “recrystallisation solvent”, is a solvent capable of bringing about crystallisation of the said optical enantiomer of modafinil, preferably at atmospheric pressure. In other words it comprises any solvent A which with at least one of the enantiomers is capable of forming at a given pressure in a first temperature and concentration domain, a monophase system comprising at least one of the enantiomers in dilute solution in solvent A, in a second temperature and concentration domain which is not the same as the former, a second two-phase system comprising crystals of the said enantiomer in the presence of saturated solution, the two domains being separated from each other by the solubility curve of the said enantiomer T (° C.)=f (enantiomer concentration) at the pressure considered. In general the crystallisation in stage ii) comprises changing from the monophase system to the two-phase system by varying the temperature and concentration. By way of a non-restrictive illustration of solvents which may be suitable for the recrystallisation process according to the invention mention may in particular be made of alcoholic solvents, carboxylic acid ester solvents, ether solvents, chlorinated solvents, aromatic solvents, and lower aliphatic ketone solvents. Other solvents are for example, carboxylic acid solvents, aprotic polar solvents, alicyclic hydrocarbons, aliphatic hydrocarbons, carbonates, heteroaromatics and water. Among the alcoholic solvents mention may be made in particular of lower alkyl alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-methyl-2-pentanol, 1,2-propanediol and t-amyl alcohol, with methanol, propanol and isopropanol being particularly preferred. Among solvents of the carboxylic acid ester type mention may be made in particular of alkyl acetates such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate and alkyl formates such as ethyl formate, with ethyl acetate being particularly preferred. Useful ether recrystallisation solvents are diethylether, tetrahydrofuran (THF), dioxan, dibutylether, isopropyl ether, t-butylmethylether and tetrahydropyran, with tetrahydrofuran being particularly preferred. Among the chlorinated solvents mention may be made of chlorinated hydrocarbons, in particular chloroform, 1,2-dichloroethane, dichloromethane and chlorinated aromatics such as chlorobenzene. As examples of aromatic solvents mention may be made of ortho, meta, and para xylene or a mixture of ortho, meta and para xylene, methoxybenzene, nitrobenzene, trifluorotoluene and toluene, with ortho, meta and para xylene being particularly preferred. Useful ketone solvents are solvents such as acetone, methylethylketone, methylisobutylketone, butan-2-one, cyclopentanone, isobutylmethylketone, 2-pentanone, 3-pentanone. As an example of a carboxylic acid solvent, mention may be made in particular of acetic acid. By way of an example of a heteroaromatic solvent, mention may be made in particular of pyridine. Examples of aprotic polar solvents are in particular acetonitrile, propionitrile, 4-methylmorpholine, N,N-dimethylacetamide, nitromethane, triethylamine, N-methyl-pyrrolidone (NMP). Examples of aliphatic hydrocarbons are in particular heptane, 2,2,4-trimethylpentane. Examples of alicyclic hydrocarbons are in particular cyclopentane, cyclohexane. Examples of carbonates are in particular alkyl carbonates such as dimethyl carbonate. According to a preferred embodiment of the process according to the invention the crystallisation solvents are selected from acetone, methanol, 1-4 dioxan, ethyl acetate, mixtures of ortho, meta, para xylene, isopropanol, n-propanol, dimethyl carbonate, tetrahydrofuran, chloroform and methylethylketone, water and alcohol/H2O mixtures. Thus, crystalline forms of the optical enantiomers of modafinil can be obtained by recrystallisation of the enantiomers in particular solvents, where the nature and possibly the conditions of crystallisation mainly determine the type of crystalline form obtained. Through its interaction with functional groups and electron-attracting or electron-donor substituents the recrystallisation solvent can in fact encourage certain molecular arrangements which give rise to a particular crystalline form under given crystallisation conditions. Generally the recrystallisation solvent used in stage i) is heated, in particular under reflux, until the optical enantiomer of modafinil is completely dissolved in the solvent. Although the concentration of the optical enantiomer of modafinil in stage i) is not a critical factor for the crystallisation, it is however preferable to work in the presence of a concentration of optical enantiomer of modafinil which is close to the saturation concentration in the recrystallisation solvent in question. According to one embodiment the optical enantiomer of modafinil is dissolved by heating the solvent under reflux and an additional quantity of the said optical enantiomer is then added in fractions in such a way as to achieve saturation. Additional solvent may be added to ensure complete dissolution. According to another embodiment the optical enantiomer of modafinil is suspended in the solvent heated under reflux and an additional quantity of solvent is then added in fractions so as to obtain a homogeneous solution and thus achieve saturation. The process of crystallisation of the optical enantiomer of modafinil in stage ii) may be accelerated using techniques known to those skilled in the art, namely cooling of the solution, evaporation of some of the solvent, the addition of an antisolvent or seeding the solution with crystals of optically active modafinil having the same crystalline form as that desired. Most commonly the mixture is stirred continually throughout the crystallisation process so as to obtain a homogeneous suspension and rapid renewal of the mother liquor around each crystallite. The crystallisation process in the process according to the invention may be carried out under thermodynamic or kinetic conditions. For the purposes of this description, by “crystallisation under thermodynamic conditions” is meant crystallisation performed under conditions in which equilibrium is maintained between the homogeneous solution and the saturated solution in the presence of crystals of l- or d-modafinil. By way of example, a thermodynamic crystallisation may be performed by slowly cooling the solution obtained in stage i), typically by allowing the solution to cool to ambient temperature or by applying a rate of cooling or a cooling gradient which is preferably less than or equal to 0.75° C./min, more preferably to 0.6° C./min and more preferably to 0.5° C./min. By “crystallisation performed under kinetic conditions” for the purposes of this description is meant a crystallisation in which equilibrium between the homogeneous solution and the saturated solution in the presence of crystals of d- or l-modafinil is suddenly displaced towards the latter two-phase domain, i.e. towards the formation of crystals. By way of illustration, a crystallisation which is said to be kinetic can be performed in particular by rapid cooling, for example by implementing a cooling gradient of 300° C./min, or by precipitation through the addition of an antisolvent to the solution obtained in stage i). By way of an illustrative and non-restrictive example these two types of thermodynamic or kinetic crystallisation are effected in this description by slow or rapid cooling. Of course any other technique of crystallisation such as evaporation of the solvent or precipitation which would make it possible for kinetic and/or thermodynamic conditions to obtain also falls within the scope of the process according to the invention. Thus according to a particular embodiment the crystallisation in stage ii) may be performed by precipitation, possibly in the presence of seed crystals of the desired crystal form. The inventors have also shown that some solvents can give rise to different crystalline forms, more specifically to polymorphic forms, according to whether the crystallisation is performed under kinetic or thermodynamic conditions. According to a particularly advantageous embodiment crystallisation comprises cooling of the solution obtained in stage i). As applicable, in a first mode, cooling is rapid and generally corresponds to quenching of the solution obtained in stage i) in a bath at a temperature at or below 0° C. such as a bath of ice water for a sufficient time to permit complete crystallisation of the solution, or again cooling with a temperature gradient of for example between −1° C. and −5° C./min. According to a second embodiment cooling is slow. In this context the solution is generally allowed to cool from the reflux temperature of the solvent to ambient temperature or the solution is cooled with a cooling gradient preferably between −0.1° C./min and −0.8° C./min, and more preferably close to −0.5° C./min, generally down to a temperature of 15° to 20° C. Among the preferred combinations of solvents/antisolvents according to the invention mention may be made in particular of the combinations water/acetone, acetonitrile/water, ethanol/water, methanol/water, acetic acid/water. Finally the crystalline forms of the optical enantiomers of modafinil can be isolated using conventional methods such as filtration and centrifuging. By way of a non-restrictive illustration the process of preparation according to the invention is more particularly implemented using the laevorotatory enantiomer of modafinil. According to a particular embodiment the crystalline form obtained according to this process is a polymorphic form. In this respect it will be noted that in general each of the (l) and (d) enantiomers of a given chemical compound yield crystalline forms, in particular polymorphic forms, having powder X-ray diffraction spectra which are identical when they are recrystallised under the same experimental conditions. In this respect reference should be made in particular to the work of J. Bernstein <<Polymorphism in molecular crystals>> 2002, University Press, Oxford, UK, and the publication by G. Coquerel, Enantiomer, 2000; 5(5): 481-498, Gordon and Breach Science Publishers. In this respect the dextrorotatory form, whose X-ray diffraction spectra for the crystalline forms are identical to those of the laevorotatory form described below and vice versa, forms part of the invention. In what follows the polymorphic forms designated forms I, II, III, IV and V also cover the CRL 40982 forms I, II, III, IV, V obtained from the laevorotatory enantiomer and the CRL 40983 forms I, II, III, IV, V obtained from the dextrorotatory enantiomer. Form I In this context, the process using a solvent selected from acetone, ethanol, 1-4 dioxan, ethyl acetate and mixtures of ortho, meta and para xylene, and a stage of crystallisation by slow cooling leads to the acquisition of form I or CRL 40982 form I. The process using a solvent selected from methanol, water or alcohol/water mixtures, in particular methanol/water and ethanol/water, and a stage of crystallisation by rapid cooling leads to the acquisition of form I or CRL 40982 form I. According to another equally preferred variant of the invention, the process using methanol and a stage of crystallisation by precipitation through the addition of cold water as an antisolvent for methanol leads to form I. Form II According to another embodiment of the invention, the process using a solvent in stage i) selected from isopropanol, ethyl acetate, n-propanol, or ethanol denatured with toluene and a stage of crystallisation by rapid cooling leads to a polymorphic form described as Form II or CRL 40982 form II. According to a variant of the process form II can also be obtained by slow cooling from isopropanol. It may also be commented that the production of form II from isopropanol does not depend on the conditions of crystallisation (thermodynamic or kinetic). Form III According to another variant of the process according to the invention the solvent used in stage i) is acetone, and crystallisation stage ii) comprises rapid cooling, this apparently leading to acquisition of a polymorphic form described as form III or CRL 40982 form III. Form IV As a variant of the process according to the invention, the solvent used in stage i) is selected from tetrahydrofuran, chloroform and methylethylketone, and crystallisation stage ii) comprises slow cooling of the solution, as a result of which a polymorphic form described as form IV or CRL 40982 form IV is obtained. Depending upon the nature of the solvent used, the process for recrystallisation of the optical enantiomers of modafinil can give rise to the production of solvates. Form V As a variant of the process according to the invention the solvent used in stage i) is selected from 2-pentanone and tetrahydrofuran, and crystallisation stage ii) comprises slow cooling of the solution in 2-pentanone and rapid cooling in THF, as a result of which a polymorphic form described as form V is obtained. Dimethyl Carbonate Solvate Thus according to a particular embodiment of the invention, when the solvent used in stage i) is dimethyl carbonate and crystallisation consists of slow cooling, a dimethyl carbonate (−)-modafinil solvate is obtained. Acetic Acid Solvate According to a particular embodiment of the invention, when the solvent used in stage i) is acetic acid and crystallisation consists of a rapid or slow cooling, an acetic acid solvate is obtained. Polymorphic Forms of (−)-Modafinil The invention also relates to the polymorphic form of the laevorotatory enantiomer of modafinil described as CRL 40982 form II, characterised in that it produces an X-ray diffraction spectrum comprising intensity peaks for the interplanar spacings: 11.33, 8.54, 7.57, 7.44, 4.56, 3.78, 3.71 Å, the intensity peaks corresponding to the interplanar spacings of 8.54, 7.57, 7.44, 4.56, 3.78, 3.71 Å being particularly characteristic. More specifically the X-ray diffraction spectrum below, in which d represents the interplanar spacing and I/Io the relative intensity: CRL 40982 FORM II 2 Theta (degrees) d (Å) I/Io (%) 11.6 11.33 54 15.4 8.54 58 17.4 7.57 41 17.7 7.44 34 23.3 5.67 19 24.8 5.33 26 27.4 4.83 19 28.9 4.59 36 29.1 4.56 97 29.8 4.45 23 32.8 4.05 29 34.3 3.88 23 35.3 3.78 100 35.9 3.71 40 40.1 3.34 21 47.7 2.83 20 53.7 2.53 32 Diffractometer: Miniflex Rigaku (Elexience) The invention also relates to the polymorphic form of the laevorotatory enantiomer of modafinil described as CRL 40982 form III, characterised by an X-ray diffraction spectrum incorporating intensity peaks at the following interplanar spacings d: 13.40, 12.28, 8.54, 7.32, 6.17, 5.01, 4.10, 3.97, 3.42, 3.20 Å, and the interplanar spacings: 12.28, 8.54, 5.01, 4.10, 3.97, 3.42, 3.20 Å corresponding to the most characteristic intensity peaks. In this context the invention relates more particularly to form III of (−)-modafinil which produces the following X-ray diffraction spectrum in which d represents the interplanar spacing and I/Io the relative intensity: CRL 40982 FORM III 2 Theta (degrees) d (Å) I/Io (%) 9.8 13.40 40 10.7 12.28 39 15.4 8.54 100 18.0 7.32 33 21.4 6.17 23 25.9 5.11 26 26.4 5.01 87 29.6 4.48 26 29.9 4.44 20 31.1 4.27 34 31.7 4.19 20 32.4 4.10 77 33.1 4.02 23 33.5 3.97 64 36.5 3.66 38 39.1 3.42 40 41.9 3.20 32 46.4 2.91 23 52.7 2.58 25 Diffractometer: Miniflex Rigaku (Elexience) The invention also relates to the polymorphic form of the laevorotatory enantiomer of modafinil described as CRL 40982 form IV, characterised in that it produces an X-ray diffraction spectrum comprising intensity peaks at the interplanar spacings: 12.38; 8.58; 7.34; 6.16; 5.00; 4.48; 4.09; 3.66 Å, the most characteristic peaks corresponding to the interplanar spacings of 12.38; 8.58; 7.34; 5.00; 4.09 Å. More specifically, form IV of (−)-modafinil is characterised in that it produces the following X-ray diffraction spectrum in which d represents the interplanar spacing and I/Io the relative intensity comprising intensity peaks at the interplanar spacings: CRL 40982 FORM IV 2 Theta (degrees) d (Å) I/Io (%) 6.37 13.88 26 7.14 12.38 69 8.60 10.27 23 10.30 8.58 100 12.04 7.34 49 14.37 6.16 24 15.65 5.66 11 17.30 5.12 29 17.72 5.00 60 19.12 4.64 15 19.81 4.48 25 20.82 4.26 10 21.24 4.18 12 21.70 4.09 51 23.28 3.82 9 24.30 3.66 30 25.18 3.53 9 26.02 3.42 21 27.13 3.28 9 27.90 3.20 15 Diffractometer: Siemens AG. The invention also relates to the polymorphic form of the dextrorotatory enantiomer of modafinil referred to as CRL 40983 form V, characterised in that it produces an X-ray diffraction spectrum comprising intensity peaks at the interplanar spacings 9.63, 5.23; 5.03, 4.74, 4.66, 4.22, 4.10, 3.77 (Å). CRL 40983 FORM V 2 Theta (degrees) d (Å) I/Io (%) 6.65 13.27 22 7.24 12.21 5 9.17 9.63 51 10.38 8.51 19 12.28 7.20 15 14.33 6.17 14 15.81 5.60 4 16.95 5.23 68 17.64 5.03 100 18.69 4.74 51 19.03 4.66 58 20.06 4.42 3 21.06 4.22 91 21.67 4.10 64 22.39 3.97 17 23.61 3.77 55 24.64 3.61 8 25.40 3.50 13 26.21 3.40 20 26.95 3.31 18 Diffractometer: Bruker GADDS The invention also relates to the dimethyl carbonate solvate of (−)-modafinil, characterised by the following diffraction spectrum in which d represents the interplanar spacing and I/Io the relative intensity: DIMETHYL CARBONATE SOLVATE 2 Theta (degrees) d (Å) I/Io (%) 7.17 12.31 38 9.12 9.69 29 9.72 9.09 16 10.35 8.54 35 12.17 7.27 100 14.25 6.21 16 16.26 5.45 10 17.36 5.10 13 17.72 5.00 21 18.35 4.83 9 19.16 4.63 9 19.88 4.46 14 21.04 4.22 12 21.49 4.13 25 21.73 4.09 24 23.49 3.78 22 24.55 3.62 35 25.24 3.53 8 26.05 3.42 9 26.88 3.32 7 27.48 3.24 13 27.81 3.21 10 28.79 3.10 8 Diffractometer: Siemens AG. The invention also relates to the acetic acid solvate of the laevorotatory and dextrorotatory enantiomers of modafinil which can be obtained by the recrystallisation process according to the invention, characterised in that it produces a X-ray diffraction spectrum comprising intensity peaks at the interplanar spacings: 9.45; 7.15; 5.13; 4.15; 3.67 (Å). ACETIC ACID SOLVATE 2-Theta (degrees) d (Å) I/Io % 6.64 13.30 8.5 7.15 12.35 15 9.36 9.45 100 10.43 8.48 6.5 12.38 7.15 25 14.38 6.16 15 16.37 5.41 8 17.29 5.13 28 17.82 4.97 21 18.24 4.86 16 18.96 4.68 7 19.24 4.61 6 20.09 4.42 20 21.40 4.15 75 22.55 3.94 21 23.42 3.80 7 24.25 3.67 40 24.92 3.57 12 25.21 3.53 9.5 26.15 3.40 11 26.78 3.33 8 26.99 3.30 6 28.43 3.14 13 28.79 3.10 14 29.63 3.01 7 30.03 2.97 4 32.33 2.77 9 33.13 2.70 7 34.29 2.61 3 34.86 2.57 7 35.90 2.50 7 Diffractomètre: Bruker GADDS According to another aspect, the invention also relates to a process for conversion from a first crystalline form of one of the enantiomers of modafinil to a second crystalline form which is different from the former, the said process comprising the stages of: i) suspending the crystalline form of the said enantiomer of modafinil in a solvent; ii) recovering the crystalline form obtained. By way of solvents which may be suitable for this process mention may be made in particular of acetonitrile. In general the initial crystalline form is held in suspension at a temperature lower than the homogenisation temperature for a sufficient length of time to permit total conversion of the initial form. This period may vary in particular according to the nature of the solvent, the initial crystalline form and the temperature of the medium. Conventionally the crystalline form is held in suspension for at least 24 hours at ambient temperature under atmospheric pressure, most commonly for approximately 72 hours. By way of illustration this process is implemented using (−)-modafinil. In this context, according to a particular embodiment of the invention, the process uses form I in acetonitrile in stage i), as a result of which an acetonitrile solvate of (−)-modafinil is obtained. By way of indication form I is held in suspension for several days, preferably for 3 days at ambient temperature, at atmospheric pressure. The invention also relates to the acetonitrile solute of (−)-modafinil which can be obtained through the recrystallisation process according to the invention. It is characterised by the following diffraction spectrum in which d represents the interplanar spacing and I/Io the relative intensity: ACETONITRILE SOLVATE 2 Theta (degrees) d (Å) I/Io (%) 5.46 16.17 46 6.25 14.14 95 7.17 12.32 51 8.28 10.66 81 9.02 9.79 68 9.51 9.29 53 10.34 8.54 53 10.84 8.15 63 11.33 7.80 79 12.47 7.09 53 14.02 6.31 45 15.20 5.83 35 15.76 5.62 34 16.37 5.41 40 17.37 5.10 51 18.10 4.90 46 19.05 4.66 44 19.36 4.58 37 19.89 4.46 39 20.48 4.33 59 21.14 4.20 55 22.10 4.02 100 22.65 3.92 60 23.17 3.835 42 23.89 3.72 33 24.72 3.60 38 24.93 3.57 37 25.81 3.45 37 26.73 3.33 55 27.52 3.24 30 27.97 3.19 30 28.89 3.09 31 29.44 3.03 27 Diffractometer: Siemens AG. Pharmaceutical Compositions Comprising Polymorphic Forms II, III, IV and V of (−)-Modafinil and (+)-Modafinil Respectively The invention also relates to pharmaceutical compositions comprising the polymorphic forms CRL 40982 form II, CRL 40982 form III, CRL 40982 form IV or CRL 40982 form V of (−)-modafinil and form CRL 40983 form II, CRL 40983 form III, CRL 40983 form IV and CRL 40983 form V respectively, possibly in association with a pharmaceutically acceptable vehicle. These compositions may be administered orally, via the mucosa (for example, the mucosa of the eye, nose, lungs, stomach, intestines, rectum, vagina or the urinary apparatus) or parenterally (for example subcutaneously, intradermally, intramuscularly, intravenously or intraperitoneally). According to a preferred embodiment the pharmaceutical compositions according to the invention are administered orally in the form of tablets, pills, gelules or immediate release or controlled release granules, in the form of powder, capsules, suspension of a liquid or in a gel or emulsion, or as a lyophilisate, or preferably in the form of tablets, capsules, suspension in a liquid or in a gel. The vehicle for administration may comprise one or more pharmaceutically acceptable excipients which are likely to ensure stability of the polymorphic forms (for example a suspension of a polymorph in an oil). The pharmaceutical compositions according to the invention comprise the II, III, IV or V polymorphic forms of (−)-modafinil and (+)-modafinil respectively, possibly as mixtures of each other and/or with one or more pharmaceutically acceptable excipients. A solid composition for oral administration is prepared by adding one or more excipients to the active ingredient, in particular a filler, and, if appropriate a binder, an exfoliating agent, a lubricant, a surfactant and an emulsifier, a solubiliser, a colouring agent, a sugar substitute or a taste modifier, with the mixture being formed for example into the form of a table or capsule. Examples of fillers include lactose, sucrose, mannitol or sorbitol; preparations based on cellulose, such as for example maize starch, rice starch, potato starch. Examples of binders include gelatine, gum tragacanth, methylcellulose, hydroxypropylcellulose, sodium carboxymethylcellulose, and/or polyvinyl pyrrolidone (PVP), povidone, copovidone, dextran, dextrin, cyclodextrin and its derivatives such as hydroxypropyl-β-cyclodextrin. Examples of sugar substitutes include aspartame, saccharin and sodium cyclamate. Examples of taste modifying agents include cocoa powder, mint in vegetable form, aromatic powder, mint in the form of oil, borneol and powdered cinnamon. Examples of surfactants and emulsifiers include in particular polysorbate 20, 60, 80, sucroester (7-11-15), poloxamer 188, 407, PEF 300, 400 and sorbitan stearate. Examples of solubilising agents include miglyol 810, 812, glycerides and their derivatives and propylene glycol. Examples of exfoliating agents include, for example, polyvinyl pyrrolidone, sodium carmellose or alginic acid or a salt of the latter such as sodium alginate. Examples of lubricants include magnesium stearate, stearyl magnesium fumarate, behenic acid and its derivatives. The pharmaceutical compositions according to this invention may also contain another crystalline form of (−)-modafinil or (+)-modafinil respectively, in particular form I and/or another active ingredient or inactive ingredient as a mixture with one or more other polymorphic forms of modafinil such as form III, form II, form IV and form V. For the purposes of this invention the term “pharmaceutically acceptable vehicle” covers solvents, dispersion media, antifungal and antibacterial agents, isotonic agents and absorption-delaying agents. The use of such media and agents for pharmaceutically active substances is well known to those skilled in the art. The invention also relates to the use of the forms CRL 40982 form II, CRL 40982 form III, CRL 40982 form IV or CRL 40982 form V of (−)-modafinil and the forms CRL 40983 form II, CRL 40983 form III, CRL 40983 form IV or CRL 40983 form V of (+)-modafinil respectively for the manufacture of a medication intended for the prevention and/or treatment of a condition selected from hypersomnia, in particular idiopathic hypersomnia and hypersomnia in patients affected by a cancer treated by morphine analgesics to relieve pain; sleep apnoeas, excessive somnolence associated with a disease, obstructive sleep apnoeas, narcolepsy; somnolence, excessive somnolence, excessive somnolence associated with narcolepsy; disturbances of the central nervous system such as Parkinson's disease; protection of the cerebral tissue against ischaemia, alertness disturbances, in particular alertness disturbances associated with Steinert's disease, attention disturbances, for example associated with hyperactivity (ADHD); the condition of fatigue, in particular that associated with multiple sclerosis and other degenerative diseases; depression, the depressive condition associated with low exposure to sunlight, schizophrenia, rotating shift working, time shifts; eating disturbances, in which modafinil acts as an appetite stimulant, the stimulation of cognitive functions in low doses. Process for the Preparation Optically Active Modafinil In accordance with another aspect the invention relates to a process for preparation of the optical enantiomers of modafinil from (±) modafinil acid, the said process comprising the following stages: i) separating the two optical enantiomers of (±) modafinil acid and recovering at least one of the enantiomers, ii) placing one of the two enantiomers obtained in contact with a lower alkyl haloformate and an alcohol in the presence of a base, iii) recovering the product obtained, iv) converting the ester obtained in stage iii) into an amide, v) recovering the product obtained in stage iv). Preferably the lower alkyl haloformate is a lower alkyl chloroformate and, better still, it comprises methyl chloroformate. Advantageously the lower alkyl haloformates, among which in particular methyl chloroformate, used in this process to bring about the esterification of modafinil acid are less toxic than the dimethyl sulphate described in the process in the prior art U.S. Pat. No. 4,927,855, giving equivalent or better yields. The process is therefore easier to use and more suitable for industrial application. Preferably the operation is conducted in the presence of an equimolar quantity of lower alkyl haloformate and base in stage ii) in relation to optically active modafinil acid. It is particularly preferred to use organic bases, more preferably nitrogen-containing bases. As a particularly preferred base mention may be made in particular of triethylamine, diisopropylamine, diethylmethylamine, diisopropylethyl amine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Preferably the solvent used in stage ii) is a lower aliphatic alcohol such as methanol, ethanol or propanol, methanol being particularly preferred. According to a particular embodiment the ester obtained from stage ii) is crystallised by the addition of iced water. Conversion of the ester to amide in stage iv) preferably consists of ammonolysis, i.e. treatment with ammonia. In this context it is generally preferably to work with an excess of ammonia. According to a particularly advantageous variant of the invention, ammonia is used in the form of gas. In a preferred embodiment the ammonolysis reaction is performed in a polar solvent, preferably a protic solvent such as lower aliphatic alcohols, for example in methanol or ethanol, methanol being particularly preferred. The (+) or (−)modafinil acid ester in stage iii) and the (+) or (−)modafinil respectively in stage iv) are recovered using conventional methods known to those skilled in the art. According to another aspect the invention relates to a process for the preparation of optical enantiomers of modafinil comprising the following stages a. resolving the two optical enantiomers of (±) modafinil acid or salts of the same according to a preferential crystallisation process, b. converting the said isolated enantiomers into an amide, c. recovering the modafinil enantiomer obtained. According to a preferred embodiment stage b) is performed in two stages: b1) converting the said enantiomers into a lower alkyl ester, b2) converting the product obtained in stage b1) into an amide. According to a particularly preferred embodiment stage b1) is carried out in the presence of a lower alkyl haloformate, an alcohol and a base, under the conditions described previously. According to a particularly advantageous embodiment, when b1) is performed in the presence of methyl chloroformate, a base and an alcohol and c1) comprises an ammonolysis such as described previously, this process in which the (±)-modafinil acid is separated by preferential crystallisation gives rise to an overall yield generally of the order of 25%. Thus the yield of the (−)-modafinil enantiomer in particular obtained by this process is markedly greater than that obtained in U.S. Pat. No. 4,927,855. The preferential crystallisation technique is a technique which is widely used in laboratories and in industry. This method is based on the alternate crystallisation of two chiral compounds referred to as R and S, forming a conglomerate in solvent A and over a given temperature range DT. This means that within this temperature range any mixture of the two antipodes in thermodynamic equilibrium with the solution comprises two types of crystals each of which only contain molecules having the same configuration, which may or may not incorporate solvent molecules (solvates). The existence of such a conglomerate, without miscibility in the solid state, is implicitly accepted in what follows, at least during the temperature range DT and in the case of solvent A. Two kinds of factors influence crystallisation of the optical antipodes, on the one hand parameters associated with ternary heterogeneous equilibria and on the other hand factors affecting the kinetics of crystallisation. The parameters associated with ternary heterogeneous equilibria comprise: the positions of the crystallisation surfaces for the solid species which are deposited at each temperature and more particularly the solubilities of the stable and metastable phases, of the s(+) racemic mixture and the antipodes s(+)=s(−) in relation to temperature, and the ratio of solubilities α=s(±)/s(+), the extent of the stable and metastable domains for the solid solutions, the racemate, the racemic solvate, the active solvates and the polymorphic varieties of the crystallised solids. The factors acting on the kinetics of crystallisation include: factors internal to the crystals, associated with the bonds between molecules, which cannot be modified by the experimenter, external factors which can be modified by the experimenter; these are the nature of the solvent, the nature and concentration of impurities, the supersaturation acquired in relation to time, the temperature range DT, the speed and manner of stirring, the mass and particle size of the nuclei, the wall effect, etc. These two kinds of factors directly influence the yield, the purity of the phases obtained and the conduct of the separation operations. The feasibility of filtration also depends on the particle size spectrum and the habits of the crystals, the viscosity of the suspension, the vapour pressure of the solvent, the supersaturation of each of the antipodes and the possible presence of a true racemate of a metastable nature. These choices may also affect the kinetics of racemisation of the antipodes or degradation of the molecule. For each combination comprising the pair of antipodes (R and S) and the solvent (A), the factors affecting the kinetics are of a particular type. Two preferred methods of crystallisation are mainly distinguished: conventional processes, described as SIPC, for “Seeded Isothermal Preferential Crystallization” and their polythermic variants, and the process referred to as AS3PC, for “Auto-Seeded Polythermic Programmed Preferential Crystallization”. In the AS3PC preferential crystallisation method which is referred to as being auto-seeded, the system is placed under conditions such that it itself generates its own seeds to produce the required enantiomer, while in the SIPC method these seeds are introduced by seeding. The two types of processes are described in greater detail below. For more information concerning resolution processes by preferential crystallisation by the AS3PC methods reference may be made in particular to the documents by G. Coquerel, M.-N. Petit and R. Bouaziz, Patent EP 0720595 B1, 1996, E. Ndzié, P. Cardinaël, A.-R. Schoofs and G. Coquerel, Tetrahedron Asymmetry, 1997, 8(17), 2913-2920, L. Courvoisier, E. Ndzie, M.-N. Petit, U. Hedtmann, U. Sprengard and G. Coquerel, Chemistry Letters, 2001, 4, 364-365. According to a particular embodiment, the process for resolution of the optical enantiomers of (±) modafinil acid or its salts is a seeded SIPC or S3PC process, the said process comprising the following stages: a) homogenisation of an combination comprising a racemic mixture of crystals in the form of a conglomerate of the first enantiomer of modafinil acid at a temperature TD, for which the defining point E, defined by the variables concentration and temperature TD, lies within the monophase domain of the dilute solution, b) rapidly cooling the solution prepared in stage a) initially at the temperature TD down to the temperature TF, c) seeding the solution obtained in stage b) while cooling (i.e. between TL and TF) or when cooling is complete (i.e. at TF) with very pure seeds of the first enantiomer, d) harvesting crystals of the first enantiomer, e) adding the racemic mixture of crystals in the form of conglomerate to the mother liquors resulting from the harvest performed in stage d) and homogenising the new combination by heating to a temperature TD, so that the defining point E′ is symmetrical for E with respect to the plane of the racemic mixture of the solvent, antipode (−), antipode (+) system, the said point E′ lying within the monophase domain of the dilute solution, f) rapidly cooling the solution obtained in stage e), initially at temperature TD, down to temperature TF, g) seeding the solution obtained in stage f) with very pure seeds of the second enantiomer, h) harvesting the crystals of the second enantiomer, i) adding the racemic mixture in the form of a conglomerate of crystals resulting from the crystal harvest made in stage h) to the mother liquors and homogenising the new combination by heating to a temperature TD in order to obtain a composition identical to that of the combination having the initial defining point E, j) repeating stages a), b), c), d), e), f), h) and j) to subsequently obtain the first and then the second of the two enantiomers. Reference is frequently made to these two methods by describing them as “SIPC” and “S3PC” respectively, the latter being a variant of SIPC as described in detail further on in the description. In what follows, for the purposes of this invention, TF represents the temperature at the end of crystallisation and filtration, located in the three-phase domain, TL represents the homogenisation temperature of the racemic mixture, TD represents the starting temperature at which the starting mixture is a homogenous solution, antipode means an enantiomer. Preferably the process for the resolution of these two optical enantiomers of (±)-modafinil acid or salts of these by preferential crystallisation is an AS3PC self-seeded process, the said process comprising the following stages: a) creating a combination comprising a racemic mixture of the crystals in the form of a conglomerate of the first enantiomer of modafinil acid and solvent, for which the defining point E, defined by the variables concentration and temperature TB, lie within the two-phase domain of the enantiomer in excess, and is in equilibrium with the saturated solution, b) applying a temperature cooling programming function to the two-phase mixture prepared in stage a), this programming function being such that the mother liquors remain slightly supersaturated, encouraging growth of the enantiomer present in the form of crystals while preventing spontaneous nucleation of the second enantiomer present in the solution, c) throughout the time of crystal growth in stage b) adopting a rate of stirring which increases slightly in relation to time so that it is at all times sufficiently slow to encourage growth of the first enantiomer while avoiding the generation of excessively large shear forces bringing about uncontrolled nucleation but sufficiently fast to achieve a homogeneous suspension and rapid renewal of the mother liquor around each crystallite of the first enantiomer, d) harvesting the crystals of the first enantiomer, e) adding the racemic mixture of crystals in the form of a conglomerate to the mother liquors resulting from the harvest performed in stage d) and bringing the new combination to a temperature threshold TB during the time necessary to achieve thermodynamic equilibrium so that the defining point E′ is symmetrical for E with respect to the plane of the racemic mixtures for the solvent, antipode (−), antipode (+) system, the said point E′ lying within the two-phase domain of the second enantiomer which is in excess and in equilibrium with its saturated solution, f) applying the same cooling programming function as in stage b) to the two-phase mixture prepared in stage e) containing the second enantiomer so that the mother liquors remain slightly supersaturated during crystallisation in order to encourage growth of the enantiomer present in the form of crystals while preventing spontaneous nucleation of the first enantiomer present in the solution, g) adopting a stirring speed which increases slightly in relation to time over the entire time of crystal growth in stage f) so that it is at all times sufficiently slow to encourage growth of the second enantiomer while avoiding generation of excessively large shear forces giving rise to uncontrolled nucleation, but sufficiently fast to obtain a homogeneous suspension and rapid renewal of the mother liquor around each crystallite of the second enantiomer, h) harvesting crystals of the second enantiomer, i) adding the racemic mixture of crystals in the form of conglomerate to the mother liquors resulting from the crystal harvest performed in stage g) in order to obtain a combination in which the composition is identical to that of the initial combination E, j) repeating stages a), b), c), d), e), f) g), h) and i) to obtain the first and then the second of the two enantiomers successively. In what follows, for the purposes of this invention, THOMO shall mean the homogenisation temperature of the combination comprising the racemic mixture, the first enantiomer and the solvent. Thus in stage (a) of the process according to the invention the choice of the solvent or solvents and the working temperature range are defined in such a way so as to obtain simultaneously: antipodes which form a conglomerate and of which any racemate is metastable in the working temperature range, liquors which are sufficiently concentrated but of low viscosity and low vapour pressure, the absence of solvolysis and racemisation, stability of the solvates if these are present at equilibrium and they are resolvable enantiomers. In stages (a) and (e) of the process according to the invention, the temperature TB is higher than the temperature TL for homogenisation of the quantity of racemic mixture present in the initial suspension, in that from the curve for the change in THOMO in relation to the excess of enantiomer and for a constant concentration of the racemic mixture XL the said temperature TB is defined in such a way that the mass of fine crystals of the first enantiomer from stages (a) and (i) and the second enantiomer from stage (e), in equilibrium with their saturated solutions, represent at most 50% and preferably between 25% and 40% of the expected harvest. In stages (b) and (f) of the process according to the invention, the function for programming cooling from temperature TB to TF, appropriate to the experimental assembly, is defined so as to: achieve slight supersaturation throughout the time for crystallisation of the enantiomer present in the form of crystals at the start of each cycle, this slight supersaturation giving rise to gentle growth and secondary nucleation, achieve maximum supersaturation of the other enantiomer at TF without primary nucleation, obtain a harvest of crystals in stages (d) and (h) which after addition of the racemic mixture and the provision of make-up in stages (e) and (i), makes it possible to perform the operations cyclically. In fact every experimental assembly has an influence on the supersaturation capacities of the mixtures used and the efficiency of stirring, and as a consequence the function programming cooling must be adapted to the circumstances in which the process is carried out. However the temperature TB, the solubilities of the racemic mixture in relation to temperature, and the THOMO curve in relation to the excess of enantiomer for a constant concentration of the racemic mixture XL are themselves wholly independent of the experimental assembly. The cooling programming function, which is the function linking temperature with time, is determined in its part from TL to TF by cooling of the solution of concentration XL from TL+1° C. to TF, where TF is lower than TL−(THOMO−TL), in order to obtain a stable saturated solution without primary nucleation while permitting a double harvest of the initial enantiomer excess and the said cooling programming function is determined in its part from TB to TL by extrapolation of the same function as established from TL+1° C. to TF. The process for the preferential crystallisation of (±)-modafinil acid or salts of the same has other advantageous features alone or in combination such that: in stages (a) and (i) the mass of fine crystals of the first enantiomer in equilibrium with the saturated solution represents between approximately 25% and 40% of the expected harvest, 50% representing a maximum limit, in stage e) the mass of fine crystals of the second enantiomer in equilibrium with its saturated solution represents between approximately 25% and 40% of the expected harvest, 50% representing a maximum limit, in stages (b) and (f) the heat released accompanying deposition of the first enantiomer and the second enantiomer is incorporated into the temperature programming function, in stages (e) and (i) compensatory additions of solvent are made, in stages (a), (e) and (i) the fine crystals of the racemic mixture in the form of conglomerate added were subjected to prior treatment to accelerate the dissolution stage, such as grinding and sieving, treatment with ultrasound waves or partial lyophilisation, before being added; these treatments being also for the purpose of providing fine crystals capable of generating a large surface area for crystal growth, in stages (a), (e) and (i) involving dissolution, the rate of stirring is high in comparison with stages (c) and (g). In addition to the heterogeneous equilibrium data required for implementing the AS3PC process, the operations are also subject to adjustable kinetic constraints, particularly the cooling function, and these are specific to each solvent/enantiomer combination. According to one embodiment the solvent used in stage a) of the SIPC, S3PC or AS3PC processes is absolute or denatured ethanol, possibly in a mixture with an organic or mineral base, or with one or more solvents capable of improving the solubility of the racemic mixture in ethanol. As a variant, the solvent used in stage a) of the SIPC, S3PC or AS3PC processes is 2-methoxyethanol or methanol, possibly mixed with an organic or mineral base, and/or one or more solvents capable of improving the solubility of the racemic mixture in ethanol. According to a particularly advantageous embodiment the solvent used in stage a) of the SIPC or AS3PC process is ethanol, 2-methoxyethanol or methanol. For (±)-modafinil acid the filtration temperature TF preferably lies between 0° C. and 40° C. In the case of ethanol the temperature TF preferably lies between 0° C. and 25° C., and better still it is close to 18° C. or 17° C. In the case of 2-methoxyethanol or methanol, the temperature TF preferably lies between 20° C. and 35° C. and in particular is close to 30° C. Preferably the concentration of the racemic mixture in stage a) then lies between 2 and 50% by mass, more preferably between 2 and 30% by mass, and, better still, close to 5.96% by mass in the case of ethanol, 15.99% in the case of 2-methoxyethanol and 25.70% in the case of methanol. In this context it is most particularly preferred that the enantiomer excess in stage a) should be between 1 and 50% by mass, more preferably between 1 and 20% by mass, and, better still, close to 11% by mass in the case of ethanol, 8% by mass in the case of 2-methoxyethanol and 10% by mass in the case of methanol. In the SIPC and S3PC processes the temperature TD, the temperature at which the starting mixture is a homogeneous solution, depends on concentration and then generally lies between 35° and 50° C. when the solvent is under reflux. The cooling from temperature TD to TF is very fast so as to remain within the monophase domain and is preferably carried out in less than 20 min, for example by quenching. According to a preferred embodiment of the AS3PC process the temperature TB then lies between the temperatures TL and THOMO. The temperature TB may in particular lie between 25° C. and 50° C. By way of example, in the case of ethanol, when the enantiomer excess is close to 11% by mass temperature TB preferably lies between 25° C. and 40° C., in particular between 30.1° C. and 36.2° C. and more preferably close to 33.5° C. or 31.5° C. In the case of 2-methoxyethanol, when the enantiomer excess is close to 8% by mass temperature TB preferably lies between 35° C. and 50° C., in particular between 39.1° C. and 47.9° C. and more preferably close to 41° C. In the case of methanol, when the enantiomer excess is close to 10% by mass, temperature TB preferably lies between 40° C. and 55° C., in particular between 45.1° C. and 53.9° C. and more preferably close to 46.5° C. It is most particularly preferred that cooling from TB to TF in stage b) be carried out in a time which is sufficiently long for the average mass of desired enantiomer crystals harvested to be large, but sufficiently short to prevent the other enantiomer from crystallising, thus obtaining a high optical purity, in particular greater than 85%. Cooling is generally monitored by polarimetry to determine the right moment for filtration. Preferably cooling takes place between 50 and 70 minutes, better still, it takes 60 minutes when the solvent used is ethanol. Likewise, the length of the plateau at temperature TF for the SIPC, AS3PC and S3PC processes is preferably sufficiently great to allow a large mass of the desired enantiomer crystals to be harvested, but not too long so as to prevent the other enantiomer from crystallising at the same time as the desired enantiomer, thus obtaining a high optical purity. According to a preferred embodiment the length of the temperature plateau TF lies between 15 and 60 minutes, preferably about 60 minutes. A person skilled in the art will be able to adjust the rate of stirring to the type of reactor used in SIPC, S3PC or AS3PC processes. By way of indication, for a 2 or 10 litre reactor the speed at which the medium is stirred may be held between 150 and 250 rpm. In a particularly useful manner these methods of preferential crystallisation make it possible to isolate the optical enantiomers of modafinil, in particular the laevorotatory enantiomer, in yields which are very much greater than those obtained by resolution using a chiral agent. The yields obtained are generally of the order of 90%, or even higher, in relation to the (+) or (−) optical enantiomer, or of the order of 45% or more in relation to the racemic mixture. AS3PC, SIPC and S3PC Methods The AS3PC and SIPC methods mentioned above are described below. Ternary Heterogeneous Equilibria: R and S Antipodes, and Solvent A For example the work by J. E. Ricci (Ed. Dover Publication Inc. New York, 1966, The Phase Rule and Heterogeneous Equilibrium) deals with the general case of heterogeneous equilibria in ternary systems. The description below will be restricted to particular aspects of the ternary system, A (achiral solvent), R and S (enantiomers which cannot be racemised in the temperature domain used), which are necessary for an understanding of the various processes of preferential crystallisation. In order to show the special role of the solvent this ternary system will be represented by a right prism having a cross-section which is a right-angled isosceles triangle on which the temperature is plotted on an axis perpendicular to the plane of concentration. The fact that the thermodynamic variables for the two enantiomers, Tf, ΔHf, solubility in a achiral solvent, etc., are identical has the result that representation of the domains is symmetrical with respect to the vertical plane A-TS-T, which includes the optically inactive mixtures, in FIG. 1. The following simplifications have been made in order to assist an initial description of this system the only phases which crystallise out are the pure constituents in a given arrangement (absence of racemate, solvate and polymorphism in the case of the antipodes), miscibility between the independent constituents is zero in the solid state, the solvent has a melting point which is appreciably lower than that of the antipodes, in the temperature range used the solubility of an antipode is not influenced by the presence of the other in the solution (Meyerhoffer's law is respected), which is reflected in the ratio having the value α=2). Representation of Ternary Equilibria as a Function of Temperature FIG. 1 shows the domains for the following phases: the monophase domain for the dilute solution (Φ=1), the two crystallisation surfaces for the constituents bounding the two-phase domains (Φ=2). the surface for deposition of the solvent is confined to the vicinity of A because the melting point of this constituent is appreciably lower than that of the other constituents, in accordance with the conditions mentioned above. the three monovariant curves (Φ=3) or eutectic valleys originating from binary eutectic points, the ternary eutectic invariant at Tε(Φ=4), above which the three constituents are crystallised. FIG. 2 shows in a superimposed fashion the two isothermal cross-sections of the ternary displayed in FIG. 1 at TD and TF. At each temperature the cross-section consists of four domains as detailed in the table below. Number of Tem- Nature of the phases in phases in perature Domain boundary equilibrium equilibrium TD A - SD - ID - S′D dilute solution 1 TD R - SD - ID solution + crystals of R 2 TD S - S′D - ID solution + crystals of S 2 TD ID - R - S solution + crystals of R and S 3 TF A - SF - IF - S′F dilute solution 1 TF R - SF - IF solution + crystals of R 2 TF S - S′F - IF solution + crystals of S 2 TF IF - R - S solution + crystals of R and S 3 Isopleth Cross-Section RYT FIG. 3 shows the isopleth cross-section R-Y-T which is fundamental to an understanding of crystallisation by the cooling of ternary solutions in thermodynamic quasi-equilibrium. This cross-section is also necessary for following non-equilibrium processes, SIPC, variants and AS3PC. This plane is the geometric locus of the points fulfilling the relationship: XA/XS=(1−Y)/Y=constant, with XA and XS providing the fractions by mass of solvent and antipodes S. In FIG. 3 it is possible to see: the monophase domain of the ternary solution, the liquidus for antipode R, this curve representing the intersection of plane R-Y in FIG. 2 with the crystallisation surface for that constituent. This stable equilibrium curve originates at the melting point of antipode R (not shown) and is bounded on the low temperature side by point L which forms part of the ternary eutectic valley for the racemic mixtures. This latter curve and the line of the conoid at TL (horizontal segment at TL) are the boundary of the two-phase domain—saturated solution plus crystals of R. It extends into the underlying three-phase domain through a solubility curve for the same antipode R which is of a metastable nature (dashed lines), the three-phase domain: crystals of T and S, plus saturated solution. This domain is bounded at the top by the horizontal line of the conoid for R, and at the bottom by the line of the invariant ternary eutectic plane and on the left by the line Lm of one of the conoids relating to the antipode S. the line KL of the crystallisation surface for antipode S which bounds the two-phase domain at the top—saturated solution plus crystals of S. This domain is bounded in its lower part by the lines of the two conoids for S gm and Lm. The location of the second line Lm of the conoid for S in relation to the metastable solubility curve for R, which is an extension of EL, will be discussed below in relation to the relative position of F1 and F in relation to the ratio of solubilities α, The ternary invariant at the temperature Tε above which the three crystallised constituents A, R and S lie. Change on Cooling and with Thermodynamic Quasi-Equilibrium of the Ternary Solutions having a Slight Excess of Enantiomer It is taken in what follows that the overall point for the system (i.e. the point representing the overall composition of the mixture) lies on the vertical passing through point E in FIGS. 2 and 3, and its precise position is defined by its temperature (or level). Only the following temperature range is considered: TD: temperature at which the starting mixture is a homogeneous solution, and TF: temperature at the end of crystallisation and filtration, which lies in the three phase domain. This overall composition E corresponds to a racemic solution which is slightly enriched by a mass M of the antipode R forming a total mass Mt (the enantiomer excess R−S/R+S generally lies between 4% and 9%). Equilibrium conditions are obtained by very slow cooling and by seeding in the solid phase(s) when the overall point E defining the mixture reaches a domain where this (these) phase(s) is (are) present at equilibrium. At the starting temperature TD the solution is homogeneous. The following are observed in succession on cooling: crystallisation of the antipode R alone, from THOMO to TL, at the same time the solution point moves on the solubility curve for antipode R, that is from point E at level THOMO to point L within the isopleth cross-section R-Y. At point L, mass M of crystals R in equilibrium with saturated solution is given by Mt (XE−XL/1−XL)=M and corresponds to the enantiomer excess present in the initial solution (FIG. 3), the abscissas of the points L, E and R correspond to the compositions, and 1 (FIG. 3). from TL the solution point moves from L to IF along the line of fixed gradient containing the solutions of racemic composition shown in FIG. 2, thus leaving the isopleth cross-section R-Y in FIG. 3, crystals of R and S are then deposited simultaneously and in equal quantities. Resolution cannot be effected under equilibrium conditions at temperatures below TL. Change in the Solution when Resolving by Conventional Control in Accordance with the SIPC Process Crystallisation of the First Antipode in Excess The previous solution E is homogenised at temperature TD (FIGS. 4 and 5). In order to make it supersaturated it is cooled rapidly to temperature TF without any crystallisation occurring. This solution, which is not in thermodynamic equilibrium, is then seeded with very pure seeds of the antipode R having the same chirality as the antipode in excess. The isothermal crystallisation of antipode R is established and the point representing the solution moves within the cross-section R-Y-T from E to the level TF with which it is first coterminous to F where filtration is rapidly performed. The mass of antipode R recovered is 2M or again is equal to Mt (XE−XF/1−XF). Crystallisation of the Second Antipode, Cyclicity of the Operations The above fundamental operation thus gave rise to a solution F enriched with antipode S. By adding a mass 2M of racemic mixture (equal to that of the antipode recovered) and heating this mixture to temperature TD a homogeneous solution E′ which is symmetrical for E with respect to the vertical plane A-(RS)-T is obtained. The process making it possible to obtain a mass 2M of antipode S will itself also be represented by symmetrical movement of the above in relation to this median plane. The following operations are then performed in sequence: solution E′ which is homogeneous at temperature TD is first cooled to TF, then, seeded with very pure seeds of antipode S, the growth of this antipode displaces the point representing the solution on the horizontal segment E′F′ (at the level TF), when the solution point is the same as F′, the solution is filtered and provides a mass 2M of antipode S, after a further addition of a mass 2M of racemic mixture and a further heating to TD a homogeneous solution is again obtained and its representative point is the same as the initial point E at level TD, the rest of the process is merely a repeat of this cycle of operations. Variants in the SIPC Process The literature (Amiard, G., 1956, Bull. Soc. Chim. Fr. 447, Collet, A., Brienne, M. J., Jacques, J., 1980, Chemical reviews 80, 3, 215-30, Noguchi Institute, 1968, patent GB 1 197 809) is based on the above general scheme; the main modifications which have appeared in the literature are classified as follows: a) Spontaneous primary nucleation of the antipode in excess When (±)-threonine is separated (Amiard, G., 1956, Bull. Soc. Chim. Fr. 447), the primary nucleation of the antipode in excess occurs spontaneously within the supersaturated homogeneous solution. This primary nucleation occurs when point E representing the composition of the whole lies within the three-phase domain and the solution is not stirred (Collet, A., Brienne, M. J., Jacques, J., 1980, Chemical Reviews 80, 3, 215-30). b) Seeding during cooling (S3PC) This protocol is the one most frequently found in the literature (Noguchi Institute, 1968, patent GB 1 197 809) when the process differs from SIPC. There are differences between the procedures cited, but nevertheless the following common broad lines can be identified: cooling of the homogeneous solution from TD to a temperature below to TL but above TF, seeding of the supersaturated homogeneous solution located in the three-phase domain with seeds of the same chirality as the antipode in excess, cooling to TF. In some cases the latter stage is controlled by precise temperature programming (Noguchi Institute, 1968, patent GB 1 197 809). These protocols will be grouped together under the same term “S3PC” for “Seeded polythermic programmed preferential crystallization” although temperature programming is not present or is limited to the second stage of cooling. Change in the Solution Point in the Case of Resolution by Programmed Control and Self-Seeding in Accordance with the AS3PC Process According to the Invention In order to achieve a better comparison between conventional processes and the AS3PC process the initial point E is chosen arbitrarily in FIGS. 6 and 7 to be the same as in the previous case; however, as will be apparent in the examples which follow, the AS3PC process makes it possible to take a point E which is further away from the plane A-(RS)-T and therefore with a larger enantiomer excess and thus improve the harvest of crystals in each operation. Crystallisation of the First Antipode in Excess At the start of the process, and contrary to conventional protocols, the whole, crystals plus solution, is no longer homogeneous but is raised to the temperature TB. The initial solution is then in equilibrium with the crystals of the enantiomers in excess (for example R in FIG. 7). The points representing the solution (SE) and the whole (E) are therefore not the same from the start of the process. The two-phase mixture is subjected to a programmed temperature reduction function without the addition of seed crystals. The point representing the solution describes a curve SEF, contained within the plane R-Y-T, which depends on the kinetics of cooling (FIG. 7). With correctly adjusted kinetics, growth of the enantiomer crystals in excess occurs at the start, crystallisation then progressing towards a simultaneous regimen of growth plus secondary nucleation. When the point representing the solution reaches the point F, filtration is performed to recover a mass 2M of crystals of antipode R. Crystallisation of the Second Antipode, Cyclic Nature of the Operations From point F, which corresponds to the above parent solution, there is a move to point E, which is symmetrical for E with respect to the vertical plane A-(RS)-T, by adding a mass 2M of the racemic mixture and heating to temperature TB. The enantiomer excess is then profited from to take up a position in the two-phase domain containing the saturated solution and the crystals of the antipode in excess. To begin with the racemic mixture added during the passage from F to E (as from F′ to E) will be ground and sieved so as to accelerate the stage of dissolution of the two antipodes and more particularly the antipode of which there is less, and thus permit the formation of a large number of crystals of the antipode in excess which has the role of the seeds added in conventional processes. The saturated solution S′E, which is symmetrical for SE with respect to the plane A-(RS)-T is subjected to the same cooling function. The crystals present from the start of cooling grow and then take part in a double mechanism of growth+secondary nucleation. As in the case of the first crystallisation no seeding is therefore necessary. During this time the point representing the solution moves along a curve SE′F′ contained within the plane of the isopleth cross-section S-Y′-T which is symmetrical with respect to the bisecting plane A-(RS)-T. When the solution reaches the representative point located at F′, filtration is performed to harvest a mass 2M of ground and sieved racemic mixture followed by raising the temperature to TB yielding the two-phase mixture at the starting equilibrium. Continuation of the process consists of repeating this cycle of operations yielding crystals of antipode R and S alternately. Necessary Conditions for Implementing the AS3PC Process a) The equimolar mixture of optical antipodes produces a conglomerate (pure antipodes or solvates) in the solvent used within the temperature range TB-TF; however the existence of a metastable racemate is not a handicap. b) The molecules which are to be resolved are stable in this solvent and in the temperature range used between TB and TF. c) It is necessary to determine the ternary equilibrium temperatures TL and THOMO. Temperature TL is the temperature at which the racemic mixture dissolves in the absence of any enantiomer excess in the solution. Once TL has been determined, the temperature THOMO corresponds to the homogenisation temperature of the solution. It depends on the starting enantiomer excess and the ratio α of the solubilities of the racemic mixture and the antipode at TL. Knowledge of the supersaturation capacities of the solutions between TL and TF is also necessary, depending upon the cooling kinetic, the form of stirring, the nature of the vessel and the particle size of the crystals of the antipode in excess. To a first approximation, the time to the appearance of crystals by primary nucleation in the homogeneous racemic solution L cooled from a temperature slightly above TL using the same kinetics yields an indication of the supersaturation capacity tolerated by the conglomerate under these experimental conditions. This method of operation has been taken into account in the examples. d) Knowledge of the kinetics of dissolution of a known mass of racemic mixture (of a given particle size) dispersed in the solution at temperature TB. A few tests will be sufficient to discover this time. In what follows the examples and figures are provided by way of a non-restrictive illustration of this invention. FIGURES FIG. 1 is a perspective view of the ternary system solvent A-antipode R-antipode S, in relation to temperature and crystallisation surfaces for each constituent and compositions of the doubly saturated solutions (monovariant curves); this figure also shows the isotherms at temperatures TD and TF and the ternary eutectic plane at the temperature Tε including four phases. FIG. 2 is a projection onto the plane of concentrations of the equilibria at TD and TF, as well as a representation of the line of the isopleth cross-section RY on which point E represents the composition of the initial mixture slightly enriched in antipode R which will deposit this same antipode. FIG. 3 is the isopleth vertical cross-section RY in FIG. 2 containing the composition points for the antipode in excess and that of the initial solution E on which the path of the solution point for a mixture of composition XE at equilibrium and on cooling is shown (as a bold line). For T<TL the solution point no longer falls within this cross-section. FIG. 4 is a projection onto the concentrations plane of the path of the solution point (as a bold line) during alternating resolution by isothermal control at temperature TF and seeded in accordance with the SIPC method. FIG. 5 is the vertical isopleth cross-section containing the straight line RY in FIG. 4 and illustrating the path of the solution point (as a bold line) from E to F during isothermal control (to TF) and seeded according to the SIPC method. FIG. 6 is a projection onto the concentrations plane of the path of the solution point (as a bold line) when resolving by the self-seeded programmed polythermal process (AS3PC). FIG. 7 is the vertical isopleth cross-section containing the straight line RY in FIG. 6 and illustrating the path of the solution point (as a bold line) from SE to F during resolution by the self-seeded programmed polythermal process according to the invention (AS3PC). FIG. 8 is a projection on the concentrations plane of the path of the solution point (as a bold line) during resolution by the self-seeded programmed polythermal process (AS3PC) and confirming the relationship s(±)<2−α. All the isothermal cross-sections and isopleths illustrated in these figures have composition variables expressed as fractions by mass. FIG. 9 shows the powder X-ray diffraction spectrum obtained corresponding to form II of the laevorotatory enantiomer and dextrorotatory enantiomer of modafinil respectively (Diffractometer: Miniflex Rigaku (Elexience). FIG. 10 shows the powder X-ray diffraction spectrum obtained corresponding to form III of the laevorotatory enantiomer and dextrorotatory enantiomer of modafinil respectively (Diffractometer: Miniflex Rigaku (Elexience). FIG. 11 shows the powder X-ray diffraction spectrum obtained corresponding to form IV of the laevorotatory enantiomer and dextrorotatory enantiomer of modafinil respectively (Diffractometer: Siemens AG). FIG. 12 shows the powder X-ray diffraction spectrum obtained corresponding to the dimethyl carbonate solvate of the laevorotatory enantiomer and the dextrorotatory enantiomer of modafinil respectively (Diffractometer Siemens AG). FIG. 13 shows the powder X-ray diffraction spectrum obtained corresponding to the acetonitrile solvate of the laevorotatory enantiomer and dextrorotatory enantiomer of modafinil respectively (Diffractometer: Siemens AG). FIG. 14 shows the powder X-ray diffraction spectrum obtained corresponding to form V of the laevorotatory enantiomer of modafinil (Diffractometer: Bruker GADDS). FIG. 15 shows the powder X-ray diffraction spectrum obtained corresponding to the acetic acid solvate of the laevorotatory enantiomer and the dextrorotatory enantiomer of modafinil respectively (Diffractometer: Bruker GADDS). FIG. 16 shows the powder X-ray diffraction spectrum obtained corresponding to the amorphous form of the laevorotatory enantiomer and dextrorotatory enantiomer of modafinil respectively (Diffractometer: Bruker GADDS). EXAMPLES Preparation of Crystalline Forms of the (−)-Modafinil Enantiomer and the (+)-Modafinil Enantiomer respectively General The new crystalline forms of the enantiomers of modafinil have been characterised respectively by powder X-ray diffraction spectroscopy, which provides a unique digital signature characteristic of the crystalline form investigated and can be used to distinguish it from amorphous enantiomers of modafinil and any other crystalline form of modafinil enantiomers. The X-ray diffraction data were measured: the D5005 system as an X-ray powder diffractometer (Siemens AG, Karlsruhe, Germany, Eva 5.0 data analysis method), with nickel-filtered copper radiation at λ=1,540 Å (with an accelerator speed of 40 KV, tube current 40 mA) and rotation of the sample during measurement (angle: 3 to 40° [2 theta] at a rate of 0.04° [2 theta].s−1, the step size being 0.04°, preparation of the sample with a preferential orientation). a Miniflex Rigaku (Elexience) system as an X-ray powder diffractometer using chromium radiation, an accelerator speed of 30 KV, a tube current of 15 mA and rotation of the sample during measurement (angle: 3 to 80° [2 theta] at a rate of 0.05° [2 theta]. s−1, the step size being 0.1°, preparation of the sample with a preferential orientation). Using a GADDS system as a X-ray powder diffractometer (Bruker, the Netherlands), equipped with a <<Hi-Star area>> detector and equipped for the analysis of plates with 96 wells. The analyses were performed at ambient temperature using CuKalpha copper radiation in the region of 2 theta angles between 3 and 42°. The diffraction spectrum for each well is collected between two domains of the value for the 2 theta angle (3°≦2 Theta≦21° and 19°≦2 Theta≦42°) with an exposure time of between 50 and 250 seconds. Of course the intensity values can vary in relation to sample preparation, the assembly and the measuring instruments. The 2 theta measurement can also be affected by variations associated with the measuring instruments, so the corresponding peaks can vary from ±0.04° to ±0.2° according to the equipment. Also a person skilled in the art will appreciate having available the interplanar spacings which constitute essential data for diffraction spectra. The interplanar spacings are calculated using Bragg's relationship [(2d sin theta=nλ, in which d=the interplanar spacing (Å), λ=the wavelength of the copper radiation, theta=the angle of rotation of the crystal (in degrees)] when this relationship is satisfied. Examples 1 to 10 Preparation of Form I of (−)-Modafinil and (+)-Modafinil Respectively Example 1 a) Enantiomer I of modafinil was dissolved in polar solvents: methanol, absolute ethanol, absolute ethanol containing 3% of water, ethanol denatured with toluene (2.5%) and containing 3% of water, and water under reflux under the experimental conditions detailed in Table 1. TABLE 1 Quantity of l-modafinil Volume of solvent Solvent (g) (ml) Yield % Methanol 8.37 ≦50 63 Absolute ethanol 7.85 115 56 Absolute ethanol + 3% 5 70 54 of water Ethanol denatured with 5 70 56 toluene + 3% of water Water 5 ≧400 88 After rapid cooling by quenching in a water and ice bath for 30 minutes the medium was filtered and then dried in a stove at 35° C. The crystallised product was identified by its powder X-ray diffraction spectrum as being the polymorph of form I of the l-enantiomer of modafinil. b) Enantiomer d of modafinil (555 g), treated under the same experimental conditions as example 1a in a mixture of ethanol denatured with toluene (2 L) and water (0.1 L), crystallised in polymorphic form I as identified by its powder X-ray diffraction spectrum with a yield of 91%. Example 2: Recrystallisation from Acetone a) 2 g of (−)-modafinil were suspended in acetone (20 ml) in a three-necked flask fitted with a condenser, a thermometer and a stirrer. The mixture was heated under reflux. The reaction mixture was stirred for 30 minutes at approximately 56° C. until the (−)-modafinil was completely dissolved. The solution was then cooled slowly at a rate of −0.5° C./min to 10° C. with stirring. The reaction mixture was filtered, and the solid obtained was dried to yield the I form of (−)-modafinil identified by its X-ray diffraction spectrum. Yield 62%. b) The same experimental conditions applied to (+)-modafinil led to the acquisition of an identical X-ray diffraction spectrum. Example 3: Recrystallisation from Methanol a) 1 g of (−)-modafinil was added to 7 ml of methanol and heated under reflux until the (−)-modafinil was completely dissolved. The reaction mixture was precipitated by adding 6 ml of water at 1° C. The suspension was stirred continuously for 1 minute and then filtered on sintered glass (No. 3). The solid isolated was dried to yield form I of (−)-modafinil identified by its X-ray diffraction spectrum. Yield 55%. b) The same experimental conditions applied to (+)-modafinil led to the acquisition of an identical X-ray diffraction spectrum. Example 4: Recrystallisation from Methanol (2nd Example) a) 2.5 g of (−)-modafinil were added to 90 ml of methanol and heated under reflux until the (−)-modafinil was completely dissolved. The clear solution was added to 200 ml of water at 1° C. and kept stirred for 10 min. The reaction mixture was filtered and the recovered solid was dried to yield form I of (−)-modafinil identified by its X-ray diffraction spectrum. Yield 78%. b) The same experimental conditions applied to (+)-modafinil led to the acquisition of an identical X-ray diffraction spectrum. Example 5: Recrystallisation from 1-4 Dioxan a) 20 mL of 1-4 dioxan were placed in a 50 mL flask and placed under reflux. 2 g of (−)-modafinil were added in order to achieve saturation; stirring was provided by a magnetic bar (300 rpm). The whole was cooled after total dissolution of the (−)-modafinil using a cooling gradient of −0.5° C./min down to 20° C. The crystals obtained were filtered on sintered glass and identified as being form I by its X-ray diffraction spectrum. Yield 51%. b) The same experimental conditions applied to (+)-modafinil led to the acquisition of an identical X-ray diffraction spectrum. Example 6: Recrystallisation from a Mixture of Ortho, Meta and Para Xylene a) 180 mL of a mixture of ortho, meta and para xylene were placed in a 250 mL flask and placed under reflux. 0.5 g of (−)-modafinil were added to achieve saturation; stirring was provided by a magnetic bar (300 rpm). The whole was cooled after total dissolution of the (−)-modafinil using a cooling gradient of −0.5° C./min down to 15° C. The crystals obtained were filtered on sintered glass and identified as being form I by its X-ray diffraction spectrum. Yield 26%. b) The same experimental conditions applied to (+)-modafinil led to the acquisition of an identical X-ray diffraction spectrum. Example 7: Recrystallisation from Ethyl Acetate a) 100 mL of ethyl acetate were placed in a 250 mL flask and placed under reflux; 2 g of (−)-modafinil were added in order to achieve saturation; stirring was provided by a magnetic bar (300 rpm). The whole was cooled after total dissolution of the (−)-modafinil using a cooling gradient of −0.5° C./min down to 20° C. The crystals obtained were filtered on sintered glass and identified as being form I by its X-ray diffraction spectrum. Yield 66%. b) (+)-modafinil (3 g) was dissolved in ethyl acetate (100 ml) under reflux. After cooling by quenching in a water and ice bath for 30 minutes, the medium was filtered and then dried in a stove at 50° C. under vacuum. The crystallised product was identified by its powder X-ray diffraction spectrum as being the polymorph of form I of (+)-modafinil. Example 8: from Other Polymorphic Forms a) CRL 40982 form IV (0.5 g) and CRL 40982 form II (0.5 g) yielded form I by heating to 100° C. Furthermore the pure form I of (−)-modafinil can be prepared by taking up a mixture of (−)-modafinil form I (0.5 g) and form II (0.5 g) and form III (0.5 g) in acetone (20 ml) for a sufficient time to achieve complete conversion (3 days). In the two procedures form I was identified by its powder X-ray diffraction spectrum. b) The use of (+)-modafinil (CRL 40983) under the same conditions yielded the same results. Example 9: from Acetonitrile Solvate a) 1 g of acetonitrile solvate of (−)-modafinil heated to 100° C. for 8 hours converted into a white solid identified as being (−)-modafinil form I by its powder X-ray diffraction spectrum. b) The use of (+)-modafinil (CRL 40983) under the same conditions led to the same results. Example 10: from Monodimethyl Carbonate Solvate a) 1 g of the monodimethyl carbonate solvate of (−)-modafinil heated to 110° C. for 16 hours converted into a white solid identified as being (−)-modafinil form I by its powder X-ray diffraction spectrum. b) The use of (+)-modafinil (CRL 40983) under the same conditions led to the same results. Examples 11 to 12 Preparation of Form II (CRL 40982 Form II) of (−)-Modafinil and (CRL 40983 Form II) of (+)-Modafinil Respectively Example 11 through Rapid Cooling a) Modafinil enantiomer I was dissolved under reflux in the solvents: ethyl acetate, isopropanol, n-propanol and ethanol denatured with toluene (2.5%), according to the experimental conditions detailed in Table 2. TABLE 2 Quantity of Volume of solvent Solvent l-modafinil (g) (ml) Yield % Ethyl acetate 6.33 385 53 Isopropanol 8 110 69 n-propanol 7.85 65 70 Ethanol denatured 5 80 54 with toluene (2.5%) After cooling by quenching in a water and ice bath for 30 minutes, the medium was filtered and then dried in a stove at 35° C. In each experimental procedure the crystallised product was identified by its powder X-ray diffraction spectrum as being the form II polymorph (CRL 40982 form II) of the l-enantiomer of modafinil. b) The d enantiomer of modafinil (3.02 g) was dissolved in 100 ml of isopropanol under reflux and then cooled by quenching in a water and ice bath for 30 minutes, filtered and dried under vacuum in a stove at 50° C. Under these experimental conditions (+)-modafinil crystallised into polymorphic form II (CRL 40983 form II) identified by its powder X-ray diffraction spectrum. Example 12: by Cooling from Isopropanol a) 100 mL of isopropanol was placed in a 250 mL flask which was placed under reflux and then 3 g of (−)-modafinil were added so as to achieve saturation, the mixture was stirred using a magnetic bar (300 rpm). After total dissolution of the (−)-modafinil the solution was slowly cooled to 20° C. at a cooling gradient of −0.5° C./min. The crystals obtained were filtered on sintered glass. The crystallised product was identified by its powder X-ray diffraction spectrum as being the form II polymorph (CRL 40982 form II) of the l-enantiomer of modafinil. Yield 42%. b) The same experimental conditions applied to (+)-modafinil led to the acquisition of an identical X-ray diffraction spectrum. Example 13 Preparation of Form III (CRL 40982 Form III) of (−)-Modafinil and (CRL 40983 Form III) of (+)-Modafinil Respectively Example 13: by Slow Cooling from Acetone a) The I enantiomer of modafinil (5 g) was dissolved under reflux in 90 ml of acetone. After rapid cooling by quenching in a water and ice bath for 30 minutes the medium was filtered and then dried in a stove at 35° C. The crystallised product was identified by its powder X-ray diffraction spectrum as being the form III polymorph of l-enantiomer of modafinil. Yield 61%. b) The same experimental conditions applied to (+)-modafinil led to the acquisition of an identical X-ray diffraction spectrum. Examples 14 to 16 Preparation of Form IV (CRL 40982 Form IV) of (−)-Modafinil and (CRL 40983 Form III) of (+)-Modafinil Respectively Example 14: Recrystallisation from Chloroform a) 20 mL of chloroform was placed in a 50 mL flask and heated under reflux. 1.5 g of (−)-modafinil were added so as to achieve saturation; stirring was provided by a magnetic bar (300 rpm). The whole was slowly cooled after total dissolution of the (−)-modafinil at a cooling gradient of −0.5° C./min down to 20° C. The crystals obtained were filtered on sintered glass and identified as being (−)-modafinil form IV by its powder X-ray diffraction spectrum. b) The same experimental conditions applied to (+)-modafinil led to the acquisition of an identical X-ray diffraction spectrum. Example 15: Recrystallisation from Methylethylketone a) 100 mL of methylethylketone was placed in a 250 mL flask and heated under reflux. 2 g of (−)-modafinil were added so as to achieve saturation; stirring was provided by a magnetic bar (300 Rpm). The whole was slowly cooled after total dissolution of the (−)-modafinil at a cooling gradient of −0.5° C./min down to 20° C. The crystals obtained were filtered on sintered glass and identified as being (−)-modafinil form IV by its powder X-ray diffraction spectrum. b) The same experimental conditions applied to (+)-modafinil led to the acquisition of an identical X-ray diffraction spectrum. Example 16: Recrystallisation from Tetrahydrofuran 20 mL of tetrahydrofuran was placed in a 50 mL flask which was heated under reflux. 1 g of (−)-modafinil was added so as to achieve saturation; stirring was provided by a magnetic bar (300 Rpm). The whole was slowly cooled after total dissolution of the (−)-modafinil with a cooling gradient of −0.5° C./min down to 10° C. The crystals obtained were filtered on sintered glass and identified as being (−)-modafinil form IV by its powder X-ray diffraction spectrum. Examples 17 and 17 B Preparation of Form V (CRL 40982 Form V) of (+)-Modafinil and (CRL 40983 Form V) of (+)-Modafinil Respectively Operating Procedure for Examples 17 and 17 b A methanol solution of the d enantiomer of modafinil (150 mg/ml) was distributed over a 96-well plate and then the methanol was evaporated under slight vacuum before adding 25 μl of various solvents (concentration=3.75 mg/25 μL of solvent) at ambient temperature. The multi-well plates were made of stainless steel (316 L) and each sealed well contained a total volume of 50 μL. The plate was heated to an initial temperature of 60° C. with a temperature gradient of 4.8° C./min. After 30 minutes the plate was cooled slowly (−0.6° C./min) or rapidly (−300° C./min) until a final temperature of 3° C. was achieved, and it was then held at that final temperature for a minimum of 1 hour or a maximum of 48 hours. The solvent was evaporated under vacuum (nitrogen atmosphere) and the crystallised product was analysed. Example 17: Recrystallisation from 2-Propanone d-modafinil crystallised from 2-propanone in accordance with the operating conditions above by applying slow cooling (−0.6° C./min) and holding the temperature at 3° C. for 1 hour. The crystals were identified as being (+)-modafinil form V (CRL 40983 form V) by its powder X-ray diffraction spectrum. Example 17 b: Recrystallisation from Tetrahydrofuran (THF) d-modafinil crystallised from THF in accordance with the operating conditions above by applying rapid cooling (−300° C./min) and holding the temperature at 3° C. for 1 hour. The crystals were identified as being (+)-modafinil form V (CRL 40983 form V) by its powder X-ray diffraction spectrum. Examples 18 to 19 Preparation of (−)-Modafinil Solvates and of (+)-Modafinil Example 18: Preparation of the Dimethyl Carbonate Solvate of (−)-Modafinil a) 20 ml of dimethyl carbonate were added to 2 g of (−)-modafinil and refluxed. The reaction mixture was stirred for 10 minutes until the (−)-modafinil completely dissolved. The solution was cooled slowly (−0.5° C./min) down to 10° C. with stirring. The reaction mixture was then filtered through sintered glass (No. 3). Analysis of the dimethyl carbonate solvate of modafinil yielded a mass of approximately 24% starting from around 50° C. down to 110° C. The stoichiometry of the dimethyl carbonate solvate is therefore 1-1. This is therefore a true solvate, identified as being the dimethyl carbonate solvate of (−)-modafinil by its powder X-ray diffraction spectrum. Yield 88%. b) The same experimental conditions applied to (+)-modafinil led to the acquisition of an identical X-ray diffraction spectrum. Example 19: Preparation of the Acetonitrile Solvate of (−)-Modafinil a) Crystals of polymorphic form I of (−)-modafinil were suspended in acetonitrile for 3 days at 20° C. The solid recovered was identified as an acetonitrile solvate by X-ray diffraction. The solvate corresponded to a true solvate having a stoichiometry of 1-1, identified as being the acetonitrile solvate of (−)-modafinil by its powder X-ray diffraction spectrum. Yield 92%. b) The same experimental conditions applied to (+)-modafinil led to the acquisition of an identical X-ray diffraction spectrum. Example 20: Preparation of the Acetic Acid Solvate a) 75 mg of d or l-modafinil were suspended in acetic acid in Minimax reactors in order to achieve a concentration of 15% (weight/volume). The crystallisation medium, which was constantly stirred, was raised to an initial temperature of 60° C. or 80° C. using a temperature gradient of 3° C./min. After 30 minutes the medium was cooled slowly (−0.6° C./min) or rapidly (−300° C./min) until a final temperature of 3° C. was obtained, and was then held at this final temperature for a minimum of 1 hour or a maximum of 48 hours. Under these experimental conditions the acetic acid solvate was obtained and identified by its powder X-ray diffraction spectrum. b) The same experimental conditions applied to (+)-modafinil led to the acquisition of an identical X-ray diffraction spectrum. Example 21: Preparation of the Amorphous Form of (−) and of (+)-Modafinil The solvate of (−) or (+)-modafinil obtained in example 20 was converted into the amorphous form by heating at 120° C. for 3 hours. The powder X-ray diffraction spectrum obtained is shown in FIG. 16. Examples 22 to 29 Resolution of (±)-Modafinil Acid by Preferential Crystallisation Using the AS3PC Method in Ethanol Conditions associated with the equilibria Solubility of the racemic mixture in ethanol: Temperature (° C.) 10.0 20.0 30.0 Solubility by mass (%) 3.0 4.1 5.96. Solubility of the pure (+)-antipode=1.99% at 20° C.; ratio α=2.06 Coordinates of point L=Concentration: 5.96% temperature: 30° C. Change in THOMO with enantiomer excess=(racemic mixture/(solvent+racemic mixture))=5.96%=constant Enantiomer excess 0 3.94 7.66 11.1 THOMO (° C.) TL = 30 32.4 34.5 36.3 Conditions associated with the kinetics By adjusting TB to be closer to TL approximately 40% of the final harvest in the form of fine crystals can be thus obtained at the start of the experiment, and then only 60% of the expected final mass has to be produced. This operation is easy to carry out when the Z ratio is sufficiently high (equal to or greater than 0.8 per percentage enantiomer excess). In the case of modafinil acid, crystallisation is carried out correctly. Z = [ ⅆ ( T HOMO ) ⅆ e . e ] ( ± ) ⁢ constant = Z = [ ⅆ ( T HOMO ) ⅆ e . e ] TLconstant = 5 9 Temperature TB1=33.5° C. and TB2=31.5° C. Temperature TF=17° C. Cooling function=T=f(t) Temperature (° C.) 33.5 17 17 t (min) 0 60 TFiltration Type I Cooling Function Temperature (° C.) 31.5 17 17 t (min) 0 60 TFiltration Type II Cooling Function In the two cases in point, from TB1 or TB2 the cooling function is a linear segment: T1=33.5−0.275 t (Type 1) T2=31.5−0.24167 t (Type 2) followed by a plateau at 17° C. Example 22: Resolution of (±)-Modafinil Acid by the AS3PC Method at the 35 cc Scale in Ethanol Initial Conditions Enantiomer excess=11% Mass of solvent Mass (±) (g) Mass (+) (g) Cooling function 38.38 2.43 0.3 Type 1 Duration of the plateau at TB1 or TB2=30 minutes. Stirring speed=200 rpm Results Mass of the pure No. antipode (g) Optical purity (%) 1 0.61 (+) 90.7 2 0.65 (−) 89.4 3 0.68 (+) 90.5 4 0.64 (−) 90.6 5 0.65 (+) 88.8 6 0.72 (−) 91.5 7 0.71 (+) 92.8 Mean mass of the crystals of the pure antipode=0.66 g Average optical purity=90.6% Example 23: Resolution of (±)-Modafinil Acid by the AS3PC Method on a Scale of 400 cc in Ethanol Initial conditions Initial enantiomer excess=11% Mass of solvent Mass (±) (g) Mass (+) (g) Cooling function 511 32.42 3.99 Type I Stirring speed=200 rpm Results Mass of the pure antipode No. (g) Optical purity (%) 1 8.41 (+) 89.4 2 8.69 (−) 90.7 3 8.57 (+) 89.8 Mean mass of the crystals of the pure antipode=8.55 g Average optical purity=89.63% Example 24: Resolution of (±) Modafinil Acid by the AS3PC Method on a 2 Litre Scale in Ethanol Initial conditions Initial enantiomer excess=11.1% Mass of solvent Mass (±) (g) Mass (+) (g) Cooling function 1874 118.4 14.84 Type I Results Mass of the pure antipode No. (g) Optical purity (%) 1 32.1 (+) 89.1 2 32.3 (−) 90.3 3 32.5 (+) 91.2 4 32.9 (−) 89.7 5 33.1 (+) 90.3 6 32.7 (−) 90.7 7 32.9 (+) 90.6 Mean mass of the crystals of the pure antipode=32.6 g Average optical purity=90.3% Example 25: Resolution of (±) Modafinil Acid by the AS3PC on a 10 Litre Scale in Ethanol Initial conditions Initial enantiomer excess=11.7% Mass of solvent Mass (±) (g) Mass (+) (g) Cooling function 6481 408 51.32 Type I or II Stirring speed=200 rpm throughout the procedure using an Impeller® moving stirrer. Results Mass of the pure antipode Optical purity Cooling No. (g) (%) Cycle length function 1 (+) 121.9 90.5 103 I 2 (−) 121.1 92.2 104 I 3 (+) 137.6 91.3 83 II 4 (−) 134.7 90.8 84 II 5 (+) 135.1 90.6 83 II 6 (−) 134.5 91.2 82 II Mean mass of the crystals of the pure antipode=130.8 g Average optical purity=89.9% Using the AS3PC Method in 2-methoxyethanol Conditions associated with the equilibria Solubility of the racemic mixture in 2-methoxyethanol: Temperature (° C.) 10.0 20.0 30.0 40.0 Solubility by mass (%) 7.4 8 13.5 16 Solubility of the pure (+) antipode=4% at 20° C. ratio α=2.53 Coordinates of point L=Concentration: 16% temperature: 39.4° C. Change in THOMO with enantiomer excess=(racemic mixture/(solvent+racemic mixture))=16%=constant Enantiomer excess 0 4% 6% 8% THOMO (° C.) TL = 39 44 46 48 Example 26: Resolution of (±)-Modafinil Acid in 2-methoxyethanol by the AS3PC Method on a 10 Litre Scale Initial conditions Enantiomer excess=10% Initial temperature TB: 41° C. Filtration temperature TF: 30° C. Linear temperature gradient from 41° C. to 30° C. in 1 hour Mass of solvent Mass (±) (g) Mass (+) (g) 8000 g 1523 132 Stirring speed=200 rpm Results Mass of the pure antipode No. (g) Optical purity (%) 1 269.86 (+) 100 2 300 (−) 97 3 348.68 (+) 100 4 369.2 (−) 99.97 5 413.97 (+) 100 6 453.2 (−) 95.5 7 423.8 (+) 98 8 456 (−) 99.7 9 494.6 (+) 99.3 10 485.4 (−) 100 11 517 (+) 92 12 487.97 (−) 95.9 13 471.24 (+) 99.5 Mean mass of the crystals of the pure antipode=422.4 g Average optical purity=98.2% Using the AS3PC Method in Methanol Conditions associated with the equilibria Solubility of the racemic mixture in methanol: Temperature (° C.) 10.0 20.0 30.0 40.0 Solubility by mass (%) 7.4 9.7 13.9 25.7 Solubility of the pure (+) antipode=4.9% at 20° C. ratio α=2.53 Coordinates of point L=Concentration: 25.6% temperature: 46.5° C. Change in THOMO with enantiomer excess=(racemic mixture/(solvent+racemic mixture))=25.7%=constant Enantiomer excess 0 4% 6% 8% 10% THOMO (° C.) TL = 45 50 52 53 54 Example 27: Resolution of (±)-Modafinil Acid by the AS3PC Method on a 1 Litre Scale in Methanol Experimental conditions Enantiomer excess=10% Initial temperature TB: 46.5° C. Filtration temperature TF: 30° C. Temperature gradient: linear from 39.4° C. to 18° C. for 1 hour Mass of solvent Mass (±) (g) Mass (+) (g) 1450 g 501.5 55.7 Stirring speed=230 rpm Results Mass of the pure antipode No. (g) Optical purity (%) 1 107.1 (+) 99.7 2 90.9 (−) 78.2 3 137.1 (+) 72.7 4 125.5 (−) 84.1 5 95.9 (+) 94.0 6 91.6 (−) 88.6 7 87.0 (+) 85.7 8 92.2 (−) 88.1 9 107.0 (+) 104.2 10 130.6 (−) 120.7 11 159.9 (+) 111.0 12 123.3 (−) 113.8 13 133.0 (+) 130.3 14 143.0 (−) 134.7 15 139.2 (+) 128.5 16 159.4 (−) 127.5 17 114.0 (+) 111.5 18 123.4 (−) 120.9 19 180.6 (+) 99.3 20 114.2 (−) 110.9 21 123.1 (+) 120.6 22 118.4 (−) 115.0 23 140.1 (+) 135.9 24 186.2 (−) 118.6 25 157.1 (+) 106.8 26 121.2 (−) 102.2 27 126.5 (+) 122.5 28 106.6 (−) 99.0 Mean mass of the crystals of the pure antipode=108 g Average optical purity=87.5% Using the SIPC Method in Ethanol Conditions associated with the equilibria (see AS3PC method) Example 28: Resolution of (±) Modafinil Acid by the SIPC Method on a 2 Litre Scale with Seeding at the end of Cooling in Ethanol Initial conditions Initial enantiomer excess=11.8% Temperature at which the starting mixture is a homogeneous solution TD=40° C. Mass of solvent Mass (±) (g) Mass (+) (g) Cooling function 1874 118.4 14.84 20 min from 40° C. to 17° C. = seeding temperature Time (plateau) at TF before adding the seeds=0 minutes Mass of seeds=1% Crystallisation time=fastest possible cooling by quenching Stirring speed=200 rpm throughout the procedure using an Impeller® mobile Results Mass of the pure antipode No. (g) Optical purity (%) 1 30.9 (+) 90.4 2 31.5 (−) 90.7 3 31.3 (+) 91.4 4 31.2 (−) 90.9 5 31.6 (+) 91.5 Mean mass of the crystals of the pure antipode=31.28 g Average optical purity=91% Example 29: Resolution of (±)-Modafinil Acid by the S3PC Method on a 2 Litre Scale with Seeding During Cooling in Ethanol Initial enantiomer excess: 11.14% Mass of solvent Mass (±) (g) Mass (+) (g) Cooling function 1874 118.4 14.84 20 min from 40° C. to 17° C. Seeding temperature=29° C. Seed mass=1% Crystallisation time=the fastest possible cooling by quenching Stirring speed=200 rpm throughout the procedure using an Impeller® mobile stirrer. Results Optical purity (%) No. Mass before purification 1 25.2 (+) 84.5 2 24.9 (−) 85.6 3 25.6 (+) 84.6 4 25.2 (−) 85.3 5 24.9 (+) 85.8 Mean mass of the crystals of the pure antipode=25.2 g Average optical purity=85.2% Examples 30 to 32 Conversion of the Optical Enantiomers of Modafinil Acid to Alkyl Ester This stage is illustrated through the use of (−)modafinil acid. Examples 30 to 31: Esterification of (−)-Modafinil Acid Example 30: in the Presence of Dimethylsulphate 3.3 litres of acetone, 0.6 litres of water, 349 g of Na2CO3 (3.29 moles), 451 g of (−)-modafinil acid (1.64 moles) were placed in a 10 litre flask and heated to achieve reflux. Then 330 ml of dimethyl sulphate (3.29 moles) were run in over half an hour. Reflux was continued for one hour and then it was allowed to cool to ambient temperature in 20 hours. The medium was then poured on to 6.6 kg of ice. Crystallisation was immediate and after 3 hours additional stirring filtration yielded a white precipitate which was washed in 6 litres of water. This product was taken up again in 6 litres of water and again filtered. The precipitate was dried under vacuum at 35° C. and in this way 436.3 g of methyl ester were obtained (Yield=92.3%). Example 31: in the Presence of Methyl Chloroformate 100 g of (−)-modafinil acid (0.36 mole) and 21.6 ml of triethylamine (0.36 mole) were added to 450 ml of methanol. 30 ml of methyl chloroformate 0.36 mole) were progressively poured onto the solution obtained after dissolution of the salt. Pouring was carried out over 15 minutes increasing from 28° C. to 35° C. (release of CO2). This was stirred for 2 hours and poured onto piled ice+water (500 g/500 ml). The ester crystallised out; after filtering and drying 94.5 g of ester was obtained. (Yield=90.1%). Example 32: Ammonolysis of the Alkyl Ester of Optically Active Modafinil Acid 1.63 litres of methanol denatured with toluene, 0.1 litres of water and 425.1 g of methyl ester (1.474 moles) were placed in a 4 litre double jacket reactor. The temperature was raised to 30° C. and bubbling of ammonia was begun maintaining this temperature. The operation lasted 1 hour and 45 minutes and the mass of ammonia introduced was 200 g. Stirring was maintained for 21 hours 30 minutes, and then it was cooled with the temperature being set to 0° C. The medium was then filtered on No. 3 sintered glass and 57.2 g was obtained straight away, together with a filtrate which was evaporated to dryness. The residue was taken up in 1.2 litres of ethanol denatured with toluene and after filtration a second amount of 308.6 g was obtained. First crystallisation: The two amounts were pooled and recrystallised in 1.83 litres of ethanol denatured with toluene. Hot filtration yielded a filtrate which when cooled yielded a product which was filtered and dried under vacuum at 30° C. 162.2 g of a white product was obtained. Second crystallisation: These 162.2 g were mixed with 810 ml of ethanol denatured with toluene and heated under reflux to achieve complete dissolution. This was then allowed to crystallise by cooling with ice and then filtered through No. 4 sintered glass and dried under vacuum at 30° C. 147.3 g (−)-modafinil (CRL 40982) was obtained. Yield=36.6%. Characteristics: Rotation power=−18.6 (4.9% solution in methanol) Melting point=163° C. Examples 33 to 34: Crystalline Structures Example 33: Structure of Modafinil Acid Modafinil crystals were obtained from acetone. This phase has the following characteristics: Hexagonal P31 or P32 depending upon the enantiomer, the modafilil is therefore a conglomerate, a=9.55, b=9.55, c=13.14 Å α=90,000, β=90,000, γ=120,000° The diffraction intensities were measured using an automatic SMART APEX (Brucker) diffractometer at 20° C. The structure was resolved using the set of Saintplus, Sadabs, Shelxs software packages. The unusual nature of this spatial group in the case of chiral organic molecules must be emphasised. The pattern repeats three times in the crystal lattice, so again Z=1. The molecules are linked together by hydrogen bonds via the acid and sulphoxide groups. It may be commented that the strongest interactions (the hydrogen bonds) wrap around the ternary helical axis along the crystallographic direction z. Example 34: Structure of (−) and (+)-modafinil form I The crystalline structure of (+)-modafinil form I, identified as being identical to that of (−)-modafinil form I, was determined. It has the following properties: Crystalline system=monoclinic, Spatial group=P21 a=5.6938, b=26.5024, c=9.3346 Å β=105.970° The diffraction intensities were measured using an automatic SMART APEX (Brucker) diffractometer at 20° C.
20060217
20061107
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A61K31165
19
KUMAR, SHAILENDRA
METHOD FOR THE PRODUCTION OF CRYSTALLINE FORMS AND CRYSTALLINE FORMS OF OPTICAL ENANTIOMERS OF MODAFINIL
UNDISCOUNTED
0
ACCEPTED
A61K
2,006
10,539,981
ACCEPTED
Leds driver
The power supply (20) for LEDs provides power to a LED light source (10) having a variable number of LEDs wired in series and/or in parallel. The power supply (20) uses current and voltage feedback to adjust power to the LEDs and provides protection to the LED light source (10). A feedback controller (27) compares sensed current and sensed voltage to a reference signal and generates a feedback signal, which is processed by a power factor corrector (124) to adjust the current flow through the transformer supplying current to the LEDs. A LED control switch (24) clamps a peak of the current to the LEDs to provide further protection to the LED light source (10). A short/open detection circuit (30) indicates any detection of a “LED outage” of the LED light source (10).
1. A power supply (20) for a LED light source (10), said power supply (20) comprising: a power converter (23) operable to provide a regulated power including a LED current and a LED voltage; and a LED control switch (24) operable to control a flow of the LED current through the LED light source (10), wherein said LED control switch (24) is further operable to clamp a peak of the LED current during an initial loading stage of the LED light source (10). 2. The power supply (20) of claim 1, wherein said LED control switch (24) includes: a switch (SW1) operable to establish a current path from the LED light source (10) to said power converter (23) when the LED current is below a peak threshold, said switch (SW1) further operable to eradicate the current path when the LED current is above the peak threshold. 3. The power supply (20) of claim 2, further comprising: a LED PWM dimmer (29) operable to provide a pulse width modulation signal to said switch (SW1) in response to an external dim command, wherein said pulse width modulation signal has a target pulse width in response to the dim command exceeding a ramp signal, and wherein said pulse width modulation signal has a minimum pulse width in response to the ramp signal exceeding the dim command. 4. The power supply (20) of claim 3, wherein said LED PWM dimmer (29) includes: an astable multivibrator circuit (129) operable to establish the minimum pulse width in a precise and temperature insensitive manner. 5. The power supply (20) of claim 2, wherein said LED PWM dimmer (29) includes: a comparator (U3) operable to establish the target pulse width in response to a reception of the dim command and the ramp signal. 6. The power supply (20) of claim 5, wherein said LED PWM dimmer (29) further includes: a ramp generator operable to provide the ramp signal to said comparator (U3) indicative of the minimum pulse width. 7. The power supply (20) of claim 6, wherein said LED PWM dimmer (29) further includes: an astable multivibrator circuit (129) operable to establish the minimum pulse width in a precise and temperature insensitive manner. 8. The power supply (20) of claim 1, further comprising: a detection circuit (30) operable to provide a detection signal indicative of an operating condition of the LED light source (10) associated with the LED voltage, wherein the detection signal has a first level representative of a load condition of the LED light source (10), and wherein the detection signal has a second level representative of either a short condition or an open condition of the LED light source (10). 9. The power supply (20) of claim 8, wherein the load operating condition indicates a magnitude of a LED voltage drop across the LED light source (10) is between zero volts and the LED voltage. 10. The power supply (20) of claim 8, wherein the short operating condition indicates a magnitude of a LED voltage drop across the LED light source (10) approximates zero volts. 11. The power supply (20) of claim 8, wherein the open operating condition indicates a magnitude of a LED voltage drop across the LED light source (10) approximates the LED voltage. 12. The power supply (20) of claim 1, further comprising: a current sensor (25) operable to sense the LED current flowing through the LED light source (10), said current sensor (25) including an operational amplifier (U6), and means for adjusting a gain of said differential amplifier. 13. The power supply (20) of claim 1, further comprising: a voltage sensor (26) operable to sense the LED voltage applied to the LED light source (10), said voltage sensor (26) including an operational amplifier (U6), and means for adjusting a gain of said differential amplifier. 14. A method of operating a LED light source (10), said method comprising: providing a regulated power to the LED light source (10), the regulated power including a LED current and a LED voltage; controlling a flow of the LED current through the LED light source (10); and clamping a peak of the LED current during an initial loading stage of the LED light source (10). 15. The method of claim 14, further comprising: generating a detection signal indicative of an operating condition of the LED light source (10) associated with the LED voltage, wherein the detection signal has a first level representative of a normal operating condition of the LED light source (10), and wherein the detection signal has a second level representative of either a short operating condition or an open operating condition of the LED light source (10).
The technical field of this disclosure is power supplies, particularly, a power supply for LEDs. Significant advances have been made in the technology of white light emitting diodes (LEDs). White light LEDs are commercially available which generate 10-15 lumens/watt. This is comparable to the performance of incandescent bulbs. In addition, LEDs offer other advantages such as longer operating life, shock/vibration resistance and design flexibility because of their small size. As a result, white light LEDs are replacing traditional incandescent sources for illumination applications such as signage, accenting, and pathway lighting. The white LEDs can be used alone or in conjunction with colored LEDs for a particular effect. The electrical characteristics of LEDs are such that small changes in the voltage applied to the LED lamp will cause appreciable current changes. In addition, ambient temperature changes will also result in LED current changes by changing the forward drop across the LEDs. Furthermore, the lumen output of LEDs depends on the LED current. The existing electrical power supplies for LED light sources are not designed to precisely regulate the LED current to prevent luminous intensity variations due to input ac voltage variations and ambient temperature. Operation of LED lamps at excessive forward current for a long period can cause unacceptable luminous intensity variations and even catastrophic failure. In addition, current electrical power supplies do not minimize power consumption to maximize energy savings. It would be desirable to have a power supply for LEDs that would overcome the above disadvantages. One form of the present invention is a power supply for a LED light source that comprises a power converter and a LED control switch. The power converter operates to provide a regulated power including a LED current and a LED voltage. The LED control switch further operates to control a flow of the LED current through the LED light source. The LED control switch further operates to clamp a peak of the LED current during an initial loading stage of the LED light source. This prevents damage to the LED light source due to a field misapplication. A second form of the present invention is a power supply for a LED light source further comprising a detection circuit operating to provide a detection signal indicative of an operating condition of the LED light source associated with the LED voltage. The detection signal has a first level representative of a load condition of the LED light source. The detection signal has a second level representative of a short condition or an open condition indicative of the LED light source. A third form of the present invention is a power supply for a LED light source further comprising a LED current sensor or a LED voltage sensor. Each sensor includes a differential amplifier and means for adjusting a gain of the differential amplifier. The foregoing forms as well as other forms, features and advantages of the present invention will become further apparent from the following detailed description of the presently preferred embodiments, read in conjunction with the accompanying drawings. The detailed description and drawings are merely illustrative of the present invention rather than limiting, the scope of the present invention being defined by the appended claims and equivalents thereof. FIG. 1 illustrates a block diagram of a power supply for an LED light source in accordance with the present invention; FIG. 2 illustrates a schematic diagram of one embodiment of the FIG. 1 power supply in accordance with the present invention; FIG. 3 illustrates a timing diagram of one embodiment of a control circuit in accordance with the present invention; FIG. 4 illustrates a schematic diagram of one embodiment of a short/open detection circuit in accordance with the present invention; and FIG. 5 illustrates a schematic diagram of one embodiment of a differential amplification circuit in accordance with the present invention. FIG. 1 illustrates a block diagram of a power supply 20 for powering an LED light source 10 including a variable number of LEDs wired in series and/or in parallel. A single-phase ac input 21 of power supply 20 provides a voltage VAC to an AC/DC converter 22 of power supply 20 whereby AC/DC converter 22 converts voltage VAC into a voltage VDC. AC/DC converter 22 provides voltage VDC to a power converter 23 of power supply 20 whereby power converter 23 generates a regulated power PREG including a LED current and a LED voltage VLED. Power converter 23 provides regulated power PREG to LED light source 10. In operation, LED control switch 24 controls a flow of the LED current through the LED light source 10. A LED current sensor 25 of power supply 20 provides a sensed current ISE indicative of a magnitude of the LED current flowing through LED light source 10. A LED voltage sensor 26 of power supply 20 provides a sensed voltage VSE indicative of a magnitude of the LED voltage VLED applied to LED light source 10. Sensed current ISE and sensed voltage VSE are fed to a feedback controller 27 of power supply 20. A signal reference 28 of power supply 20 provides a reference signal REF to a feedback controller 27, whereby feedback controller 27 provides a feedback signal FB to power converter 23 based on sensed current ISE, sensed voltage VSE and reference signal REF. LED control switch 24 further operates to clamp a peak of LED current flowing through LED light source 10 to thereby protect the LED light source 10 from electrical damage. LED control switch 24 is particularly useful when LED light source 10 transitions from an open operating state to a load operating state (i.e., an initial loading), such as, for example, a connection of LED light source 10 to power supply 20 subsequent to an energizing of power supply 20. An LED dimmer 29 of power supply 20 operates to control a desired dimming of LED light source 10 by providing a control signal CS to LED control switch 24. Control signal CS can be in one of many conventional forms, such as, for example, a pulse width modulation signal (“PWM”). A short/open detection circuit 30 provides a detection signal DS as an indication of a short condition or an open condition of LED light source 10 based on the LED voltage VLED applied to LED light source 10. The configuration of each component 21-30 of power supply 20 is without limit. Additionally, coupling among the components 21-30 of power supply 20 can be achieved in numerous ways (e.g., electrically, optically, acoustically, and/or magnetically). The number of embodiments of power supply 20 is therefore essentially limitless. FIG. 2 illustrates a schematic diagram of one embodiment 120 of power supply 20 (FIG. 1) for one embodiment 110 of LED light source 10 (FIG. 1) made in accordance with the present invention. Power supply 120 employs a flyback transformer with current feedback through a power factor corrector (“PFC”) IC to supply power to LED light source 110. To this end, power supply 120 includes an EMI filter 121, an AC/DC converter (“AC/DC”) 122, a transformer 123, a power factor corrector 124, a feedback controller 125, an optocoupler 126, a LED control switch 127, a LED PWM dimmer 129, resistors R1-R7, capacitors C1-C5, diodes D1-D3, zener diodes Z1-Z3 and a MOSFET Q1 as illustrated in FIG.2. Voltage is supplied to power supply 120 at VIN to EMI filter 121. The voltage can be an ac input and is typically 50/60 Hertz at 120/230 VRMS. EMI filter 121 blocks electromagnetic interference on the input. AC/DC 122 can be a bridge rectifier and converts the ac output of EMI filter 120 to dc. Transformer 123 includes a primary winding W1, W4 and W5, and a plurality of secondary windings W2 and W3. The windings W1/W2 constitute the flyback transformer to power the LED light source 110. The flyback transformer is controlled by PFC 124, which is a power factor corrector integrated circuit, such as model L6561 manufactured by ST Microelectronics, Inc. The flyback transformer transfers power to LED light source 110 where the LED current and the LED voltage are controlled by feedback control. The forward converter operation of windings W1/W3 charge a capacitor C3 and a reference current signal is generated between a series resistor R4 and a zener Z2. The peak voltage across capacitor C3 depends on the W1/W3 turns ratio. The output dc voltage from flyback operation of windings W1/W2 cannot be used to generate the reference current signal since the output dc voltage across LED light source 110 can have a wide range—from 2.6 Volts dc for one LED lamp to about 32 Volts dc for 8 LEDs in series. The forward converter operation of windings W1/W3 can be used instead. The forward converter operation of the W1/W5 windings can also be used to supply power to the integrated circuits, such as PFC 124. A sensed LED current ISE flows through resistor R1, which is in series with the LED light source 110 via LED control switch 127. A voltage representative of sensed LED current ISE is applied to a non-inverting input of a comparator U1. A sensed LED voltage VSE is generated by zener diode Z1. Sensed LED current ISE and sensed LED voltage VSE as well as a voltage reference VREF are fed to feedback controller 125,. whereby a voltage feedback VFB from feedback controller 125 drives an optocoupler 126 via resistor R7. In generating voltage feedback VFB, feedback controller 125 employs a pair of comparators U1 and U2, resistors R8-R12, and a capacitor C6 as illustrated in FIG. 2. Feedback controller 125 is necessary since optocouplers have a wide range of current transfer ratio (CTR). Feedback controller 125 maintains an accurate voltage feedback VFB to thereby avoid large errors in LED current flowing through LED light source 110. Optocoupler 126 isolates the dc circuit supplying the LED light source 110 from the ac circuit power supply at EMI filter 120, the two circuits being on the opposite sides of the transformer 123. The output of the optocoupler 126 is connected to PFC 124, which supplies a gate drive signal to MOSFET Q1. Control of MOSFET Q1 adjusts the current flow through winding W1 of transformer 123 to match the LED light source 110 power demand. The internal 2.5 V reference signal and an internal compensation circuit of PFC 124 maintains the voltage drop across a resistor R6 at 2.5V. Although this example uses MOSFET Q1 for adjusting the transformer current, alternate embodiments can use other types of transistors to adjust the current, such as an insulated gate bipolar transistor (“IGBT”) or a bipolar transistor. The input to PFC 124 at ZCD provides a reset signal powered from windings W2/W4. Zener diode Z1 also provides overvoltage protection for LED light source 110. Specifically, zener diode Z1 connects across the output connection to the LED light source 110 and clamps the output voltage to a specified maximum value. The nominal zener operating voltage is selected to be just over the maximum specified output voltage. In case of an output open circuit, the flyback operation of windings W1/W2 of transformer 123 would continue to build the output voltage. The increasing output voltage turns on the zener diode Z1 to thereby increase the amount of feedback to resistor R6 from feedback controller 125 via resistor R7 and optocoupler 126. This limits the gate drive signal to MOSFET Q1, preventing the flyback converter from building the output voltage to the LED light source 110 beyond a specified maximum voltage. Similarly, zener diode Z3 connected from the reset winding W4 to resistor R6 will prevent output overvoltage due to a malfunction of feedback controller 125. In alternate embodiments, either zener diode Z1 or zener diode Z3, or both zener diode Z1 and zener diode Z3 can be omitted depending on the degree of control protection required for a particular application. LED control switch 127 includes a switch SW1 in the form of a MOSFET and a switch SW2 in the form of a bipolar transistor. Switches SW1 and SW2 can be in other conventional forms, such as, for example, an IGBT. As illustrated, a drain of MOSFET switch SW1 is connected to LED light source 110. A gate of MOSFET switch SW1 is connected to a collector of bipolar switch SW2. A source of MOSFET switch SW1 and a base of bipolar switch SW2 are connected to zener diode Z1, resistor R1, and feedback controller 125. An emitter of bipolar switch SW2 is connected to ground. In operation, switch SW1 is turned on and switch SW2 is turned off when the LED current is below the desired peak. This mode permits a normal operation of the front-end components of power supply 120. Conversely, switch SW1 is turned off and switch SW2 is turned on when the LED current exceeds the desired peak. This limits the peak of the LED current to a safe level whereby damage to LED light source 110 is prevented. As will be appreciated by one having skill in the art, LED control switch 127 is particularly useful upon a connection of LED light source 110 to an energized power supply 120 whereby capacitor C2 discharges stored energy to LED light source 110 with a current having a peak clamped to thereby prevent damage to LED light source 110. MOSFET switch SW1 can be operated by a conventional gate driver (not shown) or by an illustrated LED PWM dimmer 128. LED PWM dimmer 128 provides a PWM signal (not shown) to MOSFET switch SW1 in response to an external dim command VDC. LED PWM dimmer 128 adjusts the duty cycle of the PWM signal to thereby produce a desired light output from LED light source 110. LED PWM dimmer 128 is particularly useful in producing a precise and temperature sensitive minimum dim level for LED light source 110. LED PWM dimmer 128 includes a diode D4 and a diode D5 connected to the gate of MOSFET switch SW1. A comparator U3 of LED PWM dimmer 128 is in the form of an operational amplifier having an output connected to diode D4 and a non-inverting input for receiving a dimming command VDC. A conventional astable multivibrator circuit 129 of LED PWM dimmer 128 is connected to diode D5. A ramp generator of LED PWM dimmer 128 includes a resistor R16 connected to diode D5 and a gate of transistor Q2 in the form of a MOSFET. Transistor Q2 can be in other forms, such as, for example, an IGBT. The ramp generator further includes an operational amplifier U4. A resistor R15, a resistor R17, a drain of bipolar transistor Q2, a capacitor C7, and an inverting input of comparator U3 are connected to a non-inverting input of operational amplifier U4. Resistor R15 is further connected to an output of operational amplifier U4. A resistor R13 is connected to the output and an inverting input of operational amplifier U4. A resistor R14 is connected to the inverting input of operational amplifier U4 and ground. The source of MOSFET transistor Q2 and capacitor C7 are connected to ground. Resistor R17 is further connected to a DC voltage source. In operation, LED PWM dimmer 128 achieves a precise and temperature insensitive minimum dim level for LED light source 110. Specifically, astable multivibrator circuit 129 produces a minimum pulse width (e.g., TON,MIN illustrated in FIG. 3). The duration of the minimum pulse width is a function of a resistance and capacitance of astable multivibrator circuit 129. Thus, the minimum pulse width is accurate and temperature insensitive. The ramp generator produces a ramp signal (e.g., RS illustrated in FIG. 3), which is periodically reset by the minimum pulse width. The ramp signal is supplied to the inverting input of comparator U3 whereby a comparison of the ramp signal and dim command VDC yields a target pulse width at the output of comparator U3 (e.g., TON illustrated in FIG. 3). The minimum pulse width and the target pulse width are combined to provide the PWM signal at the gate of MOSFET switch SW1. As such, the PWM signal consists of the target pulse width overlapping the minimum pulse width when the dim command VDC exceeds or is equal to the ramp signal. Conversely, the PWM signal exclusively consists of the minimum pulse width when the ramp signal exceeds the voltage dim command VDC. In practice, a suitable range for voltage dim command VDC is 0 to 10 volts. Short/Open Circuit Detection FIG. 4 illustrates one embodiment of short/open detection circuit 130. A LED voltage drop VLD across the LED light source 110 applied between a node N1 and a node N2, and an input voltage VIN is applied between node N2 and a common reference. The LED voltage drop VLD approximates zero (0) volts when LED light source 110 (FIG. 2) is shorted, and approximates the LED voltage VLED of regulated power PREG (FIG. 1) when LED light source 110 is an open circuit. The input voltage VIN is typically in the range of six (6) volts to sixteen (16) volts. A comparator U3 in the form of an operational amplifier provides a detection signal VDS at a high level to indicate a “LED outage” condition of LED light source 110 and at a low level to indicate a normal operation of LED light source 110. The “LED outage” condition is either indicative of a short or open of LED light source 110. Input voltage VIN in the illustrated embodiment is a dc voltage. A dc-dc type power converter can therefore be used to supply power to LED light source 110 (FIG. 2). In alternative embodiments, detection circuit 130 can be adapted for use in ac to dc type power converters. An emitter of a transistor Q3 in the form of a bipolar transistor, and a zener diode Z4 are also connected to node N1. Transistor Q3 can be in other conventional forms, such as, for example, an IGBT. A resistor R18, a resistor R21, and a resistor R22 are also connected to node N2. A base of bipolar transistor Q3 is connected to resistor R18. Zener diode Z4, a resistor R20 and resistor R21 are connected to an inverting input of comparator U5. A collector of bipolar transistor Q3, a diode D6, and a resistor R19 are connected to a node N3. Resistor R19 and resistor R20 are further connected to the common reference. Diode D6 and resistor R22 are connected to a non-inverting input of comparator U5. For a normal operation of LED light source 110, the LED voltage drop VLD is greater than the base-emitter junction voltage of transistor Q3 whereby transistor Q3 is on, diode D6 is in a non-conductive state, and the voltage at the collector of transistor Q3 exceeds the input voltage VIN. As a result, the input voltage VIN is applied to the inverting input of comparator U3. The conducting voltage of zener diode Z4 is chosen to be above the LED voltage drop VLD and therefore zener diode Z4 is in a non-conductive state. As a result, a voltage applied to the non-inverting input of comparator U2 will equate the input voltage VIN reduced by a voltage divider factor established by resistor R20 and resistor R21. The output of comparator U5 will be low (e.g., close to ground) since the voltage applied to the inverting input exceeds the voltage applied to the non-inverting input. For an open array condition of LED light source 110, the LED voltage drop VLD approximates the LED voltage VLED of regulated power PREG, which is chosen to be higher than the voltage of zener diode Z4. The LED voltage drop VLD is greater than the base-emitter junction voltage of transistor Q3 whereby transistor Q3 is on and the voltage at the collector transistor Q3 exceeds the input voltage VIN. As a result, the input voltage VIN is applied to the inverting input of comparator U3. The conducting voltage of zener diode Z4 is lower than the LED voltage drop VLD and zener diode Z4 is therefore in a conductive state. As a result, a voltage applied to the non-inverting input of comparator US will equate a summation of the input voltage VIN and the LED voltage drop VLD minus the conducting voltage of diode D6. The output of comparator US will be high (e.g., close to the input voltage VIN) since the voltage applied to the non-inverting input exceeds the voltage applied to the inverting input. For a short array condition of LED light source 110, the LED voltage drop VLD approximates zero (0) volts. The LED voltage drop VLD is therefore less than the base-emitter junction voltage of transistor Q3 whereby transistor Q3 is off, the voltage at the collector transistor is pulled down by resistor R19 and diode D6 is conducting. As a result, a voltage applied to the inverting input of comparator US will equate the input voltage VIN reduced by a voltage divider factor established by resistor R19 and resistor R22. The conducting voltage of zener diode Z4 exceeds the LED voltage drop VLD and zener diode Z4 is therefore in a non-conductive state. The output of comparator US will be high (e.g., close to the input voltage VIN) since the voltage applied to the non-inverting input exceeds the voltage applied to the inverting input. In an alternate embodiment, an additional zener diode or a voltage reference can be inserted in the emitter path of transistor Q3 to detect a voltage level other than less that one base-emitter junction of transistor Q3. FIG. 5 illustrates a differential amplification circuit having a voltage output VO that can be employed in LED current sensor 25 (FIG. 1) or LED current sensor 26 (FIG. 1). A resistor R23 and a resistor R25 are connected to an offset voltage source VOFF. Resistor R25, a resistor R26, and a resistor R28 are connected to an inverting input of an operational amplifier U6. A resistor R24 and a resistor R27 are connected to a non-inverting input of operational amplifier U6. Resistor R23 and resistor R24 are connected. Resistor R28 is further connected to an output of operational amplifier U6. In operation, the voltages applied to the inputs of the operational amplifier U6 are lower than the supply voltage Vdd irrespective of the size of resistor R23. In one embodiment, resistors R25 and R26 are chosen to apply half of the offset voltage VOFF to the inverting input of operational amplifier U6, and resistors R24 and R27 are chosen to obtain a proper common mode rejection (e.g., resistor R28 equaling a parallel combination of resistor R26 and R28). As a result, the gain of operational amplifier U6 can be adjusted as desired. It is important to note that FIGS. 2-5 illustrates specific applications and embodiments of the present invention, and is not intended to limit the scope of the present disclosure or claims to that which is presented therein. Upon reading the specification and reviewing the drawings hereof, it will become immediately obvious to those skilled in the art that myriad other embodiments of the present invention are possible, and that such embodiments are contemplated and fall within the scope of the presently claimed invention. While the embodiments of the invention disclosed herein are presently considered to be preferred, various changes and modifications can be made without departing from the spirit and scope of the invention. The scope of the invention is indicated in the appended claims, and all changes that come within the meaning and range of equivalents are intended to be embraced therein.
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Method for the optical characterisation of materials without using a physical model
A method of optical characterization of materials without using a model. To characterize a layer of material over an interval A of values taken by a function α(λ) (λ: wavelength), the method (1) obtains, via reflectometry and/or ellipsometry over A, a measured spectrum ψ, (2) chooses m values α1 . . . αm of α in A (m≧1), with B={α such that min(αi)≦α≦max(αi)} when m>1, and B=A when m=1, (3) chooses m values of complex indexes n+jk for the mαi, (4) if m≠1 calculates via interpolation the index n(α) over B, from (αi, ni=n(αi)), 1≦i≦m, and if m=1, n(α)=ni(αi) over B, (5) chooses M parameters, M≦2m+1, and an error function Er and, via a minimizing of Er with M parameters, (a) applies interpolation law of the (αi, ni) over B, deduces n(α), αεB, (b) using n(α) and the thickness ε of the layer, calculates a theoretical spectrum {overscore (ψ)}(n(α),ε), (c) compares ψ and {overscore (ψ)} using Er and, if Er(ψ,{overscore (ψ)})≦e or minimal, goes to (e), if not (d) makes the M parameters vary to approach the minimum of Er(ψ,{overscore (ψ)}), and goes to (a), (e) if Er(ψ,{overscore (ψ)})<e, sets the index equal to the last one obtained, otherwise increases m and goes to (2).
1-21. (canceled) 22. A method for optical characterization of at least one layer of material in an interval A of values taken by a function α of an optical wavelength λ, when λ varies in an interval of wavelengths, the at least one layer being created on a substrate, the method comprising: 1) carrying out a set of reflectometry and/or ellipsometry measurements over the interval A, the set of measurements leading to a measured spectrum, marked ψ, and choosing methods for calculating associated with a nature of the measurements and with a type of layer to be characterized; 2) choosing m initial values α1 . . . αm of the function α, belonging to the interval A, m being a whole number at least equal to 1, and defining an interval B as being the set of points α of the interval ranging from the smallest to the biggest number among α1 . . . αm, when m is greater than 1, and as being the interval A when m equals 1; 3) choosing m complex initial values of a complex refraction index n*=n+jk for the m points αi, i ranging from 1 to m; 4) when m is not 1, choosing an interpolation law that allows calculating the refraction index n(α) of the material over the interval B, from the points (αi, ni), with ni=n(αi), i ranging from 1 to m, and when m equals 1, n(α) is taken equal to the number n1(α1) over the entire interval B; 5) choosing M variable parameters, M being less than or equal to 2 m+1; 6) choosing an error function Er(ψ,{overscore (ψ)}) that characterizes the difference between a measured spectrum ψ and a theoretical spectrum {overscore (ψ)}; 7) using a minimizing function of Er(ψ,{overscore (ψ)}) with M parameters, performing: a) by applying the interpolation law of (α1, ni) over the interval B, deducing n(α), α belonging to B; b) by using n(α) and the thickness ε of the layer, and methods for calculating spectrums, calculating a theoretical spectrum {overscore (ψ)} (n(α),ε); c) comparing ψ and {overscore (ψ)} by using Er(ψ,{overscore (ψ)}) and, if Er(ψ,{overscore (ψ)}) is less than a predetermined value e, or is minimal, going to e), otherwise going to d); d) making the M variable parameters vary so as to tend to the minimum of Er(ψ,{overscore (ψ)}), and returning to a); e) if Er(ψ,{overscore (ψ)}) is less than e, then obtaining a set of M variable parameters, for which Er(ψ, {overscore (ψ)}(n(α,M),ε)) is minimal and the refraction index is then taken equal to the last one obtained, and if Er(ψ,{overscore (ψ)}) is greater or equal to e going to 8); 8) increasing the number m of initial values of the function α and returning to 2). 23. A method according to claim 22, further comprises increasing the number of initial values of the function α by adding one or plural values to extant initial values. 24. A method according to claim 23, further comprising increasing the number of initial values of the function α by replacing the extant initial values with new initial values whose number is greater than the number of extant initial values. 25. A method according to claim 23, wherein each interpolation law is chosen from among linear interpolation laws, cubic interpolation laws, polynomial interpolation laws, and interpolation laws of spline function type. 26. A method according to claim 22, wherein the initial values of the function α are evenly distributed over the interval A, the distribution of the nodes thus being homogenous. 27. A method according to claim 22, wherein α(λ) is chosen among λ, 1/λ and hc/λ, where h is the Planck's constant and c the speed of light in vacuum. 28. A method according to claim 22, further comprising measuring the error, at 6), over an interest interval C which is included in the interval B or equal to the interval B. 29. A method according to claim 22, wherein the M variable parameters are real parts of the refraction indexes at points αi, i ranging from 1 to m. 30. A method according to claim 22, wherein the M variable parameters are imaginary parts of the refraction indexes at points αi, i ranging from 1 to m. 31. A method according to claim 22, wherein the M variable parameters are constituted by the thickness of the material for which the refraction index is searched. 32. A method for optical characterization of at least one layer of a material in an interval of wavelengths [λ min, λ max], the at least one layer being created on a substrate, the method comprising: carrying out a set of reflectometry and/or ellipsometry measurements, the set of measurements leading to a measured spectrum, marked ψ; choosing m initial wavelengths λ1 . . . λm belonging to the interval, m being a whole number at least equal to 1, and associating a refraction index to each wavelength; choosing an interpolation law at least for the refraction index of the material, for wavelengths lying between the initial wavelengths λ1 . . . λm; choosing M initial parameters, M being at least equal to m, an initial refraction index ni for each initial wavelength λi, 1≦i≦m, the initial wavelengths being chosen so as to determine via interpolation at least the refraction index for any wavelength within the interval [λ min, λ max], couples (λi, ni) being nodes; choosing reflectometry and ellipsometry methods of calculation; choosing an error function Er, representative of the difference between two spectrums ψ1 and ψ2, the spectrums ψ1 and ψ2 being calculated or measured over a number of points greater than the number m of nodes; using the m initial wavelengths, the M initial parameters, and the interpolation law, implementing an optimization process of: determining a theoretical spectrum, marked {overscore (ψ)}, depending on the chosen methods of calculation, and on the index deduced via interpolation of its value at λi, i ranging from 1 to m, over the spectrum [λmin, λmax]; determining the error Er(ψ,{overscore (ψ)}), between the measured spectrum and the theoretical spectrum; minimizing the error by varying the position of the values of the unknown indexes and/or the thickness of the layer and/or the values of the refraction indexes with initial wavelengths, and obtaining a spectrum; adding other wavelengths to the initial wavelengths λi . . . λm, the added wavelengths constituting new nodes; repeating the method by choosing a number m′ of initial wavelengths, m′ being greater than m, and M′ initial parameters, M′ being greater than M, until the accuracy of each spectrum thus best represented is equal to a predetermined accuracy. 33. A method according to claim 32, wherein m is at least equal to 2. 34. A method according to claim 32, wherein m is at least equal to 1 and equal initial refraction indexes are chosen. 35. A method according to claim 32, wherein the material is non absorbent and the number M is equal to m, the extinction coefficient of the material being set equal to 0. 36. A method according to claim 32, wherein: M is at least equal to 2m; the method further comprising: choosing an interpolation law for the extinction coefficient of the material; each initial wavelength λi, 1≦i≦m, choosing an initial extinction coefficient ki, the initial wavelengths furthermore being chosen so as to be able to determine via interpolation the extinction coefficient for any wavelength of interval [λ min, λ max]; within the optimization process, minimizing the error by also varying values of the extinction coefficients at the initial wavelengths, and further placing the added wavelengths so as to best represent the spectrum of the extinction coefficient of the material. 37. A method according to claim 36, wherein m is equal to 1 and equal initial refraction indexes and equal initial extinction coefficients are chosen. 38. A method according to claim 32, wherein the layer of material has a thickness less than coherence length of light used for measuring, and further comprising choosing an additional initial parameter of an initial layer thickness, and in the optimization process the error is minimized by also varying the value of the layer thickness. 39. A method according to claim 32, wherein the layer of material is thick, and M is at most equal to 2 m. 40. A method according to claim 32, wherein the thickness of the layer of material is known with a predetermined accuracy and M is at most equal to 2 m. 41. A method according to claim 32, wherein each interpolation law is chosen from among linear interpolation laws, cubic interpolation laws, polynomial interpolation laws, and interpolation laws for example of spline function type. 42. A method according to claim 32, wherein a distribution of the nodes is homogenous.
TECHNICAL FIELD The invention relates to a method of optical characterisation of materials. This method allows to characterise thin or thick layers of these materials, which are created on substrates. The physical dimensions, that this method allows to determine, are: the thickness of a layer of material; the refraction index of this material; and the absorption coefficient of this material. Optical characterisation of materials is used for the chemical analysis of these materials (notably the study of absorption bands, of densification properties and of oxidation properties), in the fields of microelectronics, sensors, biology, medicine, or to analyse the thickness of deposits of these materials. We refer to document [1] for examples of applications which, as for the other documents cited later on, is mentioned at the end of this description. The characterisation of the optical properties of a material is also useful when the material is structured later on (to create for example etchings or surface roughness) and the optical diffraction properties of the obtained structure must be calculated (see document [2]). It can already be noted that the invention is particularly useful when the physical law applied by the complex refraction index of the material to be characterised is, a priori, unknown. STATE OF THE PRIOR ART Remember that the optical measurements can have a variety of natures. It can be reflectometric measurements. In this case, the intensity reflection coefficient of a structure is measured over a spectrum (i.e. an interval) of wavelengths [λm, λM]. The incident angle of the illuminating light may be not zero. The reflection coefficient can be measured for several incidence angles θ. Let R (θ, λ, p) be the reflectometric spectrum, where p is the polarisation of the incident beam and λ the wavelength of the latter. Generally, the angle θ is zero and the polarisation p unknown. In the event where θ is not zero, this polarisation p must be known. Generally, the latter is of (S) or (P) type. It can also be ellipsometric measurements. The measured dimensions are then the real and imaginary parts of the ratio between the polarisation reflection coefficient (P) and the polarisation reflection coefficient (S). We generally mark ρ=|ρ|exp(jΔ) this complex ratio (with j2=1). The dimensions commonly handled are |ρ|, that we mark tan(Ψ), and cos(Δ), or combinations of both. For example, the variables derived from a phase modulation ellipsometer are the following: Is=sin(2Ψ)sin(Δ) and Ic=cos(2Ψ) As for a standard ellipsometer, it supplies the following variables: α=(tan2Ψ−1)/(tan2Ψ+1) and β=cosΔ(1−α2)1/2. For generality purposes, we mark the handled dimensions S1 and S2. The spectrums Si, iε [1,2], are measured over a range of wavelengths [λm, λM]. The incidence angle can be of any value. Several spectrums can be measured at different incidence angles in order to obtain a fuller spectrum. We mark the ellipsometric spectrum s(θ,λ)={S1(θ,λ),S2(θ,λ)}. Additionally, goniometric measurements (reflection coefficient as a function of the incident angle) can be added to the measurement used for characterisation, so as to determine the thickness of the various layers, for one or several wavelengths. These measurements alone are insufficient as we want to determine the complex refraction index over a spectral range from λm to λM. So as to simplify the presentation, we mark Ψ a set of reflectometric and/or ellipsometric spectrums (and possibly goniometric spectrums for a few wavelengths). Without omitting any generality, we describe, in this description, the operating mode of the methods of the prior art and of the invention only for the case of a single thin layer of material, created on a known substrate. The thickness of this layer is marked ε and the complex refraction index of the material with the wavelength λ is marked n*(λ). In this regard, remember that the real (respectively imaginary) part of this complex refraction index is marked n(λ) (respectively k(λ)) and called “refraction index” (respectively extinction coefficient”). Additionally, we mark an error function Er(Ψ(1), Ψ(2))—for example the average quadratic gap—between two spectrums Ψ(1) and Ψ(2). For example, we can take, when there are ellipsometric spectrums over several angles θi, iε {1 . . . n}, and a reflectometric spectrum: Er ⁡ ( Ψ ( 1 ) , Ψ ( 2 ) ) = 1 λ ⁢ M - λ ⁢ m ⁢ ∫ λ ⁢ ⁢ m λ ⁢ ⁢ M ⁢ [ 1 n ⁢ ∑ i = 1 n ⁢ ⁢ [ S 1 ( 1 ) ⁡ ( θ i , λ ) - S 1 ( 2 ) ⁡ ( θ i , λ ) ] 2 + [ S 2 ( 1 ) ⁡ ( θ i , λ ) - S 2 ( 2 ) ⁡ ( θ i , λ ) ] 2 ] + [ R ( 1 ) ⁡ ( λ ) - R ( 2 ) ⁡ ( λ ) ] 2 ] ⁢ ⁢ ⅆ λ ( 1 ) with Ψ(1)(λ)={(S1(1)(θi,λ),S2(1)(θi,λ),R(1)(λ)} Ψ(2)(λ)={S1(2)(θi,λ),S2(2)(θi,λ),R(2)(λ)} and iε{1 . . . n} Weighing factors can be introduced into the integral so that the error function can take into account the variations in the accuracy of the measurements of the spectrums. The optical characterisation of layers of material is generally based around two applications. The first application is the dimension control of the deposit of thin layers that are used in microelectronics. Usually we know the deposited material, i.e. we know the complex refraction index of this material at the first wavelengths used for the characterisation. The laws applied by the complex refraction index are either tabulated or approximated by known physical laws such as, for example, the Cauchy model, the Sellmeier model (see document [3]), the Forouhi laws (see document [4]), and the harmonic oscillator laws (see document [5]). These laws are defined by a finite number of parameters. For example, a Cauchy type law without absorption, is with two parameters, is defined in the following manner: Re ⁡ [ n * ( λ ) ] = n ⁡ ( λ ) = a 0 + a 1 λ 2 Im ⁡ [ n * ( λ ) ] = k ⁡ ( λ ) = 0 When we are certain of the value of the coefficients ai(iε{0,1}) but we do not know the thickness, a search algorithm is used in order to find the thickness which minimises the error between the measurement Ψ and the theoretical result {overscore (Ψ)} taking into consideration the modelled index. The search algorithm can be, for example, the Simplex method, the Tabou search, the Levendt-Marquart method or the simulated annealing method (see chapter 10 in document [6]). When the refraction index is approximate, the coefficients ai are integrated into the adjustment process of Ψ and {overscore (Ψ)}. The search for the coefficients ai constitutes a method of characterising the refraction index. However, when the law applied by this refraction index is unknown (it happens that the material is unknown or that it is poorly described by known physical laws), this method remains approximate and the thickness risks being erroneous. The second application is the characterisation of materials. The employed method remains unchanged, except that the material is not really known. It is precisely the complex refraction index function that is the closest to reality that is targeted. The type of law can be chosen via analogy with other materials. However, the law applied by the complex refraction index can be complicated, which is for example the case of a harmonic oscillator law. [ n ⁡ ( E ) + j ⁢ ⁢ k ⁡ ( E ) ] 2 = 1 + ∑ i = 1 n ⁢ ⁢ A i E + E i + j ⁢ ⁢ Γ i - A i E - E i + j ⁢ ⁢ Γ i In the above expression, j2=−1 and the refraction index and the extinction coefficient are expressed as a function of E and not of λ, with E=1240/λ(λ in nm). In this case, the coefficients of the oscillators are difficult to find if we do not know their value range. The search is difficult to automate, as the search algorithms can give erroneous results and the time wasted can be substantial. There is an alternative to the search for coefficients: the point to point method (PAP). This PAP method proposes not to choose a physical law and to search the complex refraction index of the material for each wavelength λi, where iε [1 . . . n], with λ1=λm and λn=λM. For each λi, a search algorithm tries to find the thickness, the index n(λi) and the extinction coefficient k(λi) which minimise the error between the measured values Ψ(λi) and the theoretical result {overscore (Ψ)}(λi,n(λi),k(λi),ε). Such a method poses a problem because the different points (λi,ε,n(λi),k(λi)) are not necessarily physically compatible among themselves: for example, the found thickness can vary depending on the wavelength and the law applied by the complex refraction index, more simply called the index law, can have discontinuities. This method is usually only valid when the thickness is fully known and that the measurements are of good quality. PRESENTATION OF THE INVENTION The purpose of the invention is to resolve the previous inconveniences. The method which is the object of the invention allows to characterise a material without using a physical model, i.e. without using a physical law applied by the complex refraction index of the material under scrutiny. It is therefore especially useful when such a law is unknown. This method constitutes an alternative to the aforementioned known methods of characterisation. It can be called “method of nodes” as it uses “nodes”, i.e. points having coordinates (λi, n*i), where n*i is the value taken by the complex refraction index with the wavelength λi and i takes a limited number of values (whole numbers). Precisely, the purpose of the invention is a method for optical characterisation of at least one layer of material in an interval A of values taken by a function α of an optical wavelength λ, when λ varies in an interval of wavelengths, this layer being created on a substrate, this method being characterised in that it comprises the following stages: 1) we carry out a group of reflectometry and/or ellipsometry measurements over the interval A, this set of measurements leading to a measured spectrum, marked Ψ, and we choose the methods for calculating associated with the nature of the measurements and with the type of layer to be characterised; 2) we choose m initial values α1 . . . αm of the function α, belonging to this interval A, m being a whole number at least equal to 1, and we define an interval B as being the set of points α of the interval ranging from the smallest to the biggest number among α1 . . . αm, when m is greater than 1, and as being the interval A when m equals 1; 3) we choose m complex initial values of a complex refraction index n*=n+jk for the m points αi, i ranging from 1 to m; 4) when m is not 1, we choose an interpolation law which allows to calculate the refraction index n(α) of the material over the interval B, from the points (αi, ni), with ni=n(αi), i ranging from 1 to m, and when m equals 1, n(α) is taken equal to the number n1(α1) over the entire interval B; 5) we choose M variable parameters, M being less than or equal to 2 m+1; 6) we choose an error function Er(Ψ, {overscore (Ψ)}) which characterises the difference between a measured spectrum Ψ and a theoretical spectrum {overscore (Ψ)}; 7) using a minimising function of Er(Ψ, {overscore (Ψ)}) with M parameters, we perform the following series of stages: a) by applying the interpolation law of (αi,ni) is over the interval B, we deduce n(a), a belonging to B; b) by using n(α) and the thickness ε of the layer, and methods for calculating spectrums, we calculate a theoretical spectrum {overscore (Ψ)}(n(α),ε); c) we compare Ψ and {overscore (Ψ)} by using Er(Ψ, {overscore (Ψ)}) and, if Er(Ψ, {overscore (Ψ)}) is sufficiently small, i.e. less than a predetermined value e, or is minimal, we go to stage e), otherwise we go to stage d); d) we make the M variable parameters vary so as to tend to the minimum of Er (Ψ, {overscore (Ψ)}), and we return to stage a); e) if Er(Ψ, {overscore (Ψ)}) is less than e, we then obtain a set of M variable parameters, for which Er(Ψ, {overscore (Ψ)}(n(α,M),ε)) is minimal and the refraction index is then taken equal to the last one obtained, and if Er (Ψ, {overscore (Ψ)}) is greater or equal to e we go to stage 8). 8) we increase the number m of initial values of the function α and we return to stage 2). It is therefore, for example, possible to perform optical characterisation: over an interval of wavelengths λ, in this case the interval [λmin, λmax], or over an interval of inverse wavelengths 1/λ, in this case over an interval [(1/λ)min, (1/λ)max], where (1/λ)min is equal to 1/(λmax) and (1/λ)max is equal to 1/(λmin); or over an interval of energies E (with E=hv=hc/λ where h is the Planck's constant, c the speed of the light in the vacuum and v the frequency corresponding to (λ), in this case over an interval [E min, E max], where E min is equal to hc/(λmax) and E max is equal to hc/(λmin); or, more generally, over an interval [αmin, αmax] of values taken by a function α of the variable λ. Furthermore, it is appropriate to note that the invention can be used to characterise a spectrum or a part of a spectrum. Each interpolation law can be chosen from among the linear interpolation laws, the cubic interpolation laws, the polynomial interpolation laws and the interpolation laws for example of “spline” function type. According to a preferred embodiment of the method which is the object of the invention, the spectrum is evenly sampled in α(λ), meaning that the initial values of the function α (see the aforementioned stage 2) are evenly distributed over the interval A, the distribution of the nodes thus being homogenous. As previously seen, α(λ) can be chosen from among λ, 1/λ and hc/λ or any other function of λ, where h is the Plank's constant and c is the speed of the light in the vacuum. Preferably, in the aforementioned stage 6), we measure the error over an interest interval C which is included in the interval B or equal to this interval B. The M variable parameters can be the real parts of the refraction indexes at points αi, i ranging from 1 to m, or the imaginary parts of these refraction indexes, or these M variable parameters can be constituted by the thickness of the material for which we are searching the refraction index. Another purpose of the invention is another method for optical characterisation of at least one layer of a material in an interval of wavelengths [λ min, λ max], this layer being created on a substrate, this other method being characterised in that: we carry out a set of reflectometry and/or ellipsometry measurements, this set of measurements leading to a measured spectrum, marked Ψ; we choose m initial wavelengths λ1 . . . λm belonging to this interval, m being a whole number at least equal to 1, we associate a refraction index to each wavelength; we choose an interpolation law at least for the refraction index of the material, for wavelengths lying between the initial wavelengths λ1 . . . . λm; we choose M initial parameters, M being at least equal to m, namaly an initial refraction index ni for each initial wavelength λi, 1≦i≦m, the initial wavelengths being chosen so as to determine via interpolation at least the refraction index for any wavelength within the interval [λ min, λ max], the couples (λi, ni) being called nodes; we choose reflectometry and ellipsometry methods of calculation; we also choose an error function Er, representative of the difference between two spectrums Ψ1 and Ψ2, the spectrums Ψ1 and Ψ2 being calculated or measured over a number of points greater than the number m of nodes; using the m initial wavelengths, the M initial parameters and the interpolation law, we implement the following optimisation process: we determine a theoretical spectrum, marked {overscore (Ψ)}, depending on the chosen methods of calculation, and on the index deduced via interpolation of its value at λi, i ranging from 1 to m, over the spectrum [λmin, λmax]; we determine the error Er(Ψ, {overscore (Ψ)}), between the measured spectrum and the theoretical spectrum; we minimise this error by varying the position of the values of the unknown indexes and/or the thickness of the layer and/or the values of the refraction indexes with initial wavelengths, and we obtain a spectrum; we add other wavelengths to the initial wavelengths λi . . . λm, the added wavelengths constituting new nodes; we repeat the method by choosing a number m′ of initial wavelengths, m′ being greater than m, and M′ initial parameters, M′ being greater than M, until the accuracy of each spectrum thus best represented is equal to a predetermined accuracy. In this case, according to a first specific embodiment, m is at least equal to 2; according to a second specific embodiment, m is equal to 1 and we choose equal initial refraction indexes. Also in this case, according to a specific embodiment, the material is non absorbent and the number M is equal to m, the extinction coefficient of the material being set equal to 0; according to another specific embodiment, M is at least equal to 2m, we furthermore choose an interpolation law for the extinction coefficient of the material, for each initial wavelength λi, 1≦i≦m, furthermore we choose an initial extinction coefficient ki, the initial wavelengths furthermore being chosen so as to be able to determine via interpolation the extinction coefficient for any wavelength of the interval [λ min, λ max], and within the optimisation process, we minimise the error by also varying the values of the extinction coefficients at the initial wavelengths and the added wavelengths are furthermore placed so as to best represent the spectrum of the extinction coefficient of the material. In the case of this other specific embodiment, m can be equal to 1 and we can choose equal initial refraction indexes and equal initial extinction coefficients. Still in the case of this other method which is an object of the invention, the layer of material can be thin, i.e. with a thickness less than the coherence length of the light used for measuring, we can choose an additional initial parameter, namely an initial layer thickness, and in the optimisation process we can minimise the error by also varying the value of the layer thickness; in an alternative, the layer of material can be thick, i.e. not thin, and M can be at most equal to 2 m; in another alternative, the thickness of the layer of material can be known with sufficient accuracy and M is at most equal to 2 m. The distribution of the nodes can be homogenous. BRIEF DESCRIPTION OF THE DRAWINGS The invention will be better understood upon reading the description of the below embodiments, given by way of non-restrictive examples, making reference to the annexed drawings among which: FIG. 1 is a diagrammatic view of devices allowing to characterise a layer according to the invention; FIG. 2 shows the variations in the refraction index as a function of the wavelength, for a material obeying to a Cauchy law (curve I) and for a material characterised according to the invention (curve II); FIG. 3A (respectively 3B) shows the variations in the refraction index (respectively in the extinction coefficient) as a function of the wavelength, for a material obeying to a law with two harmonic oscillators (curve I) and for a material characterised according to the invention; and FIG. 4 diagrammatically illustrates the parameters used in a generalisation of examples of the invention. DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS The invention proposes an alternative to the aforementioned standard methods. It allows to combine the coherence of a layer model (corresponding to a continuous index law and to constant physical thicknesses), with the generality concerning the index law to be found (as in the PAP method). Furthermore, the resolution is only limited by the resolution of the measured spectrum. In the method according to the invention, the spectrum of index n*(λ) is characterised by: a limited number of “nodes” which are points having co-ordinates (λi, ni, ki) or (λi, n*i), with ni=n (λi), ki=k (λi) and n*i=ni+jki, where j2=−1, and an interpolation law between the nodes, which can be, for example, linear, cubic, of “spline” type or polynomial (of any given degree). This interpolation law allows to calculate, from the nodes, the refraction indexes and the extinction coefficients for the wavelengths located between the nodes. For example, when the refraction index is characterised by a set of value for wavelengths λ1 . . . λm, we can use a linear interpolation between two wavelengths λi and λi+1 to calculate the index n at the wavelength λ (see document [6] chapter 3): n ⁡ ( λ ) = ( λ i + 1 - λ ) ⁢ n ⁡ ( λ i ) + ( λ - λ i ) ⁢ n ⁡ ( λ i + 1 ) λ i + 1 - λ i with λi<λ<λi+1 We can do the same for the extinction coefficient. When the number of nodes makes it possible, more complex interpolation formulae, bringing into play nearby nodes, can be used (see document [6] chapter 3). A layer model is therefore characterised by a thickness ε and a family of nodes. Hereafter we present an example of the method according to the invention. In this example, the measurements Ψ are constituted of a reflectometry measurement R(λ) and an ellipsometry measurement S1,2(θ,λ) where θ is the incidence angle of the light beam that is transmitted onto the layer to be studied during measuring via ellipsometry. This layer is a thin layer so that the thickness of this layer is also a variable of the problem. Moreover, we suppose that only one layer is unknown, this layer being created on a known substrate. We will first of all briefly explain this example which uses an algorithm (algorithm of the “nodes method” according to the invention). From assumed information about the thickness ε of the scrutinised layer and about the refraction index n(λ) and about the extinction coefficient k(λ) of the material of this layer, we create initial nodes (only a few) and an initial thickness ε. We thus have m nodes and, via interpolation, we can find n(λ) and k(λ) when λ is different from the values of the wavelengths associated with the nodes. From the initial thickness ε and these initial values n(λ) and k(λ), we determine the theoretical spectrum {overscore (Ψ)} by using ellipsometric and reflectometric calculations. Furthermore, by means of ellipsometric and reflectometric devices and a spectrometer, we obtain S1,2(θ,λ) and R(λ) and we deduce the measurements marked Ψ (for measuring conditions θ and λ). We then compare Ψ and {overscore (Ψ)} by using an error function Er and we optimise the refraction index value and the extinction coefficient value at the different nodes as well as the thickness value, by trying to minimise Er(Ψ, {overscore (Ψ)}). Once these values have been optimised and if the accuracy on the spectrum n(λ), the spectrum k(λ) and the thickness ε is insufficient, we introduce new nodes, we make the thickness ε vary and we recommence the determination of {overscore (Ψ)}, the comparison of Ψ and {overscore (Ψ)} and the optimisation that are aforementioned, etc. We break the thus defined loop when the accuracy on each of the spectrums n(λ) and k(λ) and on the thickness ε is considered to be sufficient (satisfactory adjustment of Ψ and {overscore (Ψ)}). The spectrums n(λ), k(λ) and the thickness ε are thus characterised. In a non-restrictive illustration we find a layer thickness ε equal to 212.3 nm. FIG. 1 diagrammatically shows the scrutinised layer 2, created on a substrate 4. We can see the ellipsometric device 5,6, the reflectometric device 8 and the spectrometer 10. Furthermore, we can see electronic processing means 12, comprising a computer and allowing to characterise n(λ), k(λ) and ε according to the information supplied by the spectrometer 10 and according to the method of the invention. These means 12 are equipped with display means 14 which allow, in particular, to display the curve of the variation of n as a function of λ and the curve of the variation of k as a function of λ. We will now consider the illustration in greater detail. Phase 1 The method of this example firstly comprises an initialisation stage. The algorithm starts with a limited number of nodes, more precisely at least one node. We can therefore start with a single node, by imposing a refraction index and an extinction coefficient which remain constant when the wavelength varies. We chose node positions so as to, from this node family, deduce the entire spectrum via interpolation. The layer model therefore has 3 parameters or more, as the thickness is also a variable to be determined. The index table over the entire spectrum is therefore deduced from the nodes via interpolation. This is the case when the thickness of the layers is about the dimension of the wavelength (thin layers). But when the thickness of the layer is greater than the coherence length of the light source, the thickness barely enters into the calculation of the layer response, and is therefore no longer a variable of the problem. For example, in the case of optical disks (CDROM), on which a very thick layer is deposited (a thickness of about 1 millimetre), the reflection coefficient of such a layer is no longer a function of the thickness of the layer but purely of the refraction index of the latter, the coherence length of the incident light beam being less than the thickness of the layer. In this precise case, the coherence length of the incident beam is determined by the roughness of the layers. We choose, for example, to place the first two nodes at the ends λ min and λ max of the spectrum. The complex index values at these ends are chosen according to the type of material under scrutiny. For example, on an ellipsometric spectrum between 300 nm and 800 nm of a thin layer of photoresist, we take n(300 nm)=n(800 nm)=1.5 and k(300 nm)=k(800 nm)=0. When the spectrum is only characterised by two nodes, the index between the ends is determined via linear interpolation. In the case under consideration, we therefore have n(λ)=1.5 and k(λ)=0 for belonging to [300 nm, 800 nm]. From three nodes up, we rather opt for cubic interpolation in order to obtain softer forms of index law compared to those obtained via linear interpolation. The initial thickness is, itself, chosen as close as possible to the real thickness. Phase 2 We then proceed with an optimal determination of the values of the refraction index and of the extinction coefficient on the nodes and of the thickness value. To accomplish this, the spectrums {overscore (Ψ)}(λ) are calculated by means of the used layer model, resulting from the choice of nodes, the interpolation law and the thickness of the layer. The physical model used to calculate {overscore (Ψ)} of course depends on the applied method for measuring, i.e. in particular on the incidence angle of the light, on the applied spectrum and on the model of thin layers or of thick layers if appropriate (see for example the model of stacked layers in document 3)). The spectrums Ψ being constituted of a set of measurements of diverse nature (for example ellipsometric and reflectometric measurements), we use a reflectometric (respectively ellipsometric) calculation method for reflectometric (respectively ellipsometric) measurements. The reflectometric and ellipsometric measurements are combined by means of an error function Er(Ψ, {overscore (Ψ)}) which is for example of the type defined by the equation (1). Thanks to a search function, we minimise the difference between {overscore (Ψ)}(λ) and Ψ(λ), by varying the value of the refraction index and the value of the extinction coefficient at the position of each of the nodes as well as the layer thickness (if this thickness is an important factor in the calculation of {overscore (Ψ)}). When the difference is minimal, that being when Er(Ψ, {overscore (Ψ)}) is minimal, this signifies that the reflectometric and ellipsometric measurements coincide to their best (for a given number of nodes). At this stage we obtain, for a known number of nodes and a known spectral position for each of these nodes, the layer model (refraction index, extinction coefficient and thickness) which best corresponds to the real layer. The validity of the found model is better ensured as the number of measurements increases. To obtain a large number of measurements we can for example use several incidence angles of the light θi, 1≦i≦l, for the ellipsometric spectrums, carry out a reflectometric measurement and complementary goniometric measurements. Phase 3 Then, we increase the number of nodes. We add a finite number of nodes. In a first embodiment, the added nodes are positioned so as to best represent the spectrums n(λ) and k(λ). By way of example, we place these additional nodes at spots where the difference between Ψ and {overscore (Ψ)} is maximum or at spots where the nodes are the furthest apart. We then return to phase 2 as long as the accuracy on each of the spectrums n(λ) and k(λ) and on the thickness ε is insufficient, i.e. not equal to a pretedermined accuracy. In a second embodiment, we insert new nodes between two nodes of the set of previously chosen nodes, these new nodes being evenly distributed over the spectrum. All the same it is appropriate to heed the following. When we increase the number of nodes, the position of the old nodes does not need to be conserved. For example, assume that we evenly sample a spectrum from 400 nm to 800 nm with 3 nodes. These nodes are therefore respectively located at 400 nm, 600 nm and 800 nm. When we increase to 6 nodes, the three additional nodes cannot be placed so that the spectrum is evenly sampled if we conserve the position of the old nodes. The position of the 6 nodes can be defined, is we wish to have even sampling, by the values 400, 480, 560, 640, 720 and 800 nm. The old middle node at 600 nm therefore disappears. To calculate the index value at these positions from the old nodes we use interpolation. In the following we provide two common examples of application of the invention. These examples implement two types of materials which apply different laws. From ellipsometric and reflectometric measurements we propose to find the physical laws applied by these materials. We proceed in the following manner. A fictitious material is created, this material applying a known theoretical law (a Cauchy law or a harmonic oscillator law), with parameters that we arbitrarily set. The variations of the complex refraction index as a function of the wavelength are thus perfectly known. Furthermore, we impose a thickness of 200.00 nm for the material, on a silicon substrate, this latter also being well known. Fictitious measurements (ellipsometric measurements, reflectometric measurements) are calculated, then noise induced so as to introduce an apparatus defect. It all takes place as if we had used real measurements taken on the material. But contrary to reality we fully know the complex refraction index as we set it just as we set the thickness of the layer of material. Here we “blindly” test the method, that meaning we start with an erroneous thickness (220 nm) and false complex refraction indexes, as they are supposed to be unknown. We apply the method according to the invention then we compare the complex refraction index found with the is theoretical complex refraction index. We precisely find the same laws, as well as the same layer thickness. As a first example, take a material whose complex refraction index applies to a Cauchy law such as: n ⁡ ( λ ) = 1.5 + 0.1 ⁢ 300 2 λ 2 + 0.1 ⁢ 300 4 λ 4 k ⁡ ( λ ) = 0 This index law is typical of photoresists (in the spectral range from 300 nm to 800 nm). In order to find, using the nodes method (i.e. the method according to the invention), the aforementioned index law, we carry out two measurements, namely an ellipsometric measurement at a 70° angle and a reflectometric measurement. The processing conditions are as follows: the processed spectrum lies between 300 nm and 800 nm; at the start, the nodes are in the positions (300 nm, 1.6) and (800 nm, 1.6), this meaning that the index is considered as linearly varying between 300 nm and 800 nm, and that its value is constant (equal to 1.6); the number of nodes is repeatedly increased according to the sequence 2→4→6; during the node increasing procedure, the wavelength position of each node is calculated so that the sampling by 1/λ is regular (λ: wavelength), the density of points thus being increased around the low wavelengths; the interpolation law is a cubic law, when the number of nodes is greater than 2, otherwise it is linear; and the applied minimisation algorithm is a Simplex type algorithm. FIG. 2 allows to compare the refraction index corresponding to the fictitious material which perfectly applies the Cauchy law (curve I) with the refraction index which we find via the nodes method (curve II), using 6 nodes (represented by circles in FIG. 2). We have used a Ψ composed of an ellipsometric measurement {S1(λ),S2(λ)} at 70° and a reflectometric measurement R(λ). We finally find a thickness of 199.8384 nm. As for a second example, take a material whose complex refraction index applies a law with two harmonic oscillators, such as: [ n ⁡ ( E ) + j ⁢ ⁢ k ⁡ ( E ) ] 2 = 1 + ∑ i = 1 2 ⁢ ⁢ A i E + E i + j ⁢ ⁢ G i - A i E - E i + j ⁢ ⁢ G i with j2=−1 and E=1240/λ (λ in nm) A1=0.25×1.52 A2=0.25×1.52 E1=1240/400 E2=1240/300 G1=0.3 G2=0.3 In this second example, the nodes method is applied to a set of ellipsometric measurements carried out between 250 nm and 800 nm, at 75°, 70°, 60° and 45°, along with a reflectometric measurement. The real thickness of the material being 200 nm, we find a thickness of 200.25 nm with the nodes method. The adjustment to the index law considered in this second example is very good, as FIGS. 3A and 3B demonstrate. These FIGS. 3A and 3B respectively illustrate the reconstructions of the curves n(λ) and k(λ) of the material by means of the nodes method. The reconstruction is carried out using four ellipsometric spectrums and a reflectometric spectrum. The real absorption peaks are particularly well represented by the curve obtained via cubic interpolation between the nodes (represented by the circles in FIGS. 3A and 3B). In FIG. 3A, the curve I (respectively II) corresponds to a refraction index n which perfectly applies the chosen law (respectively to a refraction index n found via the nodes method). In FIG. 3B, the curve I (respectively II) corresponds to an extinction coefficient k which perfectly applies the chosen law (respectively to an extinction coefficient k found via the nodes method). Examples of the invention have just been described above. More generally speaking, we note that in the invention we consider a set X of values, with X={n1,n2, . . . ,ni, . . . nm,k1,k2, . . . ki, . . . km,ε}, where ni is the value of the refraction index (real) corresponding to λi, iε{1 . . . m}, m being the number of nodes ki is the value of the absorption coefficient at the node corresponding to λi, iε{1 . . . m}, ε is the thickness of the scrutinised layer. In this case, the operation for minimizing the error Er(Ψ, {overscore (Ψ)}) means finding the set or “vector” X such that Er is minimal. When we do not assert any specific constraints, the minimising is a minimising with 2×m+1 parameters. We can of course introduce constraints in order to reduce the number of variables. In particular, if we know that the material is non-absorbent, we impose ki=0 for all i of {1 . . . m} and X becomes: X={n1,n2 . . . ,ni, . . . nm,ε}. If through a complementary measurement (for example a goniometric measurement or a non-optical direct measurement) we know with sufficient accuracy the thickness of the scrutinised layer, the thickness ε is no longer a variable and we obtain: X={ni,n2 . . . ,ni, . . . nm,k1,k2, . . . ki, . . . ,km}. Of course, the two previous options can be combined. In the following we explain an embodiment of the invention in a more general form than the previous examples. Given that α(λ) is a function of the wavelength λ of the light used in the measurements, we can for example choose: α(λ)=(see FIGS. 3A and 3B where the spectrum is evenly sampled in λ) α(λ)=1/λ (see FIG. 2 where the spectrum is evenly samples in 1/λ) α(λ)=hc/λ where h is the Planck's constant and c the speed of light in the vacuum, α(λ) then being homogenous with an energy. Given that A is the interval of the spectrum of measurement, B is the spectral interval described by the “nodes” and C is the interval of interest. The interval C is included in the interval B or equal to this interval B. Likewise, the interval B is included in the interval A or equal to this interval A. We specify that each of the intervals A, B and C is is of [αm, αM] type where αm is less than αM and there are two wavelengths λk and λi such that αm=α(λk) and αM=α(λ1). By way of non-restrictive illustration, FIG. 4 shows an example of the intervals A, B and C and of the variation curves of Ψ and {overscore (Ψ)} as a function of α(λ), {overscore (Ψ)} in fact being a function of n*(α(λ)). The circles N represent the nodes. n* is the complex index which is expressed here as a function of α(λ) and whose real and imaginary parts are respectively marked n(α(λ)) and k(α(λ)). We also see, by way of non-restrictive example, an example of the variations curve of n (respectively k) as a function of α(λ), passing through the points having co-ordinates (ni,αi) (respectively (ki, αi), where αi=α(λi), ni=n(αi), ki=k(αi), 1≦i≦m (m being a natural number other than zero). In FIG. 4 we note the relation between the nodes N, the points (ni, αi) and the points (ki, αi). In the embodiment under consideration, we use an algorithm comprising the following stages: 1. we carry out the measurements Ψ over the interval A and we choose the calculation methods associated with the measurements (ellipsometric or reflectometric calculations); 2. we choose m numbers αi (constituting m initial values of the function α), i belonging to {1, . . . m}, with m≧−1, and {αi}⊂A (the αi corresponding to the “nodes”); when m>1, B is defined as the set of points α such that min(αi)≦α≦max(αi); when m=1, we have B=A; 3. we choose m initial values of complex index n* at the m points αi, i belonging to {1, . . . m}; 4. if m≠1 we choose an interpolation law which allows to calculate the refraction index n(a) over the interval B from the points (αi, ni), i belonging to {1, . . . , m}; if m=1, then n(α)=n1(α1) over the entire interval B; 5. we choose M variable parameters with M≦2 m+1; these parameters can be for example: the real parts of the refraction indexes at points αi, i belonging to {1, . . . , m}, or the imaginary parts of the refraction indexes at these same points, or the thickness of the material for which we are searching the refraction index; 6. we choose an error function Er(Ψ, {overscore (Ψ)}) which characterises the difference between a measured spectrum and a theoretical spectrum; generally, the error is measured over the interval C; 7. using a minimising function of Er(Ψ, {overscore (Ψ)}) with M parameters, we perform the following series of stages: a) by applying the interpolation function of (αi,ni) over B, we deduce n(x) with α belonging to B; b) by using n(α) and the thickness ε and methods for calculating spectrums, we calculate the theoretical spectrum {overscore (Ψ)} (n(α), ε); c) we compare Ψ and {overscore (Ψ)} by using Er=Er(Ψ, {overscore (Ψ)}); if Er is sufficiently small (i.e. if Er is less than a predetermined value e), or if Er is minimal, we go to stage e), otherwise we go to stage d); d) we make the M variable parameters vary so as to tend to the minimum of Er and we return to stage a); e) if Er is less than e we then obtain a set of M parameters such that Er(Ψ, {overscore (Ψ)}(n(α,M),ε)) is minimal and the refraction index calculation is completed: this index is taken equal to the last one obtained; and if Er is greater than or equal to e we go to stage 8). 8. We increase m and we return to stage 2). It is appropriate to note that the invention can not only use wavelength (λ) samplings but also frequency (c/λ or simply 1/λ) samplings, energy (hc/λ) samplings and, more generally, samplings with parameters which are functions of the wavelength. Furthermore, it is appropriate to note that an aforementioned essential stage of the algorithm (stage 8) is not restricted to adding a set of nodes to the already existing nodes: it encompasses the more general case where the number of nodes increases. This means, in a specific embodiment of the invention, that after minimising with 3 nodes, if we want to increase to 6 nodes in all, the position of the 3 old nodes is “erased” so as, for example, to have a constant density of nodes over the spectrum. In practice, this is the best option. The information about the position of the old nodes is not lost as the index value at the old nodes is used to calculate the values of the 6 new nodes (in fact 3 new nodes plus 3 old nodes). Thus, according to a specific embodiment of the method according to the invention, we can increase the number of initial values of the function α by adding one or several values to the extant initial values; however, according to a preferred embodiment, we can increase the number of initial values of the function α by replacing the extant initial values with new initial values whose number is greater than the number of extant initial values. The invention in not restricted to the characterisation of thin layers. It also applies to the characterisation of thick layers. Furthermore, the invention is not restricted to the characterisation of a single layer, created on a substrate. It also applies to the characterisation of two, or more than two, layers created on a substrate. The following documents were cited in the description: [1] R. M. A. Azzam and N. M. Bashara, Ellipsometry and Polarised Light, North-Holland Physics Publishing, 1997, chapter 6. [2] B. K. Minhas, S. A. Coulombe, S. Sohail, H. Naqvi and J. R. McNeill, Ellipsometry scatterometry for the metrology of sub-0.1-μm-linewidth structures, Applied Optics, 37(22): 5112-5115, 1998. [3] M. Born and E. Wolf, Principle of Optics, Cambridge University Press Edition. [4] A. R. Forouhi and I. Bloomer, Optical dispersion relations for amorphous semiconductors and amorphous dielectrics, Physical Review B, 34(10): 7018-7026, November 1986. [5] F. L. Terry, Jr., A modified harmonic oscillator approximation scheme for the dielectric constants of AlxGa1-xAs, Journal of Applied Physics, 70(1), 1991, pages 409-417. [6] W. H. Press, S. A. Teukolsky, W. T. Vetterling and B. P. Flannery, Numerical Recipes in C, Cambridge University Press, 1992, chapters 3 and 10.
<SOH> TECHNICAL FIELD <EOH>The invention relates to a method of optical characterisation of materials. This method allows to characterise thin or thick layers of these materials, which are created on substrates. The physical dimensions, that this method allows to determine, are: the thickness of a layer of material; the refraction index of this material; and the absorption coefficient of this material. Optical characterisation of materials is used for the chemical analysis of these materials (notably the study of absorption bands, of densification properties and of oxidation properties), in the fields of microelectronics, sensors, biology, medicine, or to analyse the thickness of deposits of these materials. We refer to document [1] for examples of applications which, as for the other documents cited later on, is mentioned at the end of this description. The characterisation of the optical properties of a material is also useful when the material is structured later on (to create for example etchings or surface roughness) and the optical diffraction properties of the obtained structure must be calculated (see document [2]). It can already be noted that the invention is particularly useful when the physical law applied by the complex refraction index of the material to be characterised is, a priori, unknown.
<SOH> BRIEF DESCRIPTION OF THE DRAWINGS <EOH>The invention will be better understood upon reading the description of the below embodiments, given by way of non-restrictive examples, making reference to the annexed drawings among which: FIG. 1 is a diagrammatic view of devices allowing to characterise a layer according to the invention; FIG. 2 shows the variations in the refraction index as a function of the wavelength, for a material obeying to a Cauchy law (curve I) and for a material characterised according to the invention (curve II); FIG. 3A (respectively 3 B) shows the variations in the refraction index (respectively in the extinction coefficient) as a function of the wavelength, for a material obeying to a law with two harmonic oscillators (curve I) and for a material characterised according to the invention; and FIG. 4 diagrammatically illustrates the parameters used in a generalisation of examples of the invention. detailed-description description="Detailed Description" end="lead"?
20050621
20071211
20060413
84356.0
G01J400
0
NGUYEN, TU T
METHOD FOR THE OPTICAL CHARACTERIZATION OF MATERIALS WITHOUT USING A PHYSICAL MODEL
UNDISCOUNTED
0
ACCEPTED
G01J
2,005
10,540,011
ACCEPTED
Method for the production of piston-type accumulators
The invention relates to a method for producing piston-type accumulators comprising an accumulator housing (10) and a separating piston which can be displaced in a longitudinal direction inside the accumulator housing (10) and separates two working spaces located therein. The end faces of the accumulator housing are sealed by means of one respective cover part (20). Previously known production methods are further improved due to the fact that the cover part (20) is fixed on one side (40) thereof via the free longitudinal edge (32) of the accumulator housing (10), which is displaced towards the cover part (20) in order to do so, such that a functionally and positionally secure connection of a cover part is ensured within the housing of a piston-type accumulator without using standard threaded connections.
1. A method for the production of piston-type accumulators having an accumulator housing (10) and a separating piston (12) displaceable in the longitudinal direction in the accumulator housing (10) which separates two working chambers (16, 18) from each other inside the accumulator housing (10), and which accumulator housing is sealed on each of the end sides by a cover component (20, 22), characterized in that on one side (40) of the cover component (20, 22) such cover component is fastened by way of the free longitudinal edge (32) of the accumulator housing (10), which for this purpose undergoes a positioning movement onto the cover component (20, 22). 2. The method as claimed in claim 1, wherein one side (36) opposite one side (40) of at least one of the two cover components (20, 22) is inserted into the accumulator housing (10) so as to come to rest against a stop (38) and/or wherein the respective cover component (20, 22) is retained in its end position by the clamping force of the positioned free longitudinal edge (32). 3. The method as claimed in claim 1, wherein a shaping tool (42) is provided for the positioning movement of the longitudinal edge (32) of the accumulator housing (10), which shaping tool (42) which positions the longitudinal edge (32) provided with least one positioning bevel (44) on the cover component (20) in such a way that this cover component (20) is secured in the accumulator housing (10) as a kind of clamping seat. 4. The method as claimed in claims 1, wherein the wall thickness of the longitudinal edge (32) is reduced in relation to that of the remainder of the accumulator housing (10) and wherein the point of transition between the different wall thicknesses forms the stop (38) for the cover component (20) inside the accumulator housing (10). 5. The method as claimed in claims 1, wherein the longitudinal edge (32) is provided with an insertion bevel (50) on its side facing the respective cover component (20, 22) and toward the exterior. 6. The method as claimed in claims 1, wherein there is provided on the opposite side (40) of the cover component (20, 22) a contact surface (46), in particular in the form of a securing bevel against which the longitudinal edge (32) rests in the secured state and wherein the cover component (20, 22) closes off the accumulator housing (10) from the exterior. 7. The method as claimed in claims 3, wherein two shaping tools (42) in a joint positioning movement execute the securing process for the respective cover component (20, 22) on opposite sides of the accumulator housing (10) by acting on the respective free longitudinal edge (32) of the accumulator housing (10). 8. The method as claimed in claims 1, wherein the cover component (20, 22) is introduced into the accumulator housing (10) up to the stop (38) by means of a feed bevel (58), by means of a positioning tool (56) which encloses the free longitudinal edge (32) of the accumulator housing (10). 9. The method as claimed in claims 1, wherein the longitudinal edge (32) is provided on the internal circumference side with an insertion bevel (50) widening toward the exterior for the cover component (20, 22). 10. The method as claimed in claims 1, wherein the height selected for the cover component (20,22) is at least twice as great as the free longitudinal; edge (38) of the accumulator housing (10) introduced for the purpose of clamping the cover component (20, 22).
The invention relates to a method for the production of piston-type accumulators having an accumulator housing and a separating piston, which is displaceable in the longitudinal direction in the accumulator housing, separating two working chambers from each other and which accumulator housing is sealed on each of the end sides by a cover component. Piston-type accumulators are, in the broadest sense of the term, so-called hydraulic accumulators, which among other things serve the purpose of admitting specific volumes of a pressurized liquid (hydraulic medium) of a hydraulic system and returning these volumes to the system when required. Since the hydraulic medium is pressurized, hydraulic accumulators are treated as pressure reservoirs and must be designed for the maximum excess operating pressure, the acceptance standards of various installing countries being taken into consideration. Hydropneumatic (gas-charged) accumulators with a separating element are currently used in most hydraulic systems, a piston which separates a fluid space as working chamber from a gas space as additional working chamber serving as separating element inside the accumulator housing of the piston-type accumulator. Nitrogen is generally used as the operating gas and the gas-tight piston to a great extent permits disconnection of the gas space from the fluid space. The fluid component is connected to the hydraulic circuit so that, as the pressure rises, the piston-type accumulator admits fluid and the gas is compressed in the process. As the pressure drops the compressed gas expands and displaces the pressurized fluid back into the hydraulic circuit. One advantage of piston-type accumulators is they can Awork@ when in any position, but preference is to be given to vertical positioning with the gas side on top, so that settling of fouling particles from the fluid on the piston seals is prevented. Consequently, the essential components of a piston-type accumulator are an outer cylindrical tube as accumulator housing, the piston as separating element with its sealing system, and the sealing covers on the end, which as cover elements simultaneously also contain a fluid and a gas connection. Two functions are regularly assigned to the accumulator housing, specifically storage of internal pressure and ensuring control of the piston inside the accumulator housing. The cover components on the front surface sealing the interior of the accumulator housing off from the exterior are provided on the outer circumference with external threading which may be screwed into a corresponding inner threading along the free longitudinal edge over an assigned path. Production of the respective threaded connection is time-consuming; this factor correspondingly increases the production costs of the piston-type accumulator. In addition, safety measures must be taken in order to secure in its position the cover component introduced. On the basis of this prior art as disclosed, the invention has the object of improving the disclosed manufacturing process for piston-type accumulators to the end that a reliable operation of a cover component secured in position in the accumulator housing is guaranteed while the otherwise customary threaded connections are avoided. This object is attained by a method having the characteristics specified in claim 1 in its entirety. In that, as specified in the characterizing part of claim 1, the cover component on one of its sides is fastened by the free longitudinal edge of the accumulator housing, which edge is for this purpose moved onto the cover component, and, the otherwise customary screw connection being avoided in the case of the respective cover component, a sort of clamping onto the free end of the accumulator housing is achieved in which the cover component is clamped at least over the free longitudinal edge of the accumulator housing after this housing has been moved onto the cover component, it being sufficient if a part of the free longitudinal edge effects the clamping in question. In one preferred embodiment of the method claimed for the invention provision is made such that at least one of the two cover components is inserted by one side opposite the other side to come up against a stop in the interior of the accumulator housing and/or such that the respective cover component is retained in its end position by the clamping force of the longitudinal edge introduced. If a stop is provided on the inside of the accumulator housing, the cover component may be immobilized against this stop during the positioning movement of the free longitudinal edge of the accumulator housing. In addition or as an alternative, however, the possibility exists of inserting the cover component into the free end of the accumulator housing and then initiating the positioning movement of the free end of the accumulator housing. The positioning movement may be effected toward the upper side of the cover if the cover component is retained in a suitable position, but it is also conceivable that an unrestrained positioning movement may be effected for the longitudinal edge and then, in the state of readiness for operation, the cover component may be moved by the piston against the free longitudinal edge, which then effects the clamping there. By preference provision is also made such that a shaping tool is provided for the positioning movement of the longitudinal edge of the accumulator housing, a tool which is provided with positioning bevels and positions the longitudinal edge of the accumulator housing on the cover component in such a way that this cover component is secured in the accumulator housing as the clamping seat referred to. In one especially preferred embodiment of the method claimed for the invention two shaping tools positioned on opposite sides carry out the fastening process for the respective end cover component in a common positioning movement to the accumulator housing, these shaping tools acting on the free longitudinal edge of the accumulator housing. It has been found to be highly advantageous for the purpose of generation of high fastening forces to position the two free ends of the cylindrical accumulator housing uniformly, the shaping tool which acts on one end of the accumulator housing being capable in addition of reliably withstanding the forces which are introduced into the accumulator housing by the other shaping tool. Other advantageous embodiments are specified in the other dependent claims. The method claimed for the invention will be described in detail below with reference to the drawing, in which, in the form of diagrams not drawn to scale, FIG. 1 presents a longitudinal section of a piston-type accumulator present in the state of the art; FIG. 2, presents a longitudinal section of the upper part of the first embodiment of a piston-type accumulator with a shaping tool positioned above it; FIGS. 3 and 4 present a longitudinal section of the positioning of a positioning tool on the free end of the accumulator housing for the purpose of fastening the respective cover component; FIGS. 5 and 6 a longitudinal section of the upper areas of the accumulator housing in the form of two different versions with insertion bevels positioned in the interior for introduction of the respective cover component; FIG. 7 also presents a longitudinal section of the upper part of a second embodiment of a piston-type accumulator housing with modified cover component. The piston-type accumulator of the prior the art shown in FIG. 1 has as accumulator housing 10 an outer cylindrical tube into which a piston 12 with its sealing system 14 on the exterior has been introduced as separating element so as to be longitudinally displaceable. Inside the accumulator housing 10 the piston 12 separates two working chambers 16, 18 from each other, one working chamber 16 serving to receive an operating gas, in particular one in the form of nitrogen, while the other working chamber 18 forms the so-called fluid space for the piston-type accumulator. The displaced position of the piston 12 and accordingly the volume percentages of gas and fluid in the working chambers 16 and 18 vary with the operating situation of the accumulator. There is mounted on the end of the accumulator housing 10 a cover component 20, 22 having a gas connection 24 for recharging with nitrogen operating gas and a fluid connection 26 for connecting the piston-type accumulator to an overall hydraulic system not shown in detail. Each of the two cover components 20, 22 is provided with external threading 28 which may be engaged with internal threading 30 which is mounted so as to extend along the free longitudinal edge 32 and outward to the exterior. On the external circumference side the respective cover component 20, 22 is provided with a seal 34 for sealing the interior of the accumulator housing 10 from the exterior. Application of the lengths of threading 28, 30 entails a certain production effort which makes the prior piston-type accumulators complex and expensive to produce. It is also necessary to secure each cover component 20, 22 from rotation in order to ensure its fixing in position inside the accumulator housing 10. One possible method of securing the respective cover component 20, 22 from rotation may be represented by providing a conventional adhesive seal along the threading 28, 30 or by keeping the cover component in its position by means of a conventional retention bore (with and without threading). On the basis of this solution of the prior art the method claimed for the invention will now be described in greater detail with reference to FIGS. 2 and the following. This solution permits cost-effective creation of a reliably operating connection of cover component and the associated accumulator housing 20. For the sake of greater simplicity of presentation, only the upper end of the accumulator housing 10 is shown in FIG. 2, along with the upper cover component 20. When reference is made to these structural components below, as with the prior art embodiment shown in FIG. 1 the respective structural components are designated by the same reference numbers as in FIG. 1. The method claimed for the invention is among other things characterized in that the respective cover component, in this instance cover component 20, is inserted by its lower side to come into contact with a stop 38 in the form of an annular surface in the interior of the accumulator housing 10, the component being secured on its opposite side 40 by the free longitudinal edge 32 of the accumulator housing 10, the longitudinal edge 32 undergoing a positioning movement to the cover component 20, as is to be explained in greater detail in what follows. A shaping tool 42 serves to position the longitudinal edge 32 of the accumulator housing 20, this shaping tool 42 being provided with at least one positioning bevel 44 which positions the longitudinal edge 32 on the cover component 10 so that this component is secured as a clamping seat in the accumulator housing 10 between the stop 38 and the longitudinal edge 32. For the purpose of establishing the respective clamping seat the upper side 40 of the cover component 20 is provided with a contact surface 46 which is mounted so as to taper toward the longitudinal axis 48 of the accumulator housing 10. The inclination of the respective contact surface 46 corresponds to the inclination of the positioning bevel 44 of the shaping tool 42. However, other obvious inclinations or bevels are also conceivable. As is shown in FIG. 2, the positioning direction for the shaping tool 42 is that of the longitudinal axis 48 of the accumulator housing 10 or of the piston-type accumulator as a whole. For the sake of greater clarity of illustration the separating element in the form of the piston 12 has been omitted from FIG. 2, as has also the gas connection 24 shown in FIG. 1, which is also an integral part of the upper cover component 20. Before the clamp connection has been effected by way of the shaping tool 42, the upper free end of the accumulator housing with its upper longitudinal edge 32 has an outline as shown in FIGS. 3 to 6. The wall thickness of the longitudinal edge 32 has been reduced in comparison to the rest of the accumulator housing 10, the area of transition between the different wall thicknesses forming the stop 38 for the cover component 20. In addition, the longitudinal edge 32 is provided with a tapering insertion bevel 50, by preference on its side facing the cover component 20, the bevel being oriented outward. The respective insertion bevel 50 facilitates introduction of the cover component 20 into the free upper end of the accumulator housing 10, as will be described in greater detail below. As is shown in FIGS. 4 and 5 in particular, the free longitudinal edge 32 may also be provided on the external circumference side with a slide bevel 52 oriented toward the free end of the accumulator housing 10. This makes it easier for the longitudinal edge 32 to effect transition from its cylindrical shape as shown in FIGS. 3 to 6 to an inclined position after being positioned, the slide bevel 52 then sliding along the positioning bevel 44 of the shaping tool 42 until the latter is visibly mounted on the accumulator housing 10 in the direction of positioning. Once the positioning movement by the shaping tool 42 has been completed, the longitudinal edge 32 is inclined along its contact surface 46 onto the cover component 20 to form a fastening bevel and in this way secures the cover component 20 against the stop 38 inside the accumulator housing 10. In order not to endanger the secure position of the cover component 20 in the accumulator housing 10 and also to protect the cover component 20 from introduction of harmful forces, the free longitudinal edge 32 is, as shown in FIG. 2, guided along its free end so as to project over the second side 40 of the cover component 20 positioned above. After the respective clamp connection has been secured, the shaping tool 42 is moved back away from the accumulator housing 10 and then, for example, assumes its upper position as illustrated in FIG. 2. By preference the shaping process for the respective longitudinal edge 32 of the accumulator housing 10 is effected as cold forming, but hot forming involving appropriate heating of the accumulator housing material and preferably the shaping tool 42 as well is also conceivable. A conventional easily shaped steel material is used as material for the accumulator housing 10 with its longitudinal edge 32. In order to introduce the clamping forces optimally into the cover component 20 and also to ensure optimal support for the cover component 20 in the accumulator housing 10 on the edge side provision is made such that the height of the cover component 20 is adapted to the application conditions assigned by operation of the accumulator. In the case illustrated the cover component 20 is at least twice as great as the length of the longitudinal edge 32 between its free end and a deflection point 54 from which the longitudinal edge 32 is moved to the top of the cover. As is illustrated in FIG. 7 for a modified embodiment, the cover component 20 may nevertheless project beyond the longitudinal edge 32 of the accumulator housing 10, or, in another embodiment not shown, may end so as to be flush at the same level. In one especially preferred embodiment (not shown) of the method claimed for the invention, the fastening process for the respective end cover component 20, 22 is carried out in a common positioning movement of two shaping tools 42 on opposite sides of the accumulator housing 10 simultaneously and with more or less equal shaping forces by acting on the respective free longitudinal edge 32 of the accumulator housing 10. It has been found that in the case of the respective shaping solution the opposite shaping tool can during shaping receive the forces of the other shaping tool such as occur during the forming process. Costly support devices may be dispensed with in this configuration on the respective opposite sides where the shaping tool 42 exerts no effect. Harmonious introduction of forces into the accumulator housing 10 without the occurrence of damaging power peaks also occur in this situation. As is shown in FIGS. 3 and 4, the respective cover component 20, 22 may be introduced into the accumulator housing 10 up to the stop 38 in the form of an annular surface, by means of a positioning tool 56, which, as is shown in FIG. 4, encloses the free longitudinal edge 32 of the accumulator housing 10. The positioning tool 56 has for the respective introduction process a feed bevel 58 along which the cover component 20, 22 may slide on the external circumference side. Use of the positioning tool 56 permits reliable prevention of possible damage to the seal 34 of the respective cover component 20,22. In addition to the feed bevel 58 the positioning tool 56 has an admission space 60 into which the upper end of the accumulator housing 10 may be introduced so that the feed bevel 58 ends flush with the upper edge of the longitudinal edge and in addition effects uninterrupted transition to the admission area 62 for the cover component 20, 22 itself in the accumulator housing 10. In the embodiments shown in FIGS. 5 and 6 the accumulator housing 10 is provided on the inner circumference side along its upper longitudinal edge 32 with an insertion bevel 50 which extends the length of the accumulator housing 10 outward, this resulting in a sort of slip edge over which the respective cover component 20, 22 may also be introduced and later secured. The respective alternative may be selected if the cover seal 34 is proved to be rugged and not overly susceptible to damage. The same reference numbers are used for the same structural parts illustrated in FIG. 7; the method employed is described only to the extent that it differs significantly from the method as presented in the foregoing. In the instance of the embodiment shown the upper cover component 20 is retained by the free longitudinal edge 32 of the accumulator housing 10 so that the upper side projects an assigned distance beyond the end of the free longitudinal edge 32. In the embodiment shown in FIG. 7 the stop 38 for the cover component 20 is provided with a bevel against which the cover component 20 leans in a stepped recess. The annular seal 34 is in turn received in the outer circumference of the recessed sectional step 64; because of the stepped arrangement illustrated of accumulator housing 10 and cover component 20, the possibility exists of machining the accumulator housing 10 as finely as possible for clean contact with the sealing ring 34 at this point and of leaving the inside of the accumulator housing 10 more or less unmachined, insofar as the delivery area for the free longitudinal edges 32 of the accumulator housing 10 is affected. The cover components 20, 22 may accordingly be fastened with high fitting accuracy, reliably, and pressure-tightly in the accumulator housings 10 by the shaping process discussed, in the widest possible variety of embodiments, while screw connections cost-intensive in mounting, which in addition remain to be secured in this position, may be dispensed with in their entirety.
20050622
20130305
20060126
65055.0
B21D5116
0
WALTERS, RYAN J
METHOD FOR THE PRODUCTION OF PISTON-TYPE ACCUMULATORS
UNDISCOUNTED
0
ACCEPTED
B21D
2,005
10,540,045
ACCEPTED
Substitituted 1-piperidin-3-yl-piperidin 4-yl-piperazine derivatives and their use as neurokinin auantagonists
This invention concerns substituted 1-piperidin-3-yl-4-piperidin-4-yl-piperazine derivatives having neurokinin antagonistic activity, in particular NK1 antagonistic activity, a combined NK1/NK3 antagonistic activity and a combined NK1/NK2/NK3 antagonistic activity, their preparation, compositions comprising them and their use as a medicine, in particular for the treatment of schizophrenia, emesis, anxiety and depression, irritable bowel syndrom (IBS), circadian rhythm disturbances, visceral pain, neurogenic inflammation, asthma, micturition disorders such as urinary incontinence and nociception. The compounds according to the invention can be represented by general Formula (I) and comprises also the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof, the N-oxide form thereof and prodrugs thereof, wherein all substituents are defined as in Claim 1. In view of their capability to antagonize the actions of tachykinins by blocking the neurokinin receptors, and in particular antagonizing the actions of substance P, Neurokinin A and Neurokinin B by blocking the NK1, NK2 and NK3 receptors, the compounds according to the invention are useful as a medicine, in particular in the prophylactic and therapeutic treatment of tachykinin-mediated conditions, such as, for instance CNS disorders, in particular schizoaffective disorders, depression, anxiety disorders, stress-related disorders, sleep disorders, cognitive disorders, personality disorders, eating disorders, neurodegenerative diseases, addiction disorders, mood disorders, sexual dysfunction, pain and other CNS-related conditions; inflammation; allergic disorders; emesis; gastrointestinal disorders, in particular irritable bowel syndrome (IBS); skin disorders; vasospastic diseases; fibrosing and collagen diseases; disorders related to immune enhancement or suppression and rheumatic diseases and body weight control.
1. A compound according to the general Formula (I) the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof, the N-oxide form thereof and prodrugs thereof, whereinn is an integer, equal to 0, 1 or 2; m is an integer, equal to 1 or 2, provided that if m is 2, then n is 1; p is an integer equal to 1 or 2; q is an integer equal to 0 or 1; Q is O or NR3; X is a covalent bond or a bivalent radical of formula —O—, —S— or —NR3; each R3 independently from each other, is hydrogen or alkyl; each R1 independently from each other, is selected from the group of Ar1, Ar1-alkyl and di(Ar1)-alkyl; R2 is Ar2, Ar2-alkyl, di(Ar2)alkyl, Het1 or Het1-alkyl Y is a covalent bond or a bivalent radical of formula —C(═O)—, —SO2—, >C═CH—R or >C═N—R, wherein R is CN or nitro; each Alk represents, independently from each other, a covalent bond; a bivalent straight or branched, saturated or unsaturated hydrocarbon radical having from 1 to 6 carbon atoms; or a cyclic saturated or unsaturated hydrocarbon radical having from 3 to 6 carbon atoms; each radical optionally substituted on one or more carbon atoms with one or more phenyl, halo, cyano, hydroxy, formyl and amino radicals; L is selected from the group of hydrogen, alkyl, alkyloxy, Ar3-oxy, alkyloxycarbonyl, alkylcarbonyloxy, mono- and di(alkyl)amino, mono- and di(Ar3)amino, Ar3, Ar3carbonyl, Het2 and Het2 carbonyl; Ar1 is phenyl, optionally substituted with 1, 2 or 3 substituents, each independently from each other, selected from the group of halo, alkyl, cyano, aminocarbonyl and alkyloxy; Ar2 is naphthalenyl or phenyl, each optionally substituted with 1, 2 or 3 substituents, each independently from each other, selected from the group of halo, nitro, amino, mono- and di(alkyl)amino, cyano, alkyl, hydroxy, alkyloxy, carboxyl, alkyloxycarbonyl, aminocarbonyl and mono- and di(alkyl)aminocarbonyl; Ar3 is naphthalenyl or phenyl, optionally substituted with 1, 2 or 3 substituents, each independently from each other, selected from the group of alkyloxy, alkyl, halo, hydroxy, Ar1carbonyloxycarbonyl, pyridinyl, morpholinyl, pyrrolidinyl, imidazo[1,2-a]pyridinyl, morpholinylcarbonyl, pyrrolidinylcarbonyl, amino and cyano; Het1 is a monocyclic heterocyclic radical selected from the the group of pyrrolyl, pyrazolyl, imidazolyl, furanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridinyl, pyrimidinyl, pyrazinyl and pyridazinyl; or a bicyclic heterocyclic radical selected from the group of quinolinyl, quinoxalinyl, indolyl, benzimidazolyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, benzisothiazolyl, benzofuranyl, benzothienyl and 4a,8a-dihydro-2H-chromenyl; each heterocyclic radical may optionally be substituted on any atom by one or more radicals selected from the group of halo, oxo and alkyl; Het2 is a monocyclic heterocyclic radical selected from the group of tetrahydrofuranyl, pyrrolidinyl, dioxolyl, imidazolidinyl, pyrrazolidinyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl, imidazolidinyl, tetrahydrofuranyl, 2H-pyrrolyl, pyrrolinyl, imidazolinyl, pyrrazolinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, furanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, thiadiazolyl, isothiazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl and triazinyl; or a bicyclic heterocyclic radical selected from the group of benzopiperidinyl, quinolinyl, quinoxalinyl, indolyl, isoindolyl, chromenyl, benzimidazolyl, imidazo[1,2-a]pyridinyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, benzisothiazolyl, benzofuranyl, benzothienyl, benzo[2,1,3]oxadiazolyl, imidazo[2,1-b]thiazolyl, 2,3-dihydrobenzo[1,4]dioxyl and octahydrobenzo-[1,4]dioxyl; each radical may optionally be substituted with one or more radicals selected from the group of Ar1, Ar1alkyl, Ar1alkyloxyalkyl, halo, hydroxy, alkyl, alkylcarbonyl, alkyloxy, alkyloxyalkyl, alkyloxycarbonyl, piperidinyl, pyridinyl, pyrrolyl, thienyl, oxo and oxazolyl; and alkyl is a straight or branched saturated hydrocarbon radical having with one or more radicals selected from the group of phenyl, halo, cyano, oxo, hydroxy, formyl and amino. 2. A compound according to claim 1, characterized in that n is 1; m is 1; p is 1; q is 0; Q is O; X is a covalent bond; each R1 is Ar1 or Ar1-alkyl; R2 is Ar2; Y is a covalent bond or a bivalent radical of formula —C(═O)—, —SO2— or >C═CH—R or >C═N—R, wherein R is CN or nitro; each Alk represents, independently from each other, a covalent bond; a bivalent straight or branched, saturated hydrocarbon radical having from 1 to 6 carbon atoms; or a cyclic saturated hydrocarbon radical having from 3 to 6 carbon atoms; each radical optionally substituted on one or more carbon atoms with one or more hydroxy radicals; L is selected from the group of hydrogen, alkyl, alkyloxy, alkylcarbonyloxy, mono- and di(alkyl)amino, mono-and di(Ar3)amino, Ar3, Het2 and Het2carbonyl; Ar1 is phenyl; Ar2 is phenyl, optionally substituted with 1, 2 or 3 alkyl radicals; Ar3 is phenyl, optionally substituted with 1, 2 or 3 substituents, each independently from each other, selected from the group of alkyloxy, alkyl, halo, hydroxy, Ar1carbonyloxycarbonyl and cyano; Het2 is a heterocyclic radical selected from the group of tetrahydrofuranyl, pyrrolidinyl, imidazolyl, pyrazolyl, furanyl, thienyl, isoxazolyl, thiazolyl, thiadiazolyl, pyridinyl, pyrazinyl, benzo [2,1,3]oxadiazolyl and imidazo[2,1-b]thiazolyl; each radical optionally substituted with one or more Ar1alkyloxyalkyl, halo, alkyl, alkylcarbonyl, pyridinyl or oxazolyl radicals; and alkyl is a straight hydrocarbon radical having 1 to 6 carbon atoms, optionally substituted with one or more radicals selected from the group of halo and hydroxy 3. A compound according to claim 1 wherein R1 is Ar1methyl and attached to the 2-position or R1 is Ar1 and attached to the 3-position. 4. A compound according to claim 1 wherein the R2—X—C(=Q)- moiety is 3,5-di-(trifluoromethyl)phenylcarbonyl. 5. A compound according to claim 1 wherein p is 1. 6. A compound according to claim 1 wherein Y is —C(═O)—. 7. A compound according to claim 1 wherein Alk is a covalent bond. 8. A compound according to claim 1 wherein L is Het2. 9. A compound selected from the group of compounds with compound number 25, 48, 79, 39, 15, 41, 64, 88, 50, 59 and 3, as described in any one of Tables 1-2. 10. A compound according to claim 1 for use as a medicine. 11. The use of a compound according to claim 1 treating tachykinin mediated conditions. 12. The use of a compound according to claim 11 for treating schizophrenia, emesis, anxiety, depression, irritable bowel syndrome (IBS), circadian rhythm disturbances, pain, neurogenic inflammation, asthma, micturition disorders and nociception. 13. A pharmaceutical composition comprising a pharmaceutically acceptable carrier and, as active ingredient, a therapeutically effective amount of a compound according to claim 1. 14. A process for preparing a pharmaceutical composition as claimed in claim 13, wherein a pharmaceutically acceptable carrier is intimately mixed with a therapeutically effective amount of a compound as claimed in claim 1. 15. A process for the preparation of a compound of Formula (I″) in which an intermediate compound of Formula (II) is reacted with an intermediate compound of Formula (III), wherein the radicals R2, X, Q, R1, m, n, p and q are as defined in claim 1. 16. A process for the preparation of a compound of Formula (I′) in which a final compound of Formula (I″) is reductively hydrogenated, wherein the radicals R2, X, Q, R1, m, n, p and q are as defined in claim 1. 17. A process for the preparation of a compound according to Formula (I′) comprising the consecutive steps of 1) obtaining a compound of Formula (I″) according to claim 15; 2) obtaining a compound of Formula (I′) according to claim 16.
FIELD OF THE INVENTION This invention concerns substituted 1-piperidin-3-yl-4-piperidin-4-yl-piperazine derivatives having neurokinin antagonistic activity, in particular NK1 antagonistic activity, a combined NK1/NK3 antagonistic activity and a combined NK1/NK2/NK3 antagonistic activity, their preparation, compositions comprising them and their use as a medicine, in particular for the treatment of schizophrenia, emesis, anxiety and depression, irritable bowel syndrom (IBS), circadian rhythm disturbances, visceral pain, neurogenic inflammation, asthma, micturition disorders such as urinary incontinence and nociception. BACKGROUND OF THE INVENTION Tachykinins belong to a family of short peptides that are widely distributed in the mammalian central and peripheral nervous system (Bertrand and Geppetti, Trends Pharmacol. Sci. 17:255-259 (1996); Lundberg, Can. J. Physiol. Pharmacol. 73:908-914 (1995); Maggi, Gen. Pharmacol. 26:911-944 (1995); Regoli et al., Pharmacol. Rev. 46 (1994)). They share the common C-terminal sequence Phe-Xaa-Gly-Leu-Met-NH2. Tachykinins released from peripheral sensory nerve endings are believed to be involved in neurogenic inflammation. In the spinal cord/central nervous system, tachykinins may play a role in pain transmission/perception and in some autonomic reflexes and behaviors. The three major tachykinins are Substance P (SP), Neurokinin A (NKA) and Neurokinin B (NKB) with preferential affinity for three distinct receptor subtypes, termed NK1, NK2, and NK3, respectively. However, functional studies on cloned receptors suggest strong functional cross-interaction between the 3 tachykinins and their corresponding receptors (Maggi and Schwartz, Trends Pharmacol. Sci. 18: 351-355 (1997)). Species differences in structure of NK1 receptors are responsible for species-related potency differences of NK1 antagonists (Maggi, Gen. Pharmacol. 26:911-944 (1995); Regoli et al., Pharmacol. Rev. 46(4):551-599 (1994)). The human NK1 receptor closely resembles the NK1 receptor of guinea-pigs and gerbils but differs markedly from the NK1 receptor of rodents. The development of neurokinin antagonists has led to date to a series of peptide compounds of which might be anticipated that they are metabolically too labile to be employed as pharmaceutically active substances (Longmore J. et al, DN&P 8(1):5-23 (1995)). The tachykinins are involved in schizophrenia, depression, (stress-related) anxiety states, emesis, inflammatory responses, smooth muscle contraction and pain perception. Neurokinin antagonists are in development for indications such as emesis, anxiety and depression, irritable bowel syndrome (IBS), circadian rhythm disturbances, visceral pain, neurogenic inflammation, asthma, micturition disorders, and nociception. In particular, NK1 antagonists have a high therapeutic potential in emesis and depression and NK2 antagonists have a high therapeutic potential in asthma treatments. NK3 antagonists seem to play a role in the treatment of pain/inflammation (Giardina, G. et al. Exp. Opin. Ther. Patents, 10(6): 939-960 (2000)) and schizophrenia. Schizophrenia The NK3 antagonist SR142801 (Sanofi) was recently shown to have antipsychotic activity in schizophrenic patients without affecting negative symptoms (Arvantis, L ACNP Meeting, December 2001). Activation of NK1 receptors causes anxiety, stressful events evoke elevated substance P (SP) plasma levels and NK1 antagonists are reported to be anxiolytic in several animal models. The NK1 antagonist from Merck, MK-869 shows antidepressant effects in major depression, but data were not conclusive due to a high placebo response rate. Moreover, the NK1 antagonist from Glaxo-Welcome (S)-GR205,171 was shown to enhance dopamine release in the frontal cortex but not in the striatum (Lejeune et al. Soc. Neurosci, November 2001). It is therefore hypothesized that NK3 antagonism in combination with NK1 antagonism would be beneficial against both positive and negative symptoms of schizophrenia Anxiety and Depression Depression is one of the most common affective disorders of modern society with a high and still increasing prevalence, particularly in the younger members of the population. The life time prevalence rates of Major depression (MDD, DSM-IV) is currently estimated to be 10-25% for women and 5-12% for men, whereby in about 25% of patients the life time MDD is recurrent, without full inter-episode recovery and superimposed on dysthymic disorder. There is a high co-morbidity of depression with other mental disorders and, particularly in younger population high association with drug and alcohol abuse. In the view of the fact that depression primarily affects the population between 18-44 years of age e.g. the most productive population, it is obvious that it imposes a high burden on individuals, families and the whole society. Among all therapeutic possibilities, the therapy with antidepressants is incontestably the most effective. A large number of antidepressants have been developed and introduced to the market in the course of the last 40 years. Nevertheless, none of the current antidepressants fulfill all criteria of an ideal drug (high therapeutic and prophylactic efficacy, rapid onset of action, completely satisfactory short- and long-term safety, simple and favourable pharmacokinetics) or is without side effects which in one or the other way limits their use in all groups and subgroups of depressed patients. Since no treatment of the cause of depression exists at present, nor appears imminent, and no antidepressant is effective in more than 60-70% of patients; the development of a new antidepressant which may circumvent any of the disadvantages of the available drugs is justified. Several findings indicate involvement of SP in stress-related anxiety states. Central injection of SP induces a cardiovascular response resembling the classical “fight or flight” reaction characterised physiologically by vascular dilatation in skeletal muscles and decrease of mesenteric and renal blood flow. This cardiovascular reaction is accompanied by a behavioural response observed in rodents after noxious stimuli or stress (Culman and Unger, Can. J. Physiol. Pharmacol. 73:885-891 (1995)). In mice, centrally administered NK1 agonists and antagonists are anxiogenic and anxiolytic, respectively (Teixeira et at., Eur. J. Pharmacol. 311:7-14 (1996)). The ability of NK1 antagonists to inhibit thumping induced by SP (or by electric shock; Ballard et al., Trends Pharmacol. Sci. 17:255-259 (2001)) might correspond to this antidepressant/anxiolytic activity, since in gerbils thumping plays a role as an alerting or warning signal to conspecifics. The NK1 receptor is widely distributed throughout the limbic system and fear-processing pathways of the brain, including the amygdala, hippocampus, septum, hypothalamus, and periaqueductal grey. Additionally, substance P is released centrally in response to traumatic or noxious stimuli and substance P-associated neurotransmission may contribute to or be involved in anxiety, fear, and the emotional disturbances that accompany affective disorders such as depression and anxiety. In support of this view, changes in substance P content in discrete brain regions can be observed in response to stressful stimuli (Brodin et al., Neuropeptides 26:253-260 (1994)). Central injection of substance P mimetics (agonists) induces a range of defensive behavioural and cardiovascular alterations including conditioned place a version (Elliott, Exp. Brain. Res. 73:354-356 (1988)), potentiated acoustic startle response (Krase et at., Behav. Brain. Res. 63:81-88 (1994)), distress vocalisations, escape behaviour (Kramer et al., Science 281:1640-1645 (1998)) and anxiety on the elevated plus maze (Aguiar and Brandao, Physiol. Behav. 60:1183-1186 (1996)). These compounds did not modify motor performance and co-ordination on the rotarod apparatus or ambulation in an activity cage. Down-regulation of substance P biosynthesis occurs in response to the administration of known anxiolytic and antidepressant drugs (Brodin et al., Neuropeptides 26:253-260 (1994); Shirayama et al., Brain. Res. 739:70-78 (1996)). Similarly, a centrally administered NK1 agonist-induced vocalisation response in guinea-pigs can be antagonised by antidepressants such as imipramine and fluoxetine as well as L-733,060, an NK1 antagonist. These studies provide evidence suggesting that blockade of central NK1 receptors may inhibit psychological stress in a manner resembling antidepressants and anxiolytics (Rupniak and Kramer, Trends Pharmacol. Sci. 20:1-12 (1999)), but without the side effects of present medications. Emesis Nausea and vomiting are among the most distressing side effects of cancer chemotherapy. These reduce the quality of life and may cause patients to delay or refuse, potentially curative drugs (Kris et al., J. Clin. Oncol., 3:1379-1384 (1985)). The incidence, intensity and pattern of emesis is determined by different factors, such as the chemotherapeutic agent, dosage and route of administration. Typically, early or acute emesis starts within the first 4 h after chemotherapy administration, reaching a peak between 4 h and 10 h, and decreases by 12 to 24 h. Delayed emesis (developing after 24 h and continuing until 3-5 days post chemotherapy) is observed with most ‘high-emetogenic’ chemotherapeutic drugs (level 4 and 5 according to Hesketh et al., J. Clin. Oncol. 15:103 (1997)). In humans, these ‘high-emetogenic’ anti-cancer treatments, including cis-platinum, induce acute emesis in >98% and delayed emesis in 60-90% of cancer patients. Animal models of chemotherapy such as cisplatin-induced emesis in ferrets (Rudd and Naylor, Neuropharmacology 33:1607-1608 (1994); Naylor and Rudd, Cancer. Surv. 21:117-135 (1996)) have successfully predicted the clinical efficacy of the 5-HT3 receptor antagonists. Although this discovery led to a successful therapy for the treatment of chemotherapy- and radiation-induced sickness in cancer patients, 5-HT3 antagonists such as ondansetron and granisetron (either or not associated with dexamethasone) are effective in the control of the acute emetic phase (the first 24 h) but can only reduce the development of delayed emesis (>24 h) with poor efficacy (De Mulder et al., Annuals of Internal Medicine 113:834-840 (1990); Roila, Oncology 50:163-167 (1993)). Despite these currently most effective treatments for the prevention of both acute and delayed emesis, still 50% of patients suffer from delayed vomiting and/or nausea (Antiemetic Subcommittee, Annals Oncol. 9:811-819 (1998)). In contrast to 5-HT3 antagonists, NK1 antagonists such as CP-99,994 (Piedimonte et al., L. Pharmacol. Exp. Ther. 266:270-273 (1993)) and aprepitant (also known as MK-869 or L1754,030; Kramer et al., Science 281:1640-1645 (1998); Rupniak and Kramer, Trends Pharmacol. Sci. 20:1-12 (1999)) have now been shown to inhibit not only the acute but also the delayed phase of cisplatin-induced emesis in animals (Rudd et al., Br. J. Pharmacol. 119:931-936(1996) ; Tattersall et al., Neuropharmacology 39:652-663 (2000)). NK1 antagonists have also been demonstrated to reduce ‘delayed’ emesis in man in the absence of concomitant therapy (Cocquyt et al., Eur. J. Cancer 37:835-842 (2001); Navari et al., N. Engl. L. Med 340:190-195 (1999)). When administered together with dexamethasone and 5-HT3 antagonists, moreover, NK1 antagonists (such as MK-869 and CJ-11,974, also known as Ezlopitant) have been shown to produce additional effects in the prevention of acute emesis (Campos et al., J. Clin. Oncol. 19:1759-1767 (2001); Hesketh et al., Clin. Oncol. 17:338-343 (1999)). Central neurokinin NK1 receptors play a major role in the regulation of emesis. NK1 antagonists are active against a wide variety of emetic stimuli (Watson et al., Br. J. Pharmacol. 115:84-94 (1995); Tattersall et al., Neuropharmacol. 35:1121-1129 (1996); Megens et al., J. Pharmacol. Exp. Ther. 302:696-709 (2002)). The compounds are suggested to act by blocking central NK1 receptors in the nucleus tractus solitarius. Apart from NK1 antagonism, CNS penetration is thus a prerequisite for the antiemetic activity of these compounds. Loperamide-induced emesis in ferrets can be used as a fast and reliable screening model for the antiemetic activity of NK1 antagonists. Further evaluation of their therapeutic value in the treatment of both the acute and the delayed phases of cisplatin-induced emesis has been demonstrated in the established ferret model (Rudd et al., Br. J. Pharmacol. 119:931-936 (1994)). This model studies both ‘acute’ and ‘delayed’ emesis after cisplatin and has been validated in terms of its sensitivity to 5-HT3 receptor antagonists, glucocorticoids (Sam et al., Eur. J. Pharmacol. 417:231-237 (2001)) and other pharmacological challenges. It is unlikely that any future anti-emetic would find clinical acceptance unless successfully treating both the ‘acute’ and ‘delayed’ phases of emesis. Irritable Bowel Syndrome (IBS) Patients with irritable bowel syndrome (IBS) experience impaired quality of life, and utilise health care resources extensively as they seek better “solutions” (including unnecessary repeated investigations or even surgery). Although these patients suffer from a ‘benign’ disorder (in other words, they will never die or develop significant complications), they nevertheless cause a significant economic burden by extensive health care resource utilisation, and absence from work. A reasonable number of pre-clinical publications over the role of NK1 receptors in visceral pain has been published. Using NK1 receptor knockout mice and NK1 antagonists in animal models, different groups have demonstrated the important role played by the NK1 receptor in hyperalgesia and visceral pain. The distribution of NK1 receptors and substance P favours a major role in visceral rather than in somatic pain. Indeed more than 80% of visceral primary afferent contain substance P compared with only 25% skin afferents. NK1 receptors are also involved in gastrointestinal motility (Tonini et al., Gastroenterol. 120:938-945 (2001); Okano et al., J. Pharmacol. Exp. Ther. 298:559-564 (2001)). Because of this dual role in both gastrointestinal motility and in nociception, NK1 antagonists are considered to have potential to ameliorate symptoms in IBS patients. BACKGROUND PRIOR ART Compounds containing the 1-piperidin-4-yl-piperazinyl moiety were published in WO 97/16440-A1, published May 9, 1997 by Janssen Pharmaceutica N.V. for use as substance P antagonists, in WO 02/32867, published Apr. 25, 2002 by Glaxo Group Ltd. for their special advantages as neurokinin antagonists (more specifically were disclosed 4-piperazin-1-yl-piperidine-1-carboxylic acid amide derivatives), in WO 01/30348-A1, published May 3, 2001 by Janssen Pharmaceutica N.V., for use as substance P antagonists for influencing the circadian timing system, and in WO 021062784-A1, published Aug. 15, 2002 by Hoffmann-La Roche AG for use as neurokinin-1 antagonists. The compounds of the present invention differ from the compounds of the prior art in the substitution of the piperazinyl moiety, being a substituted piperidinyl moiety as well as in their improved ability as potent, orally and centrally active neurokinin antagonists with therapeutic value, especially for the treatment of schizophrenia, emesis anxiety and depression, irritable bowel syndrome (IBS), circadian rhythm disturbances, visceral pain, neurogenic inflammation, asthma micturition disorders such as urinary incontinence and nociception. DESCRIPTION OF THE INVENTION The present invention relates to novel substituted 1-piperidin-3-yl-4-piperidin-4yl-piperazine derivatives according to the general Formula (I) the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof, the N-oxide form thereof and prodrugs thereof, wherein: the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof, the N-oxide form thereof and prodrugs thereof, wherein: n is an integer, equal to 0, 1 or 2; m is an integer, equal to 1 or 2, provided that if m is 2, then n is 1; p is an integer equal to 1 or 2; q is an integer equal to 0 or 1; Q is O or NR3; X is a covalent bond or a bivalent radical of formula —O—, —S— or —NR3—; each R3 independently from each other, is hydrogen or alkyl; each R1 independently from each other, is selected from the group of Ar1, Ar1-alkyl and di(Ar1)-alkyl; R2 is Ar2, Ar2-alkyl, di(Ar2)alkyl, Het1 or Het1-alkyl; Y is a covalent bond or a bivalent radical of formula —C(═O)—, —SO2—, >C═CH—R or >C═N—R, wherein R is CN or nitro; each Alk represents, independently from each other, a covalent bond; a bivalent straight or branched, saturated or unsaturated hydrocarbon radical having from 1 to 6 carbon atoms; or a cyclic saturated or unsaturated hydrocarbon radical having from 3 to 6 carbon atoms; each radical optionally substituted on one or more carbon atoms with one or more phenyl, halo, cyano, hydroxy, formyl and amino radicals; L is selected from the group of hydrogen, alkyl, alkyloxy, Ar3-oxy, alkyloxycarbonyl, alkylcarbonyloxy, mono- and di(alkyl)amino, mono-and di(Ar3)amino, Ar3, Ar3carbonyl, Het2 and Het3carbonyl; Ar1 is phenyl, optionally substituted with 1, 2 or 3 substituents, each independently from each other, selected from the group of halo, alkyl, cyano, aminocarbonyl and alkyloxy; Ar2 is naphthalenyl or phenyl, each optionally substituted with 1, 2 or 3 substituents, each independently from each other, selected from the group of halo, nitro, amino, mono- and di(alkyl)amino, cyano, alkyl, hydroxy, alkyloxy, carboxyl, alkyloxycarbonyl, aminocarbonyl and mono- and di(alkyl)aminocarbonyl; Ar3 is naphthalenyl or phenyl, optionally substituted with 1, 2 or 3 substituents, each independently from each other, selected from the group of alkyloxy, alkyl, halo, hydroxy, Ar1carbonyloxycarbonyl, pyridinyl, morpholinyl, pyrrolidinyl, imidazo[1,2-a]pyridinyl, morpholinylcarbonyl, pyrrolidinylcarbonyl, amino and cyano; Het1 is a monocyclic heterocyclic radical selected from the the group of pyrrolyl, pyrazolyl, imidazolyl, furanyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridinyl, pyrimidinyl, pyrazinyl and pyridazinyl; or a bicyclic heterocyclic radical selected from the group of quinolinyl, quinoxalinyl, indolyl, benzimidazolyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, benzisothiazolyl, benzofuranyl, benzothienyl and 4a,8a-dihydro-2H-chromenyl; each heterocyclic radical may optionally be substituted on any atom by one or more radicals selected from the group of halo, oxo and alkyl; Het2 is a monocyclic heterocyclic radical selected from the group of tetrahydrofuranyl, pyrrolidinyl, dioxolyl, imidazolidinyl, pyrrazolidinyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl, imidazolidinyl, tetrahydrofuranyl, 2H-pyrrolyl, pyrrolinyl, imidazolinyl, pyrrazolidinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, furanyl, thienyl, oxazolyl isoxazolyl, thiazolyl, thiadiazolyl, isothiazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl and triazinyl; or a bicyclic heterocyclic radical selected from the group of benzopiperidinyl, quinolinyl quinoxalinyl, indolyl, isoindolyl, chromenyl, benzimidazolyl, imidazo[1,2-a]pyridinyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, benzisothiazolyl, benzofuranyl, benzothienyl, benzo [2,1,3]oxadiazolyl, imidazo[2,1-b]thiazolyl, 2,3-dihydrobenzo[1,4]dioxyl and octahydrobenzo[1,4]dioxyl; each radical may optionally be substituted with one or more radicals selected from the group of Ar1, Ar1alkyl, Ar1alkyloxyalkyl, halo, hydroxy, alkyl, alkylcarbonyl, alkyloxy, alkyloxyalkyl, alkyloxycarbonyl, piperidinyl, pyridinyl, pyrrolyl, thienyl, oxo and oxazolyl; and alkyl is a straight or branched saturated hydrocarbon radical having from 1 to 6 carbon atoms or a cyclic saturated hydrocarbon radicals having from 3 to 6 carbon atoms; optionally substituted on one or more carbon atoms with one or more radicals selected from the group of phenyl, halo, cyano, oxo, hydroxy, formyl and amino. More in particular, the invention relates to a compound according to the general Formula (I), the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof, the N-oxide form thereof and a prodrug thereof, wherein: n is 1; m is 1; p is 1; q is 0; Q is O; X is a covalent bond; each R1 is Ar1 or Ar1-alkyl; R2 is Ar2; Y is a covalent bond or a bivalent radical of formula —C(═O)—, —SO2— or >C═H—R or >C═N—R, wherein R is CN or nitro; each Alk represents, independently from each other, a covalent bond; a bivalent straight or branched, saturated hydrocarbon radical having from 1 to 6 carbon atoms; or a cyclic saturated hydrocarbon radical having from 3 to 6 carbon atoms; each radical optionally substituted on one or more carbon atoms with one or more hydroxy radicals; L is selected from the group of hydrogen, alkyl, alkyloxy, alkylcarbonyloxy, mono- and di(alkyl)amino, mono-and di(Ar3)amino, Ar3, Het2 and Hetcarbonyl; Ar1 is phenyl; Ar2 is phenyl, optionally substituted with 1, 2 or 3 alkyl radicals; Ar3 is phenyl, optionally substituted with 1, 2 or 3 substituents, each independently from each other, selected from the group of alkyloxy, alkyl, halo, hydroxy, Ar1carbonyloxycarbonyl and cyano; He2 is a heterocyclic radical selected from the group of tetrahydrofuranyl, pyrrolidinyl, imidazolyl, pyrazolyl, furanyl, thienyl, isoxazolyl, thiazolyl, thiadiazolyl, pyridinyl, pyrazinyl, benzo [2,1,3]oxadiazolyl and imidazo[2,1-b]thiazolyl; each radical optionally substituted with one or more Ar1alkyloxyalkyl, halo, alkyl, alkylcarbonyl, pyridinyl or oxazolyl radicals; and alkyl is a straight hydrocarbon radical having 1 to 6 carbon atoms, optionally substituted with one or more radicals selected from the group of halo and hydroxy; More in particular, the invention relates to a compound according to the general Formula (I), the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof, the N-oxide form thereof and a prodrug thereof, wherein R1 is Ar1methyl and attached to the 2-position or R1 is Ar1 and attached to the 3-position, as exemplified in either of the following formulas for compounds according to Formula (I) wherein m and n are equal to 1 and Ar is an unsubstituted phenyl. More in particular, the invention relates to a compound according to the general Formula (I), the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof, the N-oxide form thereof and a prodrug thereof, wherein the R2—X—C(=Q)- moiety is 3,5di-(trifluoromethyl)phenylcarbonyl. More in particular, the invention relates to a compound according to the general Formula (I), the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof, the N-oxide form thereof and a prodrug thereof, wherein p is 1. More in particular, the invention relates to a compound according to the general Formula (I), the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof, the N-oxide form thereof and a prodrug thereof, wherein Y is —C(═O)—. More in particular, the invention relates to a compound according to the general Formula (I), the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof, the N-oxide form thereof and a prodrug thereof, wherein Alk is a covalent bond. More in particular, the invention relates to a compound according to the general Formula (I), the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof, the N-oxide form thereof and a prodrug thereof, wherein L is Het2. More in particular, the invention relates to a compound according to the general Formula (I), the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof, the N-oxide form thereof and a prodrug thereof, wherein the compound is a compound selected from the group of compounds with compound number 25, 48, 79, 39, 15, 41, 64, 88, 50, 59 and 3, as mentioned in any one of Tables 1-2 further in this application. In the framework of this application, alkyl is defined as a monovalent straight or branched saturated hydrocarbon radical having from 1 to 6 carbon atoms, for example methyl, ethyl, propyl, butyl, 1-methylpropyl, 1,1-dimethylethyl, pentyl, hexyl; alkyl further defines a monovalent cyclic saturated hydrocarbon radical having from 3 to 6 carbon atoms, for example cyclopropyl, methylcyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The definition of alkyl also comprises an alkyl radical that is optionally substituted on one or more carbon atoms with one or more phenyl halo, cyano, oxo, hydroxy, formyl and amino radicals, for example hydroxyalkyl, in particular hydroxymethyl and hydroxyethyl and polyhaloalkyl, in particular difluoromethyl and trifluoromethyl. In the framework of this application, halo is generic to fluoro, chloro, bromo and iodo. In the framework of this application, with “compounds according to the invention” is meant a compound according to the general Formula (I), the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof, the N-oxide form thereof and a prodrug thereof. In the framework of this application, especially in the moiety Alka-Y-Alkb in Formula (I), when two or more consecutive elements of said moiety denote a covalent bond, then a single covalent bond is denoted. For example, when Alka and Y denote both a covalent bond and Alkb is CH2, then the moiety Alka-Y-Alkb depotes —CH2. Similarly, if Alka, Y and Alkb each denote a covalent bond and L denotes H, then the moiety Alka-Y-Alkb denotes —H. The pharmaceutically acceptable salts are defined to comprise the therapeutically active non-toxic acid addition salts forms that the compounds according to Formula (I) are able to form. Said salts can be obtained by treating the base form of the compounds according to Formula (I) with appropriate acids, for example inorganic acids, for example hydrohalic acid, in particular hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid and phosphoric acid; organic acids, for example acetic acid, hydroxyacetic acid, propanoic acid, lactic acid, pyruvic acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, cyclamic acid, salicylic acid, p-aminosalicylic acid and pamoic acid. The compounds according to Formula (I) containing acidic protons may also be converted into their therapeutically active non-toxic metal or amine addition salts forms by treatment with appropriate organic and inorganic bases. Appropriate base salts forms comprise, for example, the ammonium salts, the alkaline and earth alkaline metal salts, in particular lithium, sodium, potassium, magnesium and calcium salts, salts with organic bases, e.g. the benzathine, N-methyl-D-glucamine, hybramine salts, and salts with amino acids, for example arginine and lysine. Conversely, said salts forms can be converted into the free forms by treatment with an appropriate base or acid. The term addition salt as used in the framework of this application also comprises the solvates that the compounds according to Formula (I) as well as the salts thereof, are able to form. Such solvates are, for example, hydrates and alcoholates. The N-oxide forms of the compounds according to Formula (I) are meant to comprise those compounds of Formula (I) wherein one or several nitrogen atoms are oxidized to the so-called N-oxide, particularly those N-oxides wherein one or more tertiary nitrogens (e.g of the piperazinyl or piperidinyl radical) are N-oxidized. Such N-oxides can easily be obtained by a skilled person without any inventive skills and they are obvious alternatives for the compounds according to Formula (I) since these compounds are metabolites, which are formed by oxidation in the human body upon uptake. As is generally known, oxidation is normally the first step involved in drug metabolism (Textbook of Organic Medicinal and Pharmaceutical Chemistry, 1977, pages 70-75). As is also generally known, the metabolite form of a compound can also be administered to a human instead of the compound per se, with much the same effects. The compounds according to the invention possess at least 2 oxydizable nitrogens (tertiary amines moieties). It is therefore highly likely that N-oxides will form in the human metabolism. The compounds of Formula (I) may be converted to the corresponding N-oxide forms following art-known procedures for converting a trivalent nitrogen into its N-oxide form. Said N-oxidation reaction may generally be carried out by reacting the starting material of Formula (I) with an appropriate organic or inorganic peroxide. Appropriate inorganic peroxides comprise, for example, hydrogen peroxide, alkali metal or earth alkaline metal peroxides, e.g. sodium peroxide, potassium peroxide; appropriate organic peroxides may comprise peroxy acids such as, for example, benzenecarboperoxoic acid or halo substituted benzenecarboperoxoic acid, e.g. 3-chlorobenzenecarboperoxoic acid, peroxoalkanoic acids, e.g. peroxoacetic acid, alkylhydroperoxides, e.g. tert-butyl hydroperoxide. Suitable solvents are, for example, water, lower alkanols, e.g. ethanol and the like, hydrocarbons, e.g. toluene, ketones, e.g. 2-butanone, halogenated hydrocarbons, e.g. dichloromethane, and mixtures of such solvents. The term “stereochemically isomeric forms” as used hereinbefore defines all the possible isomeric forms that the compounds of Formula (I) may possess. Unless otherwise mentioned or indicated, the chemical designation of compounds denotes the mixture of all possible stereochemically isomeric forms, said mixtures containing all diastereomers and enantiomers of the basic molecular structure. More in particular, stereogenic centers may have the R— or S-configuration; substituents on bivalent cyclic (partially) saturated radicals may have either the cis- or trans-configuration. Compounds encompassing double bonds can have an E or Z-stereochemistry at said double bond. Stereochemically isomeric forms of the compounds of Formula (I) are obviously intended to be embraced within the scope of this invention. Following CAS nomenclature conventions, when two stereogenic centers of known absolute configuration are present in a molecule, an R or S descriptor is assigned (based on Cahn-Ingold-Prelog sequence rule) to the lowest-numbered chiral center, the reference center. R* and S* each indicate optically pure stereogenic centers with undetermined absolute configuration. If “α” and “β” are used: the position of the highest priority substituent on the asymmetric carbon atom in the ring system having the lowest ring number, is arbitrarily always in the “α” position of the mean plane determined by the ring system. The position of the highest priority substituent on the other asymmetric carbon atom in the ring system (hydrogen atom in compounds according to Formula (I)) relative to the position of the highest priority substituent on the reference atom is denominated “α”, if it is on the same side of the mean plane determined by the ring system, or “β”, if it is on the other side of the mean plane determined by the ring system. Compounds according to Formula (I) and some of the intermediate compounds have at least two stereogenic centers in their structure, denoted by an asterisk in Tables 1 and 2. The invention also comprises derivative compounds (usually called “pro-drugs”) of the pharmacologically-active compounds according to the invention, which are degraded in vivo to yield the compounds according to the invention. Pro-drugs are usually (but not always) of lower potency at the target receptor than the compounds to which they are degraded. Pro-drugs are particularly useful when the desired compound has chemical or physical properties that make its administration difficult or inefficient. For example, the desired compound may be only poorly soluble, it may be poorly transported across the mucosal epithelium, or it may have an undesirably short plasma half-life. Further discussion on pro-drugs may be found in Stella, V. J. et al., “Prodrugs”, Drug Delivery Systems, 1985, pp. 112-176, and Drugs, 1985, 29, pp. 455-473. Pro-drugs forms of the pharmacologically-active compounds according to the invention will generally be compounds according to Formula (I), the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof and the N-oxide form thereof, having an acid group which is esterified or amidated. Included in such esterified acid groups are groups of the formula —COORx, where Rx is a C1-6alkyl, phenyl, benzyl or one of the following groups: Amidated groups include groups of the formula —CONRyRz, wherein Ry is H, C1-6alkyl, phenyl or benzyl and Rz is —OH, H, C1-6alkyl, phenyl or benzyl. Compounds according to the invention having an amino group may be derivatised with a ketone or an aldehyde such as formaldehyde to form a Mannich base. This base will hydrolyze with first order kinetics in aqueous solution. The compounds of Formula (I) as prepared in the processes described below may be synthesized in the form of racemic mixtures of enantiomers that can be separated from one another following art-known resolution procedures. The racemic compounds of Formula (I) may be converted into the corresponding diastereomeric salt forms by reaction with a suitable chiral acid. Said diastereomeric salt forms are subsequently separated, for example, by selective or fractional crystallization and the enantiomers are liberated therefrom by alkali. An alternative manner of separating the enantiomeric forms of the compounds of Formula (I) involves liquid chromatography using a chiral stationary phase. Said pure stereochemically isomeric forms may also be derived from the corresponding pure stereochemically isomeric forms of the appropriate starting materials, provided that the reaction occurs stereospecifically. Preferably if a specific stereoisomer is desired, said compound would be synthesized by stereospecific methods of preparation. These methods will advantageously employ enantiomerically pure starting materials. Pharmacology Substance P and other neurokinins are involved in a variety of biological actions such as pain transmission (nociception), neurogenic inflammation, smooth muscle contraction, plasma protein extravasation, vasodilation, secretion, mast cell degranulation, and also in activation of the immune system. A number of diseases are deemed to be engendered by activation of neurokinin receptors, in particular the NK1 receptor, by excessive release of substance P and other neurokinins in particular cells such as cells in the neuronal plexi of the gastrointestinal tract, unmyelinated primary sensory afferent neurons, sympathetic and parasympathetic neurons and nonneuronal cell types (DN&P 8(1):5-23 (1995) and Longmore 1. et al., “Neurokinin Receptors” Pharmacological Reviews 46(4):551-599 (1994)). The compounds of the present invention are potent inhibitors of neurokinin-mediated effects, in particular those mediated via the NK1, NK2 and NK3 receptor, and may therefore be described as neurokinin antagonists, especially as substance P antagonists, as may be indicated in vitro by the antagonism of substance P-induced relaxation of pig coronary arteries. The binding affinity of the present compounds for the human, guinea-pig and gerbil neurokinin receptors may also be determined in vitro in a receptor binding test using 3H-substance-P as radioligand. The subject compounds also show substance-P antagonistic activity in vivo as may be evidenced by, for instance, the antagonism of substance P-induced plasma extravasation in guinea-pigs, or the antagonism of drug-induced emesis in ferrets (Watson et al., Br. J. Pharmacol. 115:84-94 (1995)). In view of their capability to antagonize the actions of neurokinins by blocking the neurokinin receptors, and in particular by blocking the NK1, NK2 and NK3 receptor, the compounds according to the invention are useful as a medicine, in particular in the prophylactic and therapeutic treatment of tachykinin-mediated conditions. More in particular, it has been found that some compounds exhibit NK1 antagonistic activity, a combined NK1/NK3 antagonistic activity and a combined NK1/NK2/NK3 antagonistic activity as can be seen from the Table 8 in the experimental section. The invention therefore relates to a compound according to the general Formula (I), the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof, the N-oxide form thereof and prodrugs thereof, for use as a medicine. The invention also relates to the use of a compound according to the invention for the manufacture of a medicament for treating, either prophylactic or therapeutic or both, tachykinin mediated conditions. The compounds according to the invention are useful in the treatment of CNS disorders, in particular schizoaffective disorders, depression, anxiety disorders, stress-related disorders, sleep disorders, cognitive disorders, personality disorders, eating disorders, neurodegenerative diseases, addiction disorders, mood disorders, sexual dysfunction, pain and other CNS-related conditions; inflammation; allergic disorders; emesis; gastrointestinal disorders, in particular irritable bowel syndrome (IBS); skin disorders; vasospastic diseases; fibrosing and collagen diseases; disorders related to immune enhancement or suppression and rheumatic diseases and body weight control. In particular, the compounds according to the invention are useful in the treatment or prevention of schizoaffective disorders resulting from various causes, including schizoaffective disorders of the manic type, of the depressive type, of mixed type; paranoid, disorganized, catatonic, undifferentiated and residual schizophrenia; schizophreniform disorder; delusional disorder; brief psychotic disorder, shared psychotic disorder; substance-induced psychotic disorder; and psychotic disorder not otherwise specified. In particular, the compounds according to the invention are useful in the treatment or prevention of depression including but not limited to major depressive disorders including bipolar depression; unipolar depression; single or recurrent major depressive episodes with or without psychotic features, catatonic features, melancholic features, atypical features or postpartum onset, and, in the case of recurrent episodes, with or without seasonal pattern. Other mood disorders encompassed within the term “major depressive disorder” include dysthymic disorder with early or late onset and with or without atypical features, bipolar I disorder, bipolar II disorder, cyclothymic disorder, recurrent brief depressive disorder, mixed affective disorder, neurotic depression, post traumatic stress disorder and social phobia; dementia of the Alzheimer's type with early or late onset, with depressed mood; vascular dementia with depressed mood; substance-induced mood disorders such as mood disorders induced by alcohol, amphetamines, cocaine, hallucinogens, inhalants, opioids, phencyclidine, sedatives, hypnotics, anxiolytics and other substances; schizoaffective disorder of the depressed type; and adjustment disorder with depressed mood. Major depressive disorders may also result from a general medical condition including, but not limited to, myocardial infarction, diabetes, miscarriage or abortion, etc. In particular, the compounds according to the invention are useful in the treatment or prevention of anxiety disorders, including but not limited to panic attack; agoraphobia; panic disorder without agoraphobia; agoraphobia without history of panic disorder; specific phobia; social phobia; obsessive-compulsive disorder; post-traumatic stress disorder; acute stress disorder; generalized anxiety disorder; anxiety disorder due to a general medical condition; substance-induced anxiety disorder; and anxiety disorder not otherwise specified. In particular, the compounds according to the invention are useful in the treatment or prevention of stress-related disorders associated with depression and/or anxiety, including but not limited to acute stress reaction; adjustment disorders, such as brief depressive reaction, prolonged depressive reaction, mixed anxiety and depressive reaction, adjustment disorder with predominant disturbance of other emotions, adjustment disorder with predominant disturbance of conduct, adjustment disorder with mixed disturbance of emotions and conduct and adjustment disorders with other specified predominant symptoms; and other reactions to severe stress. In particular, the compounds according to the invention are useful in the treatment or prevention of stree-related disorders, including but not limited to dysomnia and/or parasomnias as primary sleep disorders; insomnia; sleep apnea; narcolepsy; circadian rhythms disorders; sleep disorders related to another mental disorder; sleep disorder due to a general medical condition; and substance-induced sleep disorder. In particular, the compounds according to the invention are useful in the treatment or prevention of cognitive disorders, including but not limited to dementia; amnesic disorders and cognitive disorders not otherwise specified, especially dementia caused by degenerative disorders, lesions, trauma, infections, vascular disorders, toxins, anoxia, vitamin deficiency or endocrinic disorders; dementia of the Alzheimer's type, with early or late onset, with depressed mood; AIDS-associated dementia or amnesic disorders caused by alcohol or other causes of thiamin deficiency, bilateral temporal lobe damage due to Herpes simplex encephalitis and other limbic encephalitis, neuronal loss secondary to anoxia/hypoglycemia/severe convulsions and surgery, degenerative disorders, vascular disorders or pathology around ventricle III. Furthermore, the compounds according to the invention are also useful as memory and/or cognition enhancers in healthy humans with no cognitive and/or memory deficit. In particular, the compounds according to the invention are useful in the treatment or prevention of personality disorders, including but not limited to paranoid personality disorder; schizoid personality disorder; schizotypical personality disorder; antisocial personality disorder; borderline personality disorder; histrionic personality disorder; narcissistic personality disorder; avoidant personality disorder; dependent personality disorder; obsessive-compulsive personality disorder and personality disorder not otherwise specified. In particular, the compounds according to the invention are also useful in the treatment or prevention of eating disorders, including anorexia nervosa; atypical anorexia nervosa; bulimia nervosa; atypical bulimia nervosa; overeating associated with other psychological disturbances; vomiting associated with other psychological disturbances; and non-specified eating disorders. In particular, the compounds according to the invention are also useful in the treatment or prevention of neurodegenerative diseases, including but not limited to Alzheimer's disease; Huntington's chorea; Creutzfeld-Jacob disease; Pick's disease; demyelinating disorders, such as multiple sclerosis and ALS; other neuropathies and neuralgia; multiple sclerosis; amyotropical lateral sclerosis; stroke and head trauma. In particular, the compounds according to the invention are also useful in the treatment or prevention of addiction disorders, including but not limited to substance dependence or abuse with or without physiological dependence, particularly where the substance is alcohol, amphetamines, amphetamine-like substances, caffeine, cocaine, hallucinogens, inhalants, nicotine, opioids (such as cannabis, heroin and morphine), phencyclidine, phencyclidine-like compounds, sedative-hypnotics, benzodiazepines and/or other substances, particularly useful for treating withdrawal from the above substances and alcohol withdrawal delirium. In particular, the compounds according to the invention are also useful in the treatment or prevention of mood disorders induced particularly by alcohol, amphetamines, caffeine, cannabis, cocaine, hallucinogens, inhalants, nicotine, opioids, phencyclidine, sedatives, hypnotics, anxiolytics and other substances. In particular, the compounds according to the invention are also useful in the treatment or prevention of sexual dysfunction, including but not limited to sexual desire disorders; sexual arousal disorders; orgasmic disorders; sexual pain disorders; sexual dysfunction due to a general medical condition; substance-induced sexual dysfunction and sexual dysfunction not otherwise specified. In particular, the compounds according to the invention are also useful in the treatment or prevention of pain, including but not limited to traumatic pain such as postoperative pain; traumatic avulsion pain such as brachial plexus; chronic pain such as arthritic pain such as occurring in osteo-rheumatoid or psoriatic arthritis; neuropathic pain such as post-herpetic neuralgia, trigeminal neuralgia, segmental or intercostal neuralgia, fibromyalgia, causalgia, peripheral neuropathy, diabetic neuropathy, chemotherapy-induced neuropathy, AIDS related neuropathy, occipital neuralgia, geniculate neuralgia, glossopharyngeal neuralgia, reflex sympathetic dystrophy and phantom limb pain; various forms of headache such as migraine, acute or chronic tension headache, temporomandibular pain, maxillary sinus pain and cluster headache; odontalgia; cancer pain; visceral pain; gastrointestinal pain nerve entrapment pain; sport's injury pain; dysmennonrhoea; menstrual pain; meningitis; arachnoiditis; musculoskeletal pain; low back pain such as spinal stenosis, prolapsed disc, sciatica, angina, ankylosing spondyolitis; gout; burns; scar pain; itch; and thalamic pain such as post stroke thalamic pain. In particular, the compounds according to the invention are also useful in the treatment or prevention of the following other CNS-related conditions: akinesia, akinetic-rigid syndromes, dyskinesia and medication-induced parkinsonism, Gilles de la Tourette syndrome and its symptoms, tremor, chorea, myoclonus, tics and dystonia, attention-deficit/hyperactivity disorder (ADHD), Parkinson's disease, drug-induced Parkinsonism, post-encephalitic Parkinsonism, progressive supranuclear palsy, multiple system atrophy, corticobasal degeneration, parkinsonism-ALS dementia complex and basal ganglia calcification, behavioral disturbances and conduct disorders in dementia and the mentally retarded, including restlessness and agitation, extra-pyramidal movement disorders, Down's syndrome and Akathisia. In particular, the compounds according to the invention are also useful in the treatment or prevention of inflammation, including but not limited to inflammatory conditions in asthma, influenza, chronic bronchitis and rheumatoid arthritis; inflammatory conditions in the gastrointestinal tract such as, but not limited to Crohn's disease, ulcerative colitis, inflammatory bowel disease and non-steroidal anti-inflammatory drug induced damage; inflammatory conditions of the skin such as herpes and eczema; inflammatory conditions of the bladder such as cystitis and urge incontinence; and eye and dental inflammation. In particular, the compounds according to the invention are also useful in the treatment or prevention of allergic disorders, including but not limited to allergic disorders of the skin such as but not limited to urticaria; and allergic disorders of the airways such as but not limited to rhinitis. In particular, the compounds according to the invention are also useful in the treatment or prevention of emesis, i.e. nausea, retching and vomiting, including but not limited to acute emesis, delayed emesis and anticipatory emesis; emesis induced by drugs such as cancer chemotherapeutic agents such as alkylating agents, for example cyclophosphamide, carmustine, lomustine and chlorambucil; cytotoxic antibiotics, for example dactinomycin, doxorubicin, mitomycin-C and bleomycin; anti-metabolites, for example cytarabine, methotrexate and 5-fluorouracil; vinca alkaloids, for example etoposide, vinblastine and vincristine; and other drugs such as cisplatin, dacarbazine, procarbazine and hydroxyurea; and combinations thereof; radiation sickness; radiation therapy, such as in the treatment of cancer; poisons; toxins such as toxins caused by metabolic disorders or by infection, such as gastritis, or released during bacterial or viral gastrointestinal infection; pregnancy; vestibular disorders, such as motion sickness, vertigo, dizziness and Meniere's disease; post-operative sickness; gastrointestinal obstruction; reduced gastrointestinal motility; visceral pain, such as myocardial infarction or peritonitis; migraine; increased intracranial pressure; decreased intracranial pressure (such as altitude sickness); opioid analgesics, such as morphine; gastro-oesophageal reflux disease; acid indigestion; over-indulgence of food or drink; acid stomach; sour stomach; waterbrash/regurgitation; heartburn, such as episodic heartburn, nocturnal heartburn and meal induced heartburn; and dyspepsia. In particular, the compounds according to the invention are also useful in the treatment or prevention of gastrointestinal disorders, including but not limited to irritable bowel syndrome (IBS), skin disorders such as psoriasis, pruritis and sunburn; vasospastic diseases such as angina, vascular headache and Reynaud's disease, cerebral ischaemia such as cerebral vasospasm following subarachnoid haemorrhage; fibrosing and collagen diseases such as scleroderma and eosinophilic fascioliasis; disorders related to immune enhancement or suppression such as systemic lupus erythematosus and rheumatic diseases such as frositis; cough; and body weight control, including obesity. Most in particular, the compounds according to the invention are useful for the manufacture of a medicament for treating schizophrenia, emesis, anxiety, depression, irritable bowel syndrome (IBS), circadian rhythm disturbances, pain, neurogenic inflammation, asthma, micturition disorders such as urinary incontinence and nociception. The present invention also relates to a method for the treatment and/or prophylaxis of tachykinin-mediated diseases, in particular for the treatment and/or prophylaxis of schizophrenia, emesis, anxiety, depression, irritable bowel syndrome (IBS), circadian rhythm disturbances, pain, neurogenic inflammation, asthma, micturition disorders such as urinary incontinence and nociception comprising administering to a human in need of such administration an effective amount of a compound according to the invention, in particular according to Formula (I), the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof, the N-oxide form thereof, as well as the pro-drugs thereof. The invention also relates to a pharmaceutical composition comprising a pharmaceutically acceptable carrier and, as active ingredient, a therapeutically effective amount of a compound according to the invention, in particular a compound according to Formula (I), the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof, the N-oxide form thereof and a prodrug thereof. The compounds according to the invention, in particular the compounds according to Formula (I), the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof, the N-oxide form thereof and the prodrugs thereof, or any subgroup or combination thereof may be formulated into various pharmaceutical forms for administration purposes. As appropriate compositions there may be cited all compositions usually employed for systemically administering drugs. To prepare the pharmaceutical compositions of this invention, an effective amount of the particular compound, optionally in addition salt form, as the active ingredient is combined in intimate admixture with a pharmaceutically acceptable carrier, which carrier may take a wide variety of forms depending on the form of preparation desired for administration. These pharmaceutical compositions are desirable in unitary dosage form suitable, in particular, for administration orally, rectally, percutaneously, by parenteral injection or by inhalation. For example, in preparing the compositions in oral dosage form, any of the usual pharmaceutical media may be employed such as, for example, water, glycols, oils, alcohols and the like in the case of oral liquid preparations such as suspensions, syrups, elixirs, emulsions and solutions; or solid carriers such as starches, sugars, kaolin, diluents, lubricants, binders, disintegrating agents and the like in the case of powders, pills, capsules and tablets. Because of their ease in administration, tablets and capsules represent the most advantageous oral dosage unit forms in which case solid pharmaceutical carriers are obviously employed. For parenteral compositions, the carrier will usually comprise sterile water, at least in large part, though other ingredients, for example, to aid solubility, may be included. Injectable solutions, for example, may be prepared in which the carrier comprises saline solution, glucose solution or a mixture of saline and glucose solution. Injectable suspensions may also be prepared in which case appropriate liquid carriers, suspending agents and the like may be employed. Also included are solid form preparations that are intended to be converted, shortly before use, to liquid form preparations. In the compositions suitable for percutaneous administration, the carrier optionally comprises a penetration enhancing agent and/or a suitable wetting agent, optionally combined with suitable additives of any nature in minor proportions, which additives do not introduce a significant deleterious effect on the skin. Said additives may facilitate the administration to the skin and/or may be helpful for preparing the desired compositions. These compositions may be administered in various ways, e.g., as a transdermal patch, as a spot-on, as an ointment. It is especially advantageous to formulate the aforementioned pharmaceutical compositions in unit dosage form for ease of administration and uniformity of dosage. Unit dosage form as used herein refers to physically discrete units suitable as unitary dosages, each unit containing a predetermined quantity of active ingredient calculated to produce the desired therapeutic effect in association with the required pharmaceutical carrier. Examples of such unit dosage forms are tablets (including scored or coated tablets), capsules, pills, powder packets, wafers, suppositories, injectable solutions or suspensions and the like, and segregated multiples thereof. Since the compounds according to the invention are potent orally administrable NK1, NK1/NK3 and NK1/NK2/NK3-antagonists, pharmaceutical compositions comprising said compounds for administration orally are especially advantageous. Synthesis The compounds according to the invention can generally be prepared by a succession of steps, each of which is known to the skilled person. The final compounds of Formula (I) are conveniently prepared by reductively N-alkylating an intermediate compound of Formula (II) with an intermediate compound of Formula (III). Said reductive N-alkylation may be performed in a reaction-inert solvent such as, for example, dichloromethane, ethanol or toluene or a mixture thereof, and in the presence of an appropriate reducing agent such as, for example, a borohydride, e.g. sodium borohydride, sodium cyanoborohydride or triacetoxy borohydride. In case a borohydride is used as a reducing agent, it may be convenient to use a complex-forming agent such as, for example, titanium(IV)isopropylate as described in J. Org. Chem, 1990, 55, 2552-2554. Using said complex-forming agent may also result in an improved cisltrans ratio in favour of the trans isomer. It may also be convenient to use hydrogen as a reducing agent in combination with a suitable catalyst such as, for example, palladium-on-charcoal or platinum-on-charcoal. In case hydrogen is used as reducing agent, it may be advantageous to add a dehydrating agent to the reaction mixture such as, for example, aluminium tert-butoxide. In order to prevent the undesired further hydrogenation of certain functional groups in the reactants and the reaction products, it may also be advantageous to add an appropriate catalyst-poison to the reaction mixture, e.g., thiophene or quinoline-sulphur. Stirring and optionally elevated temperatures and/or pressure may enhance the rate of the reaction. In this and the following preparations, the reaction products may be isolated from the reaction medium and, if necessary, further purified according to methodologies generally known in the art such as, for example, extraction, crystallization, trituration and chromatography. Especially advantageous is the preparation of a final compound according to Formula (I) according to the previously mentioned reaction scheme in which the Alk-Y-Alk-L-moiety is benzyl, thus giving rise to a compound according to Formula (I) in which the Alk-Y-Alk-L-moiety is benzyl. Said final compound is pharmacologically active and can be converted into a final compound according to the invention in which the Alk-Y-Alk-L-moiety is hydrogen by reductive hydrogenation using e.g. hydrogen as a reducing agent in combination with a suitable catalyst such as, for example, palladium-on-charcoal or platinum-on-charcoal. The resulting final compound according to the invention can then be converted into other compounds according to Formula (I) by art-known transformations, e.g. acylation and alkylation. In particular, the final compounds of Formula (Ia) can be prepared by reacting a final compound of Formula (I′) with an intermediate compound of Formula (V) wherein W1 is an appropriate leaving group such as, for example, a halogen, e.g. chloro or bromo, or a sulfonyloxy leaving group, e.g. methanesulfonyloxy or benzene-sulfonyloxy. The reaction can be performed in a reaction-inert solvent such as, for example, a chlorinated hydrocarbon, e.g. dichloromethane or a ketone, e.g. methyl isobutylketone, and in the presence of a suitable base such as, for example, sodium carbonate, sodium hydrogen carbonate or triethylamine. Stirring may enhance the rate of the reaction. The reaction may conveniently be carried out at a temperature ranging between room temperature and reflux temperature. Alternatively, the final compounds of Formula (Ia) can also be prepared by reacting a final compound of Formula (I′) with a carboxylic acid of Formula (VI). The reaction can be performed in a reaction-inert solvent such as, for example, a chlorinated hydrocarbon, e.g. dichlorometbane, in the presence of a suitable base such as, for example, sodium carbonate, sodium hydrogen carbonate or triethylamine and in the presence of an activator, such as e.g. DCC (dicyclohexylcarbodiimide), CDI (carbonyldiimidazol) and EDCI (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide.HCl). Stirring may enhance the rate of the reaction. The reaction may conveniently be carried out at a temperature ranging between room temperature and reflux temperature. In particular, the final compounds of Formula (Ib) can be prepared by reacting a final compound of Formula (I′) with a compound of Formula (VII) wherein W2 is an appropriate leaving group such as, for example, a halogen, e.g. chloro or bromo, or a sulfonyloxy leaving group, e.g. methanesulfonyloxy or benzenesulfonyloxy. The reaction can be performed in a reaction-inert solvent such as, for example, a chlorinated hydrocarbon, e.g. dichloromethane, an alcohol, e.g. ethanol, or a ketone, e.g. methyl isobutylketone, and in the presence of a suitable base such as, for example, sodium carbonate, sodium hydrogen carbonate or triethylamine. Stirring may enhance the rate of the reaction. The reaction may conveniently be carried out at a temperature ranging between room temperature and reflux temperature. The final compounds of Formula (Ic) and Formula (Id) can be prepared either by reductive amination or alkylation of a final compound of Formula (I′) with either a compound of Formula (VIII) or (IX) wherein W3 in Formula (VIII) is an appropriate leaving group such as, for example, a halogen, e.g. chloro or bromo, or a sulfonyloxy leaving group, e.g. methanesulfonyloxy or benzenesulfonyloxy and wherein —CH2-Alk in Formula (Id) is Alk. The reaction can be performed in a reaction-inert solvent such as, for example, a chlorinated hydrocarbon, e.g. dichloromethane, an alcohol, e.g. ethanol, or a ketone, e.g. methyl isobutylketone, and in the presence of a suitable base such as, for example, sodium carbonate, sodium hydrogen carbonate or triethylamine. Stirring may enhance the rate of the reaction. The reaction may conveniently be carried out at a temperature ranging between room temperature and reflux temperature. The starting materials and some of the intermediates are known compounds and are commercially available or may be prepared according to conventional reaction procedures generally known in the art. For example, intermediate compounds of Formula (II) may be prepared by reductively N-alkylating an intermediate compound of Formula (XI) with an intermediate compound of Formula (II) in which W4 is a benzyl radical, after which the resulting compound is subsequently reduced to yield an intermediate compound according to Formula (II). Said reductive N-alkylation may be performed in a reaction-inert solvent such as, for example, dichloromethane, ethanol, toluene or a mixture thereof, and in the presence of an appropriate reducing agent such as, for example, a borohydride, e.g. sodium borohydride, sodium cyanoborohydride or triacetoxy borohydride. In case a borohydride is used as a reducing agent, it may be convenient to use a complex-forming agent such as, for example, titanium(IV)iso-propylate as described in J. Org. Chem, 1990, 55, 2552-2554. Using said complex-forming agent may also result in an improved cisltrans ratio in favour of the trans isomer. It may also be convenient to use hydrogen as a reducing agent in combination with a suitable catalyst such as, for example, palladium-on-charcoal or platinum-on-charcoal. In case hydrogen is used as reducing agent, it may be advantageous to add a dehydrating agent to the reaction mixture such as, for example, aluminium tert-butoxide. In order to prevent the undesired further hydrogenation of certain functional groups in the reactants and the reaction products, it may also be advantageous to add an appropriate catalyst-poison to the reaction mixture, e.g., thiophene or quinoline-sulphur. Stirring and optionally elevated temperatures and/or pressure may enhance the rate of the reaction. The preparation of intermediate compounds (XI) and (XII) and other intermediates is described in WO 97/16440-A1, published May 9, 1997 by Janssen Pharmaceutica N.V, which is disclosed herein by reference as well as in other publications mentioned in WO 97/16440-A1, such as, e.g. EP-0,532,456-A. The following examples are intended to illustrate but not to limit the scope of the present invention. Experimental Part Hereinafter “RT” means room temperature, “THF” means tetrahydrofuran, “DIPE” means diisopropylether, “DCM” means dichloromethane, “DMF” means N,N-dimethylformamide, “MIK” means methyl isobutyl keton, “EDCT”, means 1-ethyl-3-(3′-dimethylaminopropyl)carbodiimide, and “HOBT” means 1-Hydroxy-1H-benzotriazole. A. Preparation of the Intermediate Compounds EXAMPLE A1 a. Preparation of Intermediate Compound 1 Et3N (0.55 mol) was added to a stirring mixture of 7-(phenylmethyl)-1,4-dioxa-8-azaspiro[4.5]decane (0.5 mol) in toluene (1500 ml). 3,5-Bis(trifluoromethyl)benzoyl chloride (0.5 mol) was added over a 1-hour period (exothermic reaction). The mixture was stirred at room temperature for 2 hours, then allowed to stand for the weekend and washed three times with water (500 ml, 2×250 ml). The organic layer was separated, dried, filtered and the solvent was evaporated. Yield: 245 g (100%). Part of this fraction was crystallized from petroleum ether. The precipitate was filtered off and dried. Yield: 1.06 g of intermediate compound 1. b1. Preparation of Intermediate Compound 2 HCl cp (300 ml) was added to a mixture of intermediate compound 1 (0.5 mol) in ethanol (300 ml) and H2O (300 ml). The reaction mixture was stirred at 60° C. for 20 hours. The precipitate was filtered off, ground, stirred in H2O, filtered off, washed with petroleum ether and dried. Yield: 192 g of intermediate compound 2 ((±)-1-[3,5-bis(trifluoromethyl)benzoyl]-2-(phenylmethyl)-4-piperidinone) (89.4%) (mixture of R and S enantiomers). b2. Preparation of Intermediate Compound 9 and Intermediate Compound 10. Intermediate compound 2 was separated into its optical isomers by chiral column chromatography over Chiralpak (CHIRALPAK AS 1000 Å 20 mm (DAICEL); eluent: hexane/2-propanol 70/30). Two product fractions were collected and each solvent was evaporated. Yield Fraction 1: 32.6 g of intermediate compound 9 (R) and Fraction 2: 30.4 g of intermediate compound 10 (S). c. Preparation of Intermediate Compound 3 A mixture of intermediate compound 2 (0.046 mol), 1-phenylmethyl)piperazine (0.051 mol) and Ti-tetraisopropyloxide (0.056 mol) was stirred for 2 hours at 40° C. The reaction mixture was cooled to room temperature. Ethanol, p.a. (350 ml) was added. NaBH4 (0.138 mol) was added. The resulting reaction mixture was stirred for one hour at room temperature, then for one hour at 50° C. More NaBH4 (5.2 g) was added and the reaction mixture was stirred for 2 hours at 50° C. Again, NaBH4 was added and the reaction mixture was stirred overnight at room temperature, then for 2 hours at 50° C. Water (10 ml) was added The mixture was stirred for 15 min. CH2Cl2 (200 ml) was added and the mixture was stirred for 15 min. The organic phase was separated, dried (MgSO4), dicalite was added, the mixture was filtered over dicalite, and the filtrate was evaporated. This fraction was separated into (CIS) and (TRANS) by column chromatography over silica gel. The desired (TRANS)-fractions were collected and the solvent was evaporated, giving 14.8 g of residue ((I), 1.06% (CIS)) and 4.9 g of residue ((II), 6% (CIS)). Resolution and purification of those (TRANS)-fractions (±20 g in total) was obtained by chromatography over stationary phase Chiralcel OD (1900 Gr) in Psuchrom LC110 35 bar (eluent: hexane/ethanol 90/10). The desired fractions were collected and the solvent was evaporated. Yield: 9.5 g of intermediate compound 3 (2R-trans)-1-[3,5-bis(trifluoromethyl)benzoyl]-2-phenylmethyl)-4-[4-(phenylmethyl)-1-piperazinyl]piperidine. d. Preparation of Intermediate Compound 4 A solution of intermediate compound 3 (0.288 mol) in methanol (700 ml) was hydrogenated at 40° C. with Pd/C, 10% (5 g) as a catalysl After uptake of H2 (1 equiv), the catalyst was filtered off and the filtrate was evaporated. Yielding 141.2 g of intermediate compound 4 (+-(2R-trans)-1-[3,5-bis(trifluoromethyl)benzoyl]-2-(phenylmethyl)-4-(1-piperazinyl)piperidine. EXAMPLE A2 a. Preparation of Intermediate Compound 5 NaH (0.086 mol) was added portionwise to a solution of 3-thiophene ethanol (0.078 mol) in THF at 5° C. under N2 flow. The mixture was stirred for 1 hour at 5° C. Bu4NI (0.001 mol) and (bromomethyl)benzene (0.080 mol) were added. The mixture was stirred at room temperature for 3 hours, taken up in H2O and extracted with AcOEt. The organic layer was separated, dried (MgSO4) and solvent was evaporated. The concentrate 1 (18 g) was purified by column chromatography over silica gel (gradient eluent: Cyclohexane/AcOEt 100/0 to 80/20). The pure fractions were collected and the solvent was evaporated. Yield. 9.9 g intermediate compound 5 (58%). b. Preparation of Intermediate Compound 6 To a solution of intermediate compound 16 (0.023 mol) in THF (50 ml) at −50° C., BuLi[1.6M] (0.025 mol) was added portionwise under N2 flow. The temperature was raised slowly to 0° C. The mixture was stirred at 0° C. for 1 hour and cooled to −40° C. A solution of SO2Cl2 (0.046 mol) in pentane (50 ml) was added at −40° C. The mixture was stirred at −40° C. for 1 hour. The concentrate was hydrolyzed, extracted with AcOEt, washed with a saturated solution of NaCl, dried over MgSO4 and concentrated, providing 9 g. The concentrate was purified by column chromatography over silica gel (gradient eluent: Cyclohexane/AcOEt 100/0 to 80/20). Yield 1.2 g of intermediate compound 6 (16%). EXAMPLE A3 a. Preparation of Intermediate Compound 7 NaH (60% in oil) (0.086 mol, 3.4 g) was added portionwise to a solution of 2-2-thienyl)ethanol (0.078 mol, 10 g) in THF (150 ml) under N2 flow at 5° C. The mixture was stirred at 5° C. during 1 hour. Tetrabutylammonium iodide (0.001 mol, 0.3 g) and then (bromomethyl)benzene (0.080 mol, 9.5 ml) were added to the solution. The mixture was stirred at room temperature during 3 hours, poured into water, extracted with ethyl acetate, dried over MgSO4 and concentrated. The crude product (18 g) was purified by column chromatography over silica gel (gradient eluent: CH2Cl2/Cyclohexane 0/100 to 20/80) and the product fractions were concentrated. Yield: 11.4 g of intermediate compound 7 (66%). b. Preparation of Intermediate Compound 8 n-BuLi (1.6 M) (0.015 mol, 9.45 ml) was added slowly to a solution of intermediate compound 7 (0.014 mol, 3 g) in THF (30 ml) under N2 flow at −40° C. The reaction was allowed to warm up slowly to 0° C. and cooled to −70° C. Dry ice (˜2 g) was added. The temperature was slowly allowed to rise to room temperature. NaOH (1 mol per liter, 30 ml) was added, the mixture was washed with diethyl ether. The aqueous layer was acidified with HCl (1N) and extracted with CH2Cl2. The organic layer was dried over MgSO4 and concentrated. Yield. 2.6 g of intermediate compound 8 (71%). B. Preparation of the Final Compounds EXAMPLE B1 a) Preparation of Final Compound 1 A mixture of intermediate compound 4 (0.005 mol), 1-phenylmethyl)-3-piperidinone (0.005 mol) and potassium acetate in methanol (150 ml) was hydrogenated at 50° C. with Pd/C 10% (1 g) as a catalyst in the presence of thiophene solution (1 ml). After uptake of H2 (1 equiv.), the catalyst was filtered off and the filtrate was concentrated. The residue was purified by flash column chromatography over silica gel (eluent: CH2Cl2/(MeOH/N3) 95/5). The product fractions were collected and the solvent was evaporated. Yield: 2.5 g of final compound 1 (74%). b) Preparation of Final Compound 2 A solution of final compound 1 (prepared according to B1.a) (0.09 mol) in methanol (500 ml) was hydrogenated at 50° C. with Pd/C 10% (5 g) as a catalyst. After uptake of H2 (1 equiv.), the catalyst was filtered off and the filtrate was concentrated. The residue was purified by column chromatography over silica gel (eluent: CH2C2/(MeOH/NH3) 85/15). The product fractions were collected and the solvent was evaporated. Yield: 41.3 g of final compound 2 (78.7%). c) Preparation of Final Compounds 105 and 71 Bis(1,1-dimethylethyl)dicarbonic acid ester (0.008 mol) was added to a solution of final compound 2 (prepared according to B1.b) (0.007 mol) in CH2Cl2, p.a (100 ml) and the reaction mixture was stirred for 6 hours at room temperature. The solvent was evaporated and the dry residue was filtered over silica gel (eluent: CH2Cl2/CH3OH 95/5). The product fractions were collected and the solvent was evaporated. The obtained residue was separated by Chiral separation on AD column (eluent: hexane/EtOH 95/5). Two product fractions were collected and their solvent was evaporated. Each residue was purified on a glass filter (gradient eluent: CH2Cl2/CH3OH 100/0-90/10), then the desired products were collected and their solvent was evaporated. Yield fraction 1: 1.2 g of final compound 105 ([2R-[2α,4β(R*)]]). Yield fraction 2: 0.75 g of final compound 71 ([2R-[2α,4β(S*)]]). d) Preparation of Final Compound 108 HCl/2-propanol (5 ml) was added to a solution of final compound 105 (prepared according to B1.c) (0.00175 mol) in 2-propanol (50 ml). The reaction mixture was stirred and refluxed for 90 minutes. The solvent was evaporated and the residue was suspended in DIPE. The resulting precipitate was filtered off and taken up in H2O. The mixture was alkalised with a NaOH solution and extracted with CH2Cl2. The organic layer was washed with water, dried (MgSO4), filtered off and the solvent was evaporated. Finally, the desired product was dried. Yield: 0.550 g of final compound 108 (54%) (2R-[2α,4β(R*)]). EXAMPLE B2 Preparation of Final Compound 26 Final compound 2 (prepared according to B1b) (0.007 mol) was dissolved in MIK (50 ml). Chloropyrazine (0.11 g) and Na2CO3 (0.5 g) were added. The mixture was stirred and refluxed for 44 hours, then washed with water, dried and the solvent was evaporated. The residue was purified by column chromatography over silica gel (eluent: CH2Cl2/MeOH 90/10). The product fractions were collected and the solvent was evaporated. Yield: 54 mg of final compound 26. EXAMPLE B3 Preparation of Final Compound 49 Final compound 2 (prepared according to B1b) (0.0007 mol) was dissolved in CH2Cl2 (20 ml). Benzenemethanesulfonyl chloride (0.0008 mol) was added. The reaction mixture was stirred. Then Na2CO3 (0.5 g) was added and the mixture was stirred for 3 hours. The reaction mixture was purified by column chromatography over silicagel (eluent CH2Cl2/MeOH 95/5). The desired fractions were collected and the solvent evaporated. The residue was dried. Yield. 0.237 g of final compound 49. EXAMPLE B4 Preparation of Final Compound 41 Cyclopentanecarbonyl chloride (0.0008 mol) was added to a solution of final compound 2 (prepared according to B1.b) (0.0007 mol) in CH2Cl2 (20 ml) and the mixture was stirred, then Na2CO3 (0.005 mol) was added and the reaction mixture was stirred overnight at room temperature. The mixture was purified by column chromatography over silica gel (gradient eluent: CH2Cl2/CH3OH 100/0-90/10). The product fractions were collected, the solvent was evaporated and the residue was dried. Yield: 0.296 g of final compound 41. EXAMPLE B5 Preparation of Final Compound 17 1,1′-Carbonylbis-1H-imidazole (0.0025 mol) was added to a solution of 3-furancarboxylic acid (0.0025 mol) in CH2Cl2 (50 ml) and the mixture was stirred for 2 hours at room temperature. Final compound 2 (prepared according to B1.b) (0.002 mol) was added and the reaction mixture was stirred for 18 hours at room temperature. The mixture was washed with a diluted NaOH solution and with water, dried and the solvent was evaporated. The residue was purified by column chromatography over silica gel (gradient eluent: CH2Cl2/CH3OH 98/2-90/10). The product fractions were collected, the solvent was evaporated and the residue was dried. Yield: 0.915 g of final compound 17. EXAMPLE B6 Preparation of Final Compound 24 and 21 A mixture of α-oxo-2-furanacetic acid (0.001 mol) and 1,1′-carbonylbis-1H-imidazole (0.0011 mol) in CH2Cl2 (50 ml) was stirred for 4 hours at room temperature, then final compound 2 (prepared according to B1.b) (0.001 mol) was added and the reaction mixture was stirred overnight. The mixture was washed for 30 min. with a diluted NaOH solution and with water, dried and the solvent was evaporated. The residue was purified by column chromatography (gradient eluent: CH2Cl2/CH3OH 98/2-90/10). Two product fractions were collected, their solvent was evaporated and each residue was dried. Yield fraction 1: 0.120 g of compound 24 and yield fraction 2: 0.147 g of compound 21. EXAMPLE B7 Preparation of Final Compound 54 Et3N (0.0051 mol) was added to a mixture of (2S)-1-(1,1-dimethylethyl)-1,2-pyrrolidinedicarboxylic acid ester (0.0028 mol), N′-(ethylcarbonimidoyl)-N,N-dimethyl-1,3-propanediamine (0.0038 mol) and final compound 2 (prepared according to B1.b) (0.0025 mol) in CH2Cl2, p.a (50 ml). The reaction mixture was stirred at room temperature for 1.5 hours and was left to stand overnight. The solution was washed with NaOH (0.3N); the organic layer was separated, dried MgSO4), filtered off and the solvent was evaporated The residue was purified by column chromatography over silica gel (gradient eluent: CH2Cl2/CH3OH from 100/0 to 90/10). The product fractions were collected, the solvent was evaporated and the residue was dried (vacuum) at 50° C. for 2 days. Yield. 1.01 g of final compound 54 (52%). EXAMPLE B8 Preparation of Final Compound 67 EDCI (0.001 mol) was added portionwise to a solution of final compound 2 (prepared according to B1.b) (0.001 mol), 4-hydroxybenzoic acid (0.001 mol), HOBT (0.001 mol) and Et3N (0.001 mol) in CH2Cl2 (5 ml). The mixture was stirred at room temperature for 8 hours then washed with H2O. The organic layer was separated, dried (MgSO4), filtered, and the solvent was evaporated. The residue (0.5 g) was purified by column chromatography over silica gel (eluent: CH2Cl2/CH3OH/NH4OH 96/4/0.1). The pure fractions were collected and the solvent was evaporated. The residue was crystallized from diethyl ether. The precipitate was filtered off and dried. Yield: 0.14 g of final compound 67 (23%). EXAMPLE B9 Preparation of Final Compound 66 2-Isocyanatopropane (0.0007 mol) was added at room temperature to a mixture of final compound 2 (prepared according to B1.b) (0.0006 mol) in THF (5 ml). The mixture was stirred at room temperature for 2 hours. H2O was added. The mixture was extracted with CH2Cl2. The organic layer was separated, dried (MgSO4), filtered, and the solvent was evaporated. The residue (0.4 g) was purified by column chromatography over kromasil (eluent: CH2Cl2/CH3OH/OH 95/5/0.1). The pure fractions were collected and the solvent was evaporated. Yield: 0.2 g of compound 66 (43%). EXAMPLE B10 a. Preparation of Final Compound 77 A mixture of final compound 2 (prepared according to B1.b) (0.001 mol), 2-thienylboronic acid (0.001 mol) and 1,4-dioxane-2,5-diol (0.001 mol) in ethanol (5 ml) was stirred at room temperature for 18 hours. The solvent was evaporated till dryness. The residue was dissolved in CH2Cl2. The organic layer was washed with K2CO3 10%, dried (MgSO4), filtered and the solvent was evaporated. The residue (0.6 g) was purified by column chromatography over silica gel (eluent: CH2Cl2/CH3OH/NH4OH 97/3/0.5). The pure fractions were collected and the solvent was evaporated. Yield: 0.13 g of final compound 77 (21%). b. Preparation of Final Compound 124 Acetic anhydride (0.003 ml, 0.301 mmol) was added to a mixture of final compound 89 (prepared according to B10.a) (0.185 g, 0.251 mmol) and dimethylaminopyridine (0.05 g, 0.376 mmol) in CH2Cl2 (2 ml) at room temperature. The mixture was stirred at room temperature for 1 hour, poured in K2CO3 10%, extracted with CH2Cl2, dried over MgSO4, filtered and concentrated under vacuum. The residue was purified by column chromatography over silica gel (eluent: CH2Cl2/MeOH/NH4OH 97/3/0.3). The pure fractions were collected and the solvent evaporated. Yield: 0.147 g of final compound 124 (75%). EXAMPLE B11 Preparation of Final Compound 91 A mixture of dimethyl-N-cyanodithioiminocarbonate (1 g; 6.8 mmol) and isopropylamine (0.6 ml; 6.8 mmol) in 10 ml of acetonitrile was heated under reflux for 5 hours. After cooling the solution to −10° C., final compound 2 (prepared according to B1.b) (3.87 g; 6.8 mmol) and a 3N NaOH solution (2.3 ml; 6.8 mmol) were consecutively added. The mixture was stirred for 5 minutes and silver nitrate (1.16 g; 6.8 mmol) in acetonitrile (5 ml) was added dropwise. The reaction mixture was stirred at 0° C. for 2 hours then at room temperature for 2 hours. The reaction mixture was filtered and the residue washed with acetonitrile. The solvent was evaporated and the residue was purified by column chromatography over silica gel (eluent: CH2Cl2/MeOH/NH4OH 95/5/0.5). The pure fractions were collected and the solvent evaporated. Yield: 0.96 g of final compound 91 (21%). EXAMPLE B12 Preparation of Final Compound 103 A mixture of 1,1-bis(methylthio)-2-nitroethylene (0.30 g; 1.8 mmol) and isopropylamine (0.16 ml; 1.8 mmol) in acetonitrile (5 ml) was heated under reflux overnight. After cooling the solution to −10° C., final compound 2 (prepared according to B1.b) (0.529 g; 0.9 mmol) and a 3N sodium hydroxide solution (0.9 ml; 0.9 mmol) were consecutively added. The mixture was stirred for 5 minutes and a solution of silver nitrate (0.16 g; 0.9 mmol) in acetonitrile (5 ml) was added dropwise. The reaction mixture was stirred at 0° C. for 2 hours then at room temperature overnight. The solution was filtered and the residue washed with acetonitrile. The solvent was evaporated and the residue was purified by column chromatography over silica gel (Kromasil 10 μm, eluent: CH2Cl2/MeOH/NH4OH 96/4/0.1). The pure fractions were collected and evaporated. Yield. 0.217 g of final compound 103 (34%). EXAMPLE B13 a. Preparation of Final Compound 83 Intermediate compound 6 (prepared according to A2.b) (0.002 mol. 055 g) was added portionwise to a solution of final compound 2 (prepared according to B1.b) (0.002 mol, 1.0 g) in dichloromethane at room temperature. The mixture was stirred at room temperature during 18 hours, washed with K2CO3 10%, dried over MgSO4 and concentrated. The crude product (1.6 g) was purified by column chromatography over silica gel (Kromasil 10 μm, eluent: CH2Cl2/MeOH/NH4OH 99/1/0.2). The pure fractions were collected and evaporated. Yield: 1. 19 g of final compound 83 (77%). b. Preparation of Final Compound 96 Boron tribromide (1M in CH2Cl2) (0.009 mol, 5.2 ml) was slowly added to a solution of final compound 83 (prepared according to B13.a) (0.001 mol, 0.9 g) in dichloromethane (10 ml) at −70° C. under N2 flow. The temperature of the reaction was allowed to rise slowly to −50° C. and the mixture was stirred at −50° C. for 1 hour. The mixture was hydrolyzed with K2CO3 10%, extracted with dichloromethane, dried over MgSO4 and concentrated. The crude product (0.65 g) was purified by column chromatography over silica gel (Kromasil 10 μm, gradient eluent CH2Cl2/MeOH OH 96/4/0.1 to 92/8/0.5). The pure fractions were collected and evaporated Yield: 0.11 g of final compound 96 (14%). EXAMPLE B14 a. Preparation of Final Compound 93 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (0.002 mol, 0.32 g) was added portionwise to a solution of final compound 2 (prepared according to B1.b) (0.002 mol, 1 g), intermediate compound 8 (prepared according to A3.b) (0.002 mol, 0.54 g), 1-hydroxybenzotriazole (0.002 mol, 0.28 g) and triethylamine (0.003 mol, 0.36 ml) in dichloromethane (10 ml) at room temperature. The mixture was stirred at room temperature during 18 hours, then washed with K2CO3 10%, dried over MgSO4 and concentrated. The crude product was purified by column chromatography over silica gel (Kromasil 10 μm, eluent: CH2Cl2/MeOH/NH4OH 97/3/0.1). The pure fractions were collected and evaporated. Yield: 1.07 g of final compound 93 (65%). b. Preparation of Final Compound 98 The same procedure as described in Example B13.b but instead of the use of final compound 83 (prepared according to B13.a), final compound 93 (prepared according to B14.a) was used. EXAMPLE B15 Preparation of Final Compound 3 3,5-Dimethylbenzoylchloride (0.00309 mol) was added to a solution of final compound 2 (prepared according to B1.b) (0.00257 mol), Et3N p.a. (0.0035 mol) and N,N-dimethyl-4-pyridinamine (0.01 g) in CH2Cl2 p.a (10 ml) at room temperature and the mixture was stirred overnight. The reaction mixture was partitioned between H2O and CH2Cl2. The separated organic layer was washed with H2O, dried and was concentrated. The residue was purified by column chromatography over silica gel (eluent: CH2Cl2/MeOH 95/5). The product fractions were collected and the solvent was evaporated. This fraction (pale yellow oil) was purified again by column chromatography over silica gel (eluent: CH2Cl2/MeOH 98/2). The product fractions were collected and the solvent was evaporated. Yield: 1.75 g. This fraction was washed with a NaOH-solution and H2O, then dried and the solvent was evaporated. Yield. 1.3 g of final compound 3. EXAMPLE B16 Preparation of Final Compound 78 BBr3 (0.005 mol) was added slowly at −70° C. to a solution of final compound 72 (prepared according to B3) (0.001 mol) in CH2Cl2 (10 ml). The mixture was cooled slowly to room temperature then stirred for 18 hours. H2O was added. The mixture was basified with NH4OH and extracted with CH2Cl2. The organic layer was separated, dried (MgSO4), filtered, and the solvent was evaporated. The residue (0.8 g) was purified by column chromatography over silica gel (eluent: CH2Cl2/CH3OH/NH4OH 97/3/0.1). The pure fractions were collected and the solvent was evaporated. Yield: 0.497 g of final compound 78 (63%). The compounds exemplified in the following Tables 1 and 2 were prepared in a manner analogous to one of the foregoing examples. TABLE 1 Co. Nr. Exp. Nr. Alka Y Alkb L Stereo descriptors 2 B1.b cb cb cb H 2R-trans 108 B1.d cb cb cb H [2R[2α,4β(R*)]] 109 B1.d cb cb cb H [2R[2α,4β(S*)]] 4 B1.b cb cb cb H cis: (E)-2-butene- dioate(1:2) 26 B2 cb cb cb 2R-trans 1 B1.a —CH2— cb cb 2R-trans 6 B1.a —CH2— cb cb cis 5′ B1.a —CH2— cb cb cis; (E)-2-butene-di- oate(1:2) 77 B10.a cb cb 2R-trans 76 B10.a cb cb 2R-trans 79 B10.a cb cb 2R-trans 89 B10.a cb cb 2R-trans 106 B10.a cb cb 2R-trans 124 B10.b cb cb 2R-trans 66 B11 cb C═O cb 2R-trans 65 B11 cb C═O cb 2R-trans 74 B11 cb C═O cb 2R-trans 105 B1.c cb C═O cb [2R-[2α,4β(R*)]] 71 B1.c cb C═O cb [2R-[2α,4β(S*)]] 24 B6 cb C═O cb 2R-trans 51 B4 cb C═O cb [2R-[2α,4β(R*)]] 52 B4 cb C═O cb [2R-[2α,4β(S*)]] 15 B4 cb C═O cb 2R-trans 14 B5 cb C═O cb 2R-trans 61 B8 cb C═O cb 2R-trans 41 B4 cb C═O cb 2R-trans 60 B7 cb C═O cb 2R-trans 53 B7 cb C═O cb 2R-trans 54 B7 cb C═O cb 2R-trans 16 B5 cb C═O cb 2R-trans 17 B5 cb C═O cb 2R-trans 18 B4 cb C═O cb 2R-trans 19 B5 cb C═O cb 2R-trans 20 B4 cb C═O cb 2R-trans 98 B14.b cb C═O cb 2R-trans 93 B14.a cb C═O cb 2R-trans 100 B14.b cb C═O cb 2R-trans 85 B14.a cb C═O cb 2R-trans 99 B14.a cb C═O cb 2R-trans 97 B14.b cb C═O cb 2R-trans 101 B14.b cb C═O cb 2R-trans 88 B14.a cb C═O cb 2R-trans 102 B14.a cb C═O cb 2R-trans 21 B6 cb C═O cb 2R-trans 42 B4 cb C═O cb 2R-trans 63 B8 cb C═O cb 2R-trans 22 B4 cb C═O cb 2R-trans 23 B4 cb C═O cb 2R-trans 8 B4 cb C═O cb 2R-trans 11 B4 cb C═O cb 2R-trans 82 B8 cb C═O cb 2R-trans 75 B8 cb C═O cb 2R-trans 9 B4 cb C═O cb 2R-trans 10 B4 cb C═O cb 2R-trans 47 B4 cb C═O cb 2R-trans 57 B5 cb C═O cb 2R-trans 70 B8 cb C═O cb 2R-trans 62 B5 cb C═O cb 2R-trans 67 B8 cb C═O cb 2R-trans 64 B4 cb C═O cb 2R-trans 12 B4 cb C═O cb 2R-trans 3 B4 cb C═O cb 2R-trans 13 B15 cb C═O cb 2R-cis; (E)-2-butene- dioate(1:2) 43 B4 cb C═O 2R-trans 48 B4 cb C═O 2R-trans 56 B8 cb C═O 2R-trans 35 B3 cb cb 2R-trans 25 B3 cb cb 2R-trans 55 B3 cb cb [2R-[2α,4β(R*)]] 59 B3 cb cb [2R-[2α,4β(S*)]] 36 B3 cb cb 2R-trans 38 B3 cb cb 2R-trans 92 B13.b cb cb 2R-trans 86 B13.b cb cb 2R-trans 87 B13.a cb cb 2R-trans 95 B13.a cb cb 2R-trans 34 B3 cb cb 2R-trans 37 B3 cb cb 2R-trans 84 B13.a cb cb 2R-trans 96 B13.b cb cb 2R-trans 83 B13.a cb cb 2R-trans 90 B13.a cb cb 2R-trans 29 B3 cb cb 2R-trans 104 B13.a cb cb 2R-trans 33 B3 cb cb 2R-trans 40 B3 cb cb 2R-trans 32 B3 cb cb 2R-trans 39 B3 cb cb 2R-trans 44 B3 cb cb 2R-trans 28 B3 cb cb 2R-trans 30 B3 cb cb 2R-trans 27 B3 cb cb 2R-trans 50 B3 cb cb 2R-trans 81 B16 cb cb 2R-trans 68 B3 cb cb 2R-trans 31 B3 cb cb 2R-trans 80 B16 cb cb 2R-trans 69 B3 cb cb 2R-trans 107 B16 cb cb 2R-trans 7 B3 cb cb 2R-trans 78 B16 cb cb 2R-trans 73 B13.b cb cb 2R-trans 72 B3 cb cb 2R-trans 58 B13.a cb cb 2R-trans 45 B3 cb cb 2R-trans 46 B3 cb cb 2R-trans 49 B3 cb 2R-trans 91 B11 cb C═N—CN cb 2R-trans 94 B11 cb C═N—CN cb 2R-trans 103 B12 cb C═CH—NO2 cb 2R-trans cb: covalent bond TABLE 2 Co. Nr. Exp. Nr. Alka Y Alkb L Stereo descriptors 113 B2 cb cb cb H 2R-cis 117 B2 cb cb cb H 2R-trans 123 B2 cb cb cb H 2R-trans + 2R-cis 110 B1 —CH2— cb cb 2R-cis 111 B1 —CH2— cb cb 2R-trans 114 B4 cb C═O cb 2R-cis 121 B5 cb C═O cb 2R-cis 115 B5 cb C═O cb 2R-trans 112 B5 cb C═O cb 2R-cis 116 B5 cb C═O cb 2R-trans 119 B4 cb C═O cb 2R-cis 118 B4 cb C═O cb 2R-trans 120 B3 cb cb 2R-cis 122 B3 cb cb 2R-trans cb = covalent bond C. Analytical Data For a number of compounds, either melting points, LCMS data or optical rotations were recorded. 1. Melting Points If possible, melting points (or ranges) were obtained with a Leica VMHB Koffler bank. The melting points are uncorrected. TABLE 3 Melting points for selected compounds. Compound no. Result (° C.) 56 83° C. 61 104° C. 62 114° C. 63 110° C. 65 94° C. 66 97° C. 67 150° C. 2. LCMS Conditions Method A The HPLC gradient was supplied by a Waters Alliance HT 2790 system (Waters, Milford, Mass.) with a columnheater set at 40° C. Flow from the column was split to a Waters 996 photodiode array (PDA) detector and a Waters-Micromass ZQ mass spectrometer with an electrospray ionization source operated in positive and negative ionization mode. Reversed phase HPLC was carried out on a Xterra MS C18 column (3.5 mm, 4.6×100 mm) with a flow rate of 1.6 ml/min. Three mobile phases (mobile phase A: 95% 25 mM ammonium acetate +5% acetonitrile; mobile phase B: acetonitrile; mobile phase C: methanol) were employed to run a gradient condition from 100% A to 50% B and 50% C in 6.5 min., to 100% B in 1 min, 100% B for 1 min. and re-equilibrate with 100% A for 1.5 min. An injection volume of 10 μL was used. Mass spectra were acquired by scanning from 100 to 1000 in 1 s using a dwell time of 0.1 s. The capillary needle voltage was 3 kV and the source temperature was maintained at 140° C. Nitrogen was used as the nebulizer gas. Cone voltage was 10 V for positive ionization mode and 20 V for negative ionization mode. Data acquisition was performed with a Waters-Micromass MassLynx-Openlynx data system. TABLE 4 LCMS parent peak and retention time for selected compounds. Compound LCMS MS(MH+) Retention no. Meth. A time 1 673 6.36 2 583 5.09 3 715 6.34 4 583 5.24 6 673 6.55 8 687 6.02 9 705 6.01 10 721 6.12 11 701 6.14 12 723 6.05 13 715 6.5 14 665 5.93 15 651 5.84 16 681 5.67 17 677 5.82 18 677 5.86 19 691 5.96 20 693 5.99 21 677 5.6 22 709 5.86 23 688 5.61 24 705 5.78 25 729 6.49 26 651 6.01 27 757 6.26 28 723 6.14 29 729 6.44 30 737 6.08 31 767 6.18 32 741 5.63 33 757 6.38 34 806 6.69 35 689 5.94 36 763 6.68 37 796 6.48 38 758 6.51 39 742 6.5 40 761 6.43 41 679 6.58 42 705 6.2 43 707 6.39 44 803 6.57 45 765 6.51 46 803 6.52 47 717 6.36 48 715 6.61 49 737 6.49 50 791 6.66 51 651 6.20 52 651 6.22 53 780 6.11 54 780 6.10 55 729 5.82 57 712 6.23 58 843 6.50 59 729 5.83 60 722 5.55 64 755 6.26 72 753 6.16 73 753 5.78 74 727 5.90 76 709 6.06 77 709 5.93 78 739 5.84 79 693 5.78 80 739 5.91 82 821 6.39 83 773 5.87 84 863 6.53 85 813 6.37 86 863 6.53 87 849 6.48 88 813 6.39 89 737 6.27 90 819 6.30 91 692 5.79 92 759 5.82 93 827 6.49 94 756 5.86 95 759 6.18 96 773 5.87 97 723 5.75 98 737 5.72 99 827 6.46 100 737 5.74 101 737 5.80 102 827 6.47 103 711 5.61 104 849 6.45 108 583 5.10 109 583 5.13 Method B The HPLC gradient was supplied by a Waters Alliance HT 2790 system (Waters, Milford, Mass.) with a columnheater set at 40° C. Flow from the column was split to a Waters 996 photodiode array (PDA) detector and a Waters-Micromass ZQ mass spectrometer with an electrospray ionization source operated in positive and negative ionization mode. Reversed phase HPLC was carried out on a Xterra MS C18 column (5 mm, 3.9×150 mm) with a flow rate of 1 ml/min. Two mobile phases (mobile phase A: 85% 6.5 mM ammonium acetate +15% acetonitrile; mobile phase B: 20% 6.5 mM amminium acatate +80% acetonibfile) were employed to run a gradient condition from 100% A for 3 min to 100% B in 5 min., 100% B for 6 min to 100% A in 3 min, and re-equilibrate with 100% A for 3 min). Mass spectra were acquired as in Method A. TABLE 5 LCMS parent peak and retention time for selected compounds. Compound LCMS MS(MH+) Retention no. Meth. B time 68 752 5.10 69 752 5.30 70 703 4.40 75 702 4.50 81 738 4.90 110 687 3.57 111 687 3.43 112 691 4.70 114 665 4.77 115 695 4.30 116 691 4.64 118 735 5.14 119 735 4.30 Method C The HPLC gradient was supplied by a Waters Alliance HT 2790 system (Wates, Milford, Mass.) with a columnheater set at 40° C. Flow from the column was split to a Waters 996 photodiode array (PDA) detector and a Waters-Micromass ZQ mass spectrometer with an electrospray ionization source operated in positive and negative ionization mode. Reversed phase HPLC was carried out on a Kromasil C18 column (5 mm, 4.6×150 mm) with a flow rate of 1 ml/min. Two mobile phases (mobile phase A: 30% 6.5 mM ammonium acetate +40% acetonitrile +30% formic acid (2 ml/l); mobile phase B: 100% acetonitrile) were employed to run a gradient condition from 100% A for 1 min to 100% B in 4 min., 100% B for 5 min to 100% A in 3 min, and re-equilibrate with 100% A for 2 min). Mass spectra were acquired as in Method A. TABLE 6 LCMS parent peak and retention time for selected compounds. Compound LCMS MS(MH+) Retention no. Meth. B time 120 743 10.2 121 695 8.90 122 743 9.90 Optical Rotations Optical rotations were recorded on a polarimeter (Perkin Elmer) at 20° C. in methanol, using a cell pathlength=1 dm, a volume=5 ml at a concentration=0.5 mgl/l. TABLE 7 Optical rotation data for selected compounds. Compound Wavelength No. [α] (nm) 52 +29.84 589 nm 57 −27.07 589 nm D. Pharmacological Example EXAMPLE C.1 Binding Experiment for h-NK1, h-NK2 and h-NK3 Receptors The compounds according to the invention were investigated for interaction with various neurotransmitter receptors, ion channels and transporter binding sites using the radioligand binding technique. Membranes from tissue homogenates or from cells, expressing the receptor or transporter of interests, were incubated with a radioactively labelled substance ([3H—] or [125I] ligand) to label a particular receptor. Specific receptor binding of the radioligand was distinguished from the non-specific membrane labelling by selectively inhibiting the receptor labelling with an unlabelled drug (the blank), known to compete with the radioligand for binding to the receptor sites. Following incubation, labelled membranes were harvested and rinsed with excessive cold buffer to remove non-bound radioactivity by rapid filtration under suction. Membrane bound radioactivity was counted in a scintillation counter and results were expressed in counts per minute (cpm). The compounds were dissolved in DMSO and tested at 10 concentrations ranging from 10−10 to 10−5 M. The ability of the compounds according to the invention to displace [3H]-Substance P from cloned human h-NK1 receptors expressed in CHO cells, to displace [3H]-SR-48968 from cloned human h-NK2 receptors expressed in Sf9 cells, and to displace [3H-SR-142801 from cloned human h-NK3 receptors expressed in CHO cells was evaluated. The receptor binding values (pIC50) for the h-NK1 ranges for all compounds according to the invention between 10 and 6. EXAMPLE C.2 Signal Transduction (ST) This test evaluates in vitro functional NK1 antagonistic activity. For the measurements of intracellular Ca++ concentrations the cells were grown on 96-well (black wall/transparent bottom) plates from Costar for 2 days until they reached confluence. The cells were loaded with 2 μM Fluo3 in DMEM containing 0.1% BSA and 2.5 mM probenecid for 1 h at 37° C. They were washed 3× with a Krebs buffer (140 mM NaCl, 1 mM MgCl2×6H2O, 5 mM KCl, 10 mM glucose, 5 mM HEPES; 1.25 mM CaCl2; pH 7.4) containing 2.5 mM probenecid and 0.1% BSA (Ca++-buffer). The cells were preincubated with a concentration range of antagonists for 20 min at RT and Ca++-signals after addition of the agonists were measured in a Fluorescence Image Plate Reader (FLIPR from Molecular Devices, Crawley, England). The peak of the Ca++-transient was considered as the relevant signal and the mean values of corresponding wells were analysed as described below. The sigmoidal dose response curves were analysed by computerised curve-fitting, using the GraphPad Program. The EC50-value of a compound is the effective dose showing 50% of maximal effect. For mean curves the response to the agonist with the highest potency was normalised to 100%. For antagonist responses the IC50-value was calculated using non-linear regression. The pIC50 data for the signal transduction testing for a representative selection of compounds are presented in Table 8. The last columns indicates—without being limited thereto—for which action the compounds might be most suitable. Of course, since for some neurokinin receptors no data was determined, it is obvious that these compounds might be attributed to another suitable use. TABLE 8 Pharmacological data for the signal transduction for selected compounds pIC50 pIC50 pIC50 Co. No. NK1 NK2 NK3 Suitable for 5 6.1 n.d. n.d. NK1 13 6.3 n.d. 5.0 NK1 124 6.4 5.3 5.6 NK1 87 6.5 6.1 5.1 NK1 58 6.6 5.7 5.0 NK1 111 6.6 n.d. 5.1 NK1 99 6.7 5.2 5.5 NK1 110 6.7 n.d. 5.0 NK1 120 6.7 n.d. 5.1 NK1 90 6.8 5.7 5.0 NK1 112 6.8 n.d. 5.0 NK1 93 6.9 5.0 5.3 NK1 114 6.9 n.d. 5.1 NK1 119 6.9 n.d. 5.0 NK1 121 6.9 n.d. 5.1 NK1 50 7.0 5.2 5.1 NK1 122 7.0 n.d. 5.0 NK1 3 7.1 n.d. 5.7 NK1 85 7.1 5.4 5.3 NK1 108 7.1 5.0 5.0 NK1 44 7.2 n.d. 5.3 NK1 82 7.2 5.5 5.1 NK1 89 7.2 5.3 5.1 NK1 118 7.2 n.d. 5.6 NK1 1 7.3 n.d. n.d. NK1 34 7.3 n.d. 5.7 NK1 109 7.3 5.0 5.0 NK1 116 7.3 n.d. 5.4 NK1 115 7.4 n.d. 5.2 NK1 17 7.5 n.d. 5.6 NK1 12 7.6 n.d. 5.5 NK1 19 7.6 n.d. 5.7 NK1 24 7.6 n.d. 5.4 NK1 31 7.6 n.d. 5.5 NK1 2 7.7 n.d. n.d. NK1 18 7.7 n.d. 5.6 NK1 21 7.7 n.d. 5.9 NK1 23 7.7 5.4 5.7 NK1 75 7.7 5.6 5.5 NK1 81 7.7 5.6 5.8 NK1 59 7.8 5.5 5.7 NK1 14 7.9 n.d. 5.7 NK1 77 7.9 5.7 5.5 NK1 98 7.9 5.3 5.7 NK1 35 8.0 n.d. 5.7 NK1 62 8.0 5.4 5.5 NK1 65 8.0 5.8 5.2 NK1 74 8.0 5.4 5.5 NK1 91 8.0 6.0 5.4 NK1 97 8.0 5.4 5.6 NK1 103 8.0 5.2 5.0 NK1 42 8.1 n.d. 5.6 NK1 56 8.1 6.0 5.7 NK1 61 8.1 5.5 5.2 NK1 67 8.2 5.3 5.8 NK1 60 8.3 n.d. 5.2 NK1 63 8.3 5.5 5.2 NK1 66 8.3 5.5 5.5 NK1 84 6.6 6.3 5.9 NK1/NK2/NK3 83 6.8 6.1 6.4 NK1/NK2/NK3 104 6.9 5.9 6.5 NK1/NK2/NK3 48 7.5 6.0 6.2 NK1/NK2/NK3 45 7.7 5.8 6.4 NK1/NK2/NK3 25 7.8 6.4 7.1 NK1/NK2/NK3 30 7.8 6.2 6.2 NK1/NK2/NK3 46 7.8 6.3 6.1 NK1/NK2/NK3 49 7.8 6.2 6.5 NK1/NK2/NK3 96 7.8 6.4 7.0 NK1/NK2/NK3 79 7.9 5.8 6.0 NK1/NK2/NK3 92 7.9 6.3 6.8 NK1/NK2/NK3 55 8.0 6.1 7.0 NK1/NK2/NK3 80 8.0 6.1 6.3 NK1/NK2/NK3 68 8.0 5.8 5.8 NK1/NK2/NK3 73 8.1 6.1 6.6 NK1/NK2/NK3 29 8.2 5.9 6.5 NK1/NK2/NK3 38 8.2 6.7 6.6 NK1/NK2/NK3 39 8.2 6.2 6.3 NK1/NK2/NK3 86 8.2 6.4 6.3 NK1/NK2/NK3 32 8.3 6.2 7.0 NK1/NK2/NK3 78 8.4 6.1 6.5 NK1/NK2/NK3 7 7.3 n.d. 6.0 NK1/NK3 33 7.4 n.d. 6.0 NK1/NK3 88 7.4 5.6 6.2 NK1/NK3 20 7.5 5.7 6.6 NK1/NK3 36 7.5 5.3 6.2 NK1/NK3 95 7.5 5.5 5.9 NK1/NK3 10 7.6 5.4 6.3 NK1/NK3 40 7.6 5.1 6.6 NK1/NK3 8 7.7 5.0 6.6 NK1/NK3 11 7.7 5.5 6.0 NK1/NK3 27 7.7 n.d. 5.9 NK1/NK3 72 7.7 5.7 5.9 NK1/NK3 76 7.7 5.7 5.8 NK1/NK3 94 7.7 5.4 6.0 NK1/NK3 9 7.8 5.6 6.1 NK1/NK3 47 7.8 5.3 6.3 NK1/NK3 69 7.8 5.6 6.2 NK1/NK3 107 7.8 n.d. 5.9 NK1/NK3 15 7.9 5.2 6.8 NK1/NK3 16 7.9 5.0 6.0 NK1/NK3 37 7.9 5.7 6.2 NK1/NK3 57 7.9 5.5 6.1 NK1/NK3 64 7.9 5.2 6.1 NK1/NK3 22 8.0 5.6 6.3 NK1/NK3 28 8.0 5.7 6.8 NK1/NK3 43 8.0 5.7 6.3 NK1/NK3 26 8.1 5.1 6.1 NK1/NK3 41 8.1 5.5 7.0 NK1/NK3 70 8.1 5.4 5.9 NK1/NK3 53 8.3 5.7 7.3 NK1/NK3 54 8.3 5.7 6.6 NK1/NK3 52 8.4 5.5 6.3 NK1/NK3 51 8.5 5.0 6.1 NK1/NK3 (n.d. = not determined). E. Composition Examples “Active ingredient” (A.I.) as used throughout these examples relates to a compound of Formula (I), the pharmaceutically acceptable acid or base addition salts thereof, the stereochemically isomeric forms thereof, the N-oxide form thereof and prodrugs thereof. EXAMPLE E.1 Oral Drops 500 Grams of the A.I. was dissolved in 0.5 l of 2-hydroxypropanoic acid and 1.5 l of the polyethylene glycol at 60-80° C. After cooling to 30-40° C. there were added 35 l of polyethylene glycol and the mixture was stirred well. Then there was added a solution of 1750 grams of sodium saccharin in 2.5 l of purified water and while stirring there were added 2.5 l of cocoa flavor and polyethylene glycol q.s. to a volume of 50 l, providing an oral drop solution comprising 10 mg/ml of A.I. The resulting solution was filled into suitable containers. EXAMPLE E.2 Oral Solution 9 Grams of methyl 4-hydroxybenzoate and 1 gram of propyl 4-hydroxybenzoate were dissolved in 4 l of boiling purified water. In 3 l of this solution were dissolved first 10 grams of 2,3-dihydroxybutanedioic acid and thereafter 20 grams of the A.I. The latter solution was combined with the remaining part of the former solution and 12 11,2,3-propanetriol and 3 l of sorbitol 70% solution were added thereto. 40 Grams of sodium saccharin were dissolved in 0.5 l of water and 2 ml of raspberry and 2 ml of gooseberry essence were added. The latter solution was combined with the former, water was added q.s. to a volume of 20 l providing an oral solution comprising 5 mg of the active ingredient per teaspoonful (5 ml). The resulting solution was filled in suitable containers. EXAMPLE E.3 Film-Coated Tablets Preparation of Tablet Core A mixture of 100 grams of the A.I., 570 grams lactose and 200 grams starch was mixed well and thereafter humidified with a solution of 5 grams sodium dodecyl sulfate and 10 grams polyvinylpyrrolidone in about 200 ml of water. The wet powder mixture was sieved, dried and sieved again. Then there was added 100 grams microcrystalline cellulose and 15 grams hydrogenated vegetable oil. The whole was mixed well and compressed into tablets, giving 10.000 tablets, each containing 10 mg of the active ingredient. Coating To a solution of 10 grams methyl cellulose in 75 ml of denaturated ethanol there was added a solution of 5 grams of ethyl cellulose in 150 ml of dichloromethane. Then there were added 75 ml of dichloromethane and 2.5 ml 1,2,3-propanetriol. 10 Grams of polyethylene glycol was molten and dissolved in 75 ml of dichloromethane. The latter solution was added to the former and then there were added 2.5 grams of magnesium octadecanoate, 5 grams of polyvinylpyrrolidone and 30 ml of concentrated colour suspension and the whole was homogenated. The tablet cores were coated with the thus obtained mixture in a coating apparatus. EXAMPLE E.4 Injectable Solution 1.8 Grams methyl 4-hydroxybenzoate and 0.2 grams propyl 4-hydroxybenzoate were dissolved in about 0.5 l of boiling water for injection. After cooling to about 50° C. there were added while stirring 4 grams lactic acid, 0.05 grams propylene glycol and 4 grams of the A.I. The solution was cooled to room temperature and supplemented with water for injection q.s. ad 1 l, giving a solution comprising 4 mg/ml of A.I. The solution was sterilized by filtration and filled in sterile containers.
<SOH> BACKGROUND OF THE INVENTION <EOH>Tachykinins belong to a family of short peptides that are widely distributed in the mammalian central and peripheral nervous system (Bertrand and Geppetti, Trends Pharmacol. Sci. 17:255-259 (1996); Lundberg, Can. J. Physiol. Pharmacol. 73:908-914 (1995); Maggi, Gen. Pharmacol. 26:911-944 (1995); Regoli et al., Pharmacol. Rev. 46 (1994)). They share the common C-terminal sequence Phe-Xaa-Gly-Leu-Met-NH 2 . Tachykinins released from peripheral sensory nerve endings are believed to be involved in neurogenic inflammation. In the spinal cord/central nervous system, tachykinins may play a role in pain transmission/perception and in some autonomic reflexes and behaviors. The three major tachykinins are Substance P (SP), Neurokinin A (NK A ) and Neurokinin B (NK B ) with preferential affinity for three distinct receptor subtypes, termed NK 1 , NK 2 , and NK 3 , respectively. However, functional studies on cloned receptors suggest strong functional cross-interaction between the 3 tachykinins and their corresponding receptors (Maggi and Schwartz, Trends Pharmacol. Sci. 18: 351-355 (1997)). Species differences in structure of NK 1 receptors are responsible for species-related potency differences of NK 1 antagonists (Maggi, Gen. Pharmacol. 26:911-944 (1995); Regoli et al., Pharmacol. Rev. 46(4):551-599 (1994)). The human NK 1 receptor closely resembles the NK 1 receptor of guinea-pigs and gerbils but differs markedly from the NK 1 receptor of rodents. The development of neurokinin antagonists has led to date to a series of peptide compounds of which might be anticipated that they are metabolically too labile to be employed as pharmaceutically active substances (Longmore J. et al, DN & P 8(1):5-23 (1995)). The tachykinins are involved in schizophrenia, depression, (stress-related) anxiety states, emesis, inflammatory responses, smooth muscle contraction and pain perception. Neurokinin antagonists are in development for indications such as emesis, anxiety and depression, irritable bowel syndrome (IBS), circadian rhythm disturbances, visceral pain, neurogenic inflammation, asthma, micturition disorders, and nociception. In particular, NK 1 antagonists have a high therapeutic potential in emesis and depression and NK 2 antagonists have a high therapeutic potential in asthma treatments. NK 3 antagonists seem to play a role in the treatment of pain/inflammation (Giardina, G. et al. Exp. Opin. Ther. Patents, 10(6): 939-960 (2000)) and schizophrenia. Schizophrenia The NK 3 antagonist SR142801 (Sanofi) was recently shown to have antipsychotic activity in schizophrenic patients without affecting negative symptoms (Arvantis, L ACNP Meeting, December 2001). Activation of NK 1 receptors causes anxiety, stressful events evoke elevated substance P (SP) plasma levels and NK 1 antagonists are reported to be anxiolytic in several animal models. The NK 1 antagonist from Merck, MK-869 shows antidepressant effects in major depression, but data were not conclusive due to a high placebo response rate. Moreover, the NK 1 antagonist from Glaxo-Welcome (S)-GR205,171 was shown to enhance dopamine release in the frontal cortex but not in the striatum (Lejeune et al. Soc. Neurosci, November 2001). It is therefore hypothesized that NK 3 antagonism in combination with NK 1 antagonism would be beneficial against both positive and negative symptoms of schizophrenia Anxiety and Depression Depression is one of the most common affective disorders of modern society with a high and still increasing prevalence, particularly in the younger members of the population. The life time prevalence rates of Major depression (MDD, DSM-IV) is currently estimated to be 10-25% for women and 5-12% for men, whereby in about 25% of patients the life time MDD is recurrent, without full inter-episode recovery and superimposed on dysthymic disorder. There is a high co-morbidity of depression with other mental disorders and, particularly in younger population high association with drug and alcohol abuse. In the view of the fact that depression primarily affects the population between 18-44 years of age e.g. the most productive population, it is obvious that it imposes a high burden on individuals, families and the whole society. Among all therapeutic possibilities, the therapy with antidepressants is incontestably the most effective. A large number of antidepressants have been developed and introduced to the market in the course of the last 40 years. Nevertheless, none of the current antidepressants fulfill all criteria of an ideal drug (high therapeutic and prophylactic efficacy, rapid onset of action, completely satisfactory short- and long-term safety, simple and favourable pharmacokinetics) or is without side effects which in one or the other way limits their use in all groups and subgroups of depressed patients. Since no treatment of the cause of depression exists at present, nor appears imminent, and no antidepressant is effective in more than 60-70% of patients; the development of a new antidepressant which may circumvent any of the disadvantages of the available drugs is justified. Several findings indicate involvement of SP in stress-related anxiety states. Central injection of SP induces a cardiovascular response resembling the classical “fight or flight” reaction characterised physiologically by vascular dilatation in skeletal muscles and decrease of mesenteric and renal blood flow. This cardiovascular reaction is accompanied by a behavioural response observed in rodents after noxious stimuli or stress (Culman and Unger, Can. J. Physiol. Pharmacol. 73:885-891 (1995)). In mice, centrally administered NK 1 agonists and antagonists are anxiogenic and anxiolytic, respectively (Teixeira et at., Eur. J. Pharmacol. 311:7-14 (1996)). The ability of NK 1 antagonists to inhibit thumping induced by SP (or by electric shock; Ballard et al., Trends Pharmacol. Sci. 17:255-259 (2001)) might correspond to this antidepressant/anxiolytic activity, since in gerbils thumping plays a role as an alerting or warning signal to conspecifics. The NK 1 receptor is widely distributed throughout the limbic system and fear-processing pathways of the brain, including the amygdala, hippocampus, septum, hypothalamus, and periaqueductal grey. Additionally, substance P is released centrally in response to traumatic or noxious stimuli and substance P-associated neurotransmission may contribute to or be involved in anxiety, fear, and the emotional disturbances that accompany affective disorders such as depression and anxiety. In support of this view, changes in substance P content in discrete brain regions can be observed in response to stressful stimuli (Brodin et al., Neuropeptides 26:253-260 (1994)). Central injection of substance P mimetics (agonists) induces a range of defensive behavioural and cardiovascular alterations including conditioned place a version (Elliott, Exp. Brain. Res. 73:354-356 (1988)), potentiated acoustic startle response (Krase et at., Behav. Brain. Res. 63:81-88 (1994)), distress vocalisations, escape behaviour (Kramer et al., Science 281:1640-1645 (1998)) and anxiety on the elevated plus maze (Aguiar and Brandao, Physiol. Behav. 60:1183-1186 (1996)). These compounds did not modify motor performance and co-ordination on the rotarod apparatus or ambulation in an activity cage. Down-regulation of substance P biosynthesis occurs in response to the administration of known anxiolytic and antidepressant drugs (Brodin et al., Neuropeptides 26:253-260 (1994); Shirayama et al., Brain. Res. 739:70-78 (1996)). Similarly, a centrally administered NK 1 agonist-induced vocalisation response in guinea-pigs can be antagonised by antidepressants such as imipramine and fluoxetine as well as L-733,060, an NK 1 antagonist. These studies provide evidence suggesting that blockade of central NK 1 receptors may inhibit psychological stress in a manner resembling antidepressants and anxiolytics (Rupniak and Kramer, Trends Pharmacol. Sci. 20:1-12 (1999)), but without the side effects of present medications. Emesis Nausea and vomiting are among the most distressing side effects of cancer chemotherapy. These reduce the quality of life and may cause patients to delay or refuse, potentially curative drugs (Kris et al., J. Clin. Oncol., 3:1379-1384 (1985)). The incidence, intensity and pattern of emesis is determined by different factors, such as the chemotherapeutic agent, dosage and route of administration. Typically, early or acute emesis starts within the first 4 h after chemotherapy administration, reaching a peak between 4 h and 10 h, and decreases by 12 to 24 h. Delayed emesis (developing after 24 h and continuing until 3-5 days post chemotherapy) is observed with most ‘high-emetogenic’ chemotherapeutic drugs (level 4 and 5 according to Hesketh et al., J. Clin. Oncol. 15:103 (1997)). In humans, these ‘high-emetogenic’ anti-cancer treatments, including cis-platinum, induce acute emesis in >98% and delayed emesis in 60-90% of cancer patients. Animal models of chemotherapy such as cisplatin-induced emesis in ferrets (Rudd and Naylor, Neuropharmacology 33:1607-1608 (1994); Naylor and Rudd, Cancer. Surv. 21:117-135 (1996)) have successfully predicted the clinical efficacy of the 5-HT 3 receptor antagonists. Although this discovery led to a successful therapy for the treatment of chemotherapy- and radiation-induced sickness in cancer patients, 5-HT 3 antagonists such as ondansetron and granisetron (either or not associated with dexamethasone) are effective in the control of the acute emetic phase (the first 24 h) but can only reduce the development of delayed emesis (>24 h) with poor efficacy (De Mulder et al., Annuals of Internal Medicine 113:834-840 (1990); Roila, Oncology 50:163-167 (1993)). Despite these currently most effective treatments for the prevention of both acute and delayed emesis, still 50% of patients suffer from delayed vomiting and/or nausea (Antiemetic Subcommittee, Annals Oncol. 9:811-819 (1998)). In contrast to 5-HT 3 antagonists, NK 1 antagonists such as CP-99,994 (Piedimonte et al., L. Pharmacol. Exp. Ther. 266:270-273 (1993)) and aprepitant (also known as MK-869 or L1754,030; Kramer et al., Science 281:1640-1645 (1998); Rupniak and Kramer, Trends Pharmacol. Sci. 20:1-12 (1999)) have now been shown to inhibit not only the acute but also the delayed phase of cisplatin-induced emesis in animals (Rudd et al., Br. J. Pharmacol. 119:931-936(1996) ; Tattersall et al., Neuropharmacology 39:652-663 (2000)). NK 1 antagonists have also been demonstrated to reduce ‘delayed’ emesis in man in the absence of concomitant therapy (Cocquyt et al., Eur. J. Cancer 37:835-842 (2001); Navari et al., N. Engl. L. Med 340:190-195 (1999)). When administered together with dexamethasone and 5-HT 3 antagonists, moreover, NK 1 antagonists (such as MK-869 and CJ-11,974, also known as Ezlopitant) have been shown to produce additional effects in the prevention of acute emesis (Campos et al., J. Clin. Oncol. 19:1759-1767 (2001); Hesketh et al., Clin. Oncol. 17:338-343 (1999)). Central neurokinin NK 1 receptors play a major role in the regulation of emesis. NK 1 antagonists are active against a wide variety of emetic stimuli (Watson et al., Br. J. Pharmacol. 115:84-94 (1995); Tattersall et al., Neuropharmacol. 35:1121-1129 (1996); Megens et al., J. Pharmacol. Exp. Ther. 302:696-709 (2002)). The compounds are suggested to act by blocking central NK 1 receptors in the nucleus tractus solitarius. Apart from NK 1 antagonism, CNS penetration is thus a prerequisite for the antiemetic activity of these compounds. Loperamide-induced emesis in ferrets can be used as a fast and reliable screening model for the antiemetic activity of NK 1 antagonists. Further evaluation of their therapeutic value in the treatment of both the acute and the delayed phases of cisplatin-induced emesis has been demonstrated in the established ferret model (Rudd et al., Br. J. Pharmacol. 119:931-936 (1994)). This model studies both ‘acute’ and ‘delayed’ emesis after cisplatin and has been validated in terms of its sensitivity to 5-HT 3 receptor antagonists, glucocorticoids (Sam et al., Eur. J. Pharmacol. 417:231-237 (2001)) and other pharmacological challenges. It is unlikely that any future anti-emetic would find clinical acceptance unless successfully treating both the ‘acute’ and ‘delayed’ phases of emesis. Irritable Bowel Syndrome (IBS) Patients with irritable bowel syndrome (IBS) experience impaired quality of life, and utilise health care resources extensively as they seek better “solutions” (including unnecessary repeated investigations or even surgery). Although these patients suffer from a ‘benign’ disorder (in other words, they will never die or develop significant complications), they nevertheless cause a significant economic burden by extensive health care resource utilisation, and absence from work. A reasonable number of pre-clinical publications over the role of NK 1 receptors in visceral pain has been published. Using NK 1 receptor knockout mice and NK 1 antagonists in animal models, different groups have demonstrated the important role played by the NK 1 receptor in hyperalgesia and visceral pain. The distribution of NK 1 receptors and substance P favours a major role in visceral rather than in somatic pain. Indeed more than 80% of visceral primary afferent contain substance P compared with only 25% skin afferents. NK 1 receptors are also involved in gastrointestinal motility (Tonini et al., Gastroenterol. 120:938-945 (2001); Okano et al., J. Pharmacol. Exp. Ther. 298:559-564 (2001)). Because of this dual role in both gastrointestinal motility and in nociception, NK 1 antagonists are considered to have potential to ameliorate symptoms in IBS patients.
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BERNHARDT, EMILY A
SUBSTITITUTED 1-PIPERIDIN-3-YL-PIPERIDIN 4-YL-PIPERAZINE DERIVATIVES AND THEIR USE AS NEUROKININ ANTAGONISTS
UNDISCOUNTED
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ACCEPTED
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Method and communication device for expanding the range of data transmission rates in wireless local area networks
A communication device and a method for transmitting data in wireless local area networks is provided. The device and method are deployed in networks in which the data information elements include an element identification part, a length statement part and an information part. The device and method enable a broad range of data transmission rates and are full compatible with communicating units operating according to previous modes in which a first data transmission rule defines the acceptable range of values of element identification parts. In the method, a second data transmission rule is implemented in at least one of the communicating units to extend the acceptable range of values of element identifications. The range of values is extended so that a second standard portion of the element identification part marks the information element as a second information element.
1.-18. (canceled) 19. A method for data transmission in wireless local area networks in which data transmission is implemented between a first and a second communicant, and in which a first standardized data transmission rule is implemented requiring transmission and/or reception of information elements with variant element formats on electromagnetic signal paths, with the information elements comprising an element identification part, a length statement part and an information part, and the element identification part having a permissible value range in which a first standardized value of the element identification part identifies the information element as a first information element whose information part contains parameters which relate to the data transmission of the communicant in accordance with a first data transmission rule as the transmitter, a receiving communicant storing the parameters for the transmitting communicant in order to set the data transmission for return to the transmitting communicant, and each of the communicants, as the receiver determining the length of the information part from the length statement part on identification of a value of the element identification part outside the permissible value range, and jumping over the information part corresponding to the determined length, the method comprising the step of: at least in the case of one of the communicants, implementing in addition to the first data transmission rule a second data transmission rule expanding the permissible value range so that a second standardized value of the element identification part identifies the information element as a second information element whose information part contains parameters which relate to the data transmission of the transmitting communicant in accordance with the second data transmission rule. 20. The method as claimed in claim 19, characterized in that the first information element contains only parameters which relate to the data transmission in accordance with the first data transmission rule, and the second information element contains only parameters which relate to the data transmission in accordance with the second data transmission rule. 21. The method of claim 19 further comprising the step of jumping over the second information element when a communicant in which only the first data transmission rule is implemented receives the second information element. 22. The method of claim 19 further comprising the step of storing the parameters which relate to the first and second information elements when a communicant in which both data transmission rules are implemented receives the second information element. 23. The method of claim 19 wherein the values in the information part of second information elements represent a set of data transmission rates which are supported by the transmitting communicant in such a way that each value corresponds to one supported data transmission rate. 24. The method of claim 23 wherein the difference between a data transmission rate which corresponds to one value and the data transmission rate which corresponds to the next value is greater than or equal to 500 Kbit/s. 25. The method of claim 24 wherein the difference is 1 Mbit/s. 26. The method of claim 23 wherein at most eight values correspond to the data transmission rates of the first data transmission rule, and all other values correspond to the data transmission rates of the second data transmission rule. 27. The method of claim 23 wherein the second information element additionally contains the values of the data transmission rates which are equal to values for data transmission rates of the first data transmission rule. 28. The method of claim 27 further comprising the step of storing only the parameters which relate to the second information element when a communicant in which both data transmission rules are implemented receives the second information element. 29. The method of claim 23, further comprising the step of: in addition to the second information element, forming a third or further information element or elements which represents or represent third or further data transmission rules, respectively. 30. The method of claim 23 wherein the data rates in the information element are represented by value pairs, wherein one value codes the data transmission rule itself and the other value codes the data rate, and wherein the coding of the data rate depends on the data transmission rule. 31. A communication device for data transmission in wireless networks, wherein the communication device can be connected as the first communicant in such networks to a second communicant via electromagnetic signal paths and which has at least one transmitting unit, wherein a first data transmission rule that defines a first information element comprising an element identification part, a length statement part and an information part, is implemented in the communication device, wherein the first data transmission rule defines a permissible value range for the element identification part, the communication device further comprising: an implementation of a second data transmission rule which expands the value range of the element identification part, and a transmitting unit configured to send second information elements which are defined by a second standardized value of the element identification part, and whose information part contains parameters which relate to the data transmission in accordance with the second data transmission rule. 32. The communication device of claim 31, further comprising a receiving unit configured for reception of a first and of a second information element. 33. The communication device of claim 31 which is switchable between the first and second data transmission rules in response to the reception of information elements during transmission. 34. The communication device of claim 31, further comprising a memory which is arranged to store parameters which relate to received second information elements. 35. The communication device of claim 31, further comprising a memory which is arranged to store parameters which relate to received first and second information elements. 36. The communication device of claim 31, further comprising an implementation of at least a third data transmission rule which is similar to the implementation of the second data transmission rule.
CROSS REFERENCE TO RELATED APPLICATIONS This application claims the benefit of International Patent Application No. PCT/DE2003/004218 filed Dec. 19, 2003, which claims priority to German Patent Application No. 103 00 366.5 filed Jan. 6, 2003, both of which applications are hereby incorporated by reference in their entireties herein. FIELD OF THE INVENTION The invention relates to methods for data transmission in wireless local area networks. The invention, in particular, relates to methods for increasing data transmission rates between communication units which may be operating in diverse modes. BACKGROUND OF THE INVENTION Data transfer in wireless local area networks between a first and second communicant may involve a first standardized data transmission rule or format and transmission and/or reception on electromagnetic signal paths of information elements with variant element formats. The information elements in this case may include an element identification part, a length statement part and an information part. The element identification part has a permissible value range from which a first standardized value of the element identification part identifies the information element as a first information element. The information part of the first information element contains parameters which relate to the data transmission of the communicant in accordance with a first data transmission rule as the transmitter. A receiving communicant stores the parameters which relate to the transmitting communicant in order to set the data transmission in the reply to the transmitting communicant. On identification of a value of the element identification part outside the permissible value range, each of the communicants, as the receiver determines the length of the information part from the length statement part, and jumps over the information part corresponding to the determined length. A communication device for data transmission in wireless networks may be connected as the first communicant in such networks to a second communicant via electromagnetic signal paths. The communication device has at least one transmitting unit. In this case, a first data transmission rule (which defines first information elements comprising an element identification part, a length statement part and an information part) is implemented in the communication device and defines a permissible value range for the element identification part. The importance of wireless networks has increased continuously in recent years. Their usage capabilities appear to be unlimited. The simplest option is to use two or more hosts (communicants) with wireless network cards in a so-called ad-hoc network. If it is intended to connect the wireless network (WLAN) to a wire-based local area network (LAN), an access point (AP) is required. A network structure such as this is also referred to as a distribution system (DS). An access point (first communicant) forms a radio cell with at least one individual station (second communicant). The increase in coverage is achieved by additional cells with two or more access points. Each access point acts like a traditional network bridge. One problem which has prevented wider use of WLANs was the inadequate standardization for a long time. This situation has now changed with an increasing tempo since the Institution of Electrical and Electronics Engineering (IEEE) has adopted WLAN Standards in recent years. See e.g., Publication XP002206839, IEEE standard for information technology telecommunication and information exchange between systems—local and metropolitan area networks—specific requirement, Part II: wireless LAN medium access control (MAC) and physical layer (PHY) specification, (ISO/IEC 8802-11, ANSI/IEEE Std. 802.11-1999), Aug. 20, 1999. One such disadvantage was also that wireless networks did not allow such high data transmission rates as wire-based networks. This was because the bandwidths provided by the regulators are limited and wireless networks have to introduce additional security mechanisms and expanded information in the data packets in order to make it possible to take account of the characteristic of a radio link. Since radio links are more susceptible to interference than cables, additional correction mechanisms have been introduced in the MAC layer in Standard 802.11. In the event of data transmission errors, these correction mechanisms ensure that the data packets are sent again, without any involvement of higher protocol layers in this process. This may now possibly lead to lengthened data transmission times in comparison to the quite error-free connection in a cable-based network. The IEEE Committee continued the further development of the already established WLAN Standard 802.11 by supplementing 802.11a for 5 Ghz and 802.11b for 2.4 Ghz. At the moment, a further increase in the data rate in the 2.4 Ghz band is being worked on in the IEEE 802.11g working group. One important feature of the new standard is the backwards compatibility with the established IEEE 802.11b Standard. The provider companies found out quite quickly that lack of compatibility detracts from the acceptance of their products for wireless local area network technology. In order to allow matching to different radio channels, the 802.11 Standard and its extensions 802.11a and b allow various data transmission rates. The data rates are coded in an information element which, in accordance with IEEE 802.11, allows a maximum number of 8 rates and is transmitted in the beacon signal. The IEEE 802.11g Standard provides for more than 8 data rates to be allowed. Intraoperability tests have shown that, when more than 8 data rates are notified in the conventional information element, backwards compatibility with existing solutions is no longer guaranteed. Consideration is now being given to improving communication devices and network data transmission methods. In particular attention is directed to communication devices and data transmission methods which can achieve a wide range of data transmission rates while remaining fully compatible with communicants operating in diverse modes including legacy modes. SUMMARY OF THE INVENTION Communication devices and data transmission methods are provided for networked communications with diverse communicants. The data transmission methods may be implemented to achieve a wide range of data transmission rates which are fully compatible with the various operating modes of the diverse communicants. In an inventive data transmission method, at least in the case of one of the communicants, the first and a second data transmission rule are implemented, and the permissible value range is expanded in such a way that a second standardized value of the element identification part identifies the information element as a second information element whose information part contains parameters which relate to the data transmission of the transmitting communicant in accordance with the second data transmission rule. This makes it possible, in addition to the parameters for data transmission in accordance with the first data transmission rule, to also transmit parameters for data transmission in accordance with the second data transmission rule from the transmitting communicant to the receiving communicant. The second data transmission rule therefore allows a wider range of parameters than the first, for example. Parameters which relate to the second data transmission rule can thus be used alternatively or in addition to the parameters which relate to the first data transmission rules. The parameters which relate to the first and the second data transmission rules are expediently clearly separated in that the first information element contains only parameters which relate to the data transmission in accordance with the first data transmission rule, and the second information element contains only parameters which relate to the data transmission in accordance with the second data transmission rule. In conjunction with the fact that information elements whose element identification does not correspond to the range of values are jumped over by each communicant, the method is also backwards-compatible. The second information element is advantageously jumped over on reception of the second information element by a communicant in which only the first data transmission rule is implemented. If second information elements are sent in this case to communicants in which only the first data transmission rule is implemented, then the element identification of the second information element is outside the permissible value range, and the second information element is jumped over by the receiving communicant, and therefore does not cause any disturbance. The advantage of the greater variation of parameters which relate to data transmission is achieved in particular in that when a communicant in which both data transmission rules are implemented receives the second information element, the parameters which relate to the first and second information elements are stored. The method is advantageously carried out in such a way that the values in the information part of second information elements represent a set of data transmission rates which are supported by the transmitting communicant, in such a way that each value corresponds to one supported data transmission rate. A transmitting communicant thus informs the receiving communicant about all of the data transmission rates which it can process. The receiving communicant can then select a suitable data transmission rate in the acknowledgement. A refinement of the method according to the invention provides that the difference between a data transmission rate which corresponds to one value and the data transmission rate which corresponds to the next value is greater than or equal to 500 Kbit/s. A wide variation range of data transmission rates is thus available. In this case, it is particularly expedient for the difference to be 1 Mbit/s. A further refinement in the method provides that at most eight values correspond to the data transmission rates of the first data transmission rule, and all the other values correspond to the data transmission rates of the second data transmission rule. This corresponds to older standard requirements in which at most eight values were provided for the variation of the data transmission rates. For this purpose, it is also possible for the second information element additionally to contain values for data transmission rates which are equal to values for data transmission rates of the first data transmission rule. In this case, it is possible that when a communicant in which both data transmission rules are implemented receives the second information element, only the parameters which relate to the second information element are stored. The method according to the invention can also be expanded in a manner which corresponds to the first and second information elements in that, in addition to the second information element, a third or further information element or elements is or are also formed, which represents or represent third or further data transmission rules. One refinement of the method according to the invention provides that the data transmission rates are coded with the aid of value pairs instead of single values. In this case, the one value of the pair codes the data transmission rule itself and the other value codes the data rate. In this case, it is particularly expedient to make the coding of the data rate dependent on the data transmission rule. This allows very flexible extension for new data transmission rules. The object is also achieved by a communication device in which a second data transmission rule with an expanded value range of the element identification part is implemented. The transmitting unit can send two information elements which are defined by a second standardized value of the element identification part. In this case, its information part contains parameters which relate to the data transmission in accordance with the second data transmission rule. When the second communicant is unknown, this communication device makes it possible, for example, first of all to attempt to send information elements in accordance with the second data transmission rule. In this case, an element identification part is provided with the standardized value. At the receiver end, it is thus possible to identify a transmitter which can operate in accordance with the second data transmission rule. If the second communicant can likewise operate using the second data transmission rule, it can be set to the appropriate operating mode. If it can operate only in accordance with the first data transmission rule, it will not be able to “understand” the standardized value, since this is outside the permissible value range. This receiver will therefore jump over the information element. A communication device designed in this way does not interfere with second communicants which are implemented as communication devices in which only the first data transmission rule is implemented. In one embodiment of the invention, a receiving unit which is designed for reception of a first and of a second information element is arranged in the communication device. The communication device according to the invention is thus suitable not only for transmission but also for reception of information both in accordance with the first and the second data transmission rule. A further embodiment of the communication device according to the invention can be switched between first and second data transmission rules as a function of the reception of information elements during transmission. The communication device is thus both backwards and forwards compatible. Specifically, if information is received in accordance with the first data transmission rule, the communication device can switch to operate with the first data transmission rule, and both communicants then continue their communication on the basis of the first data transmission rule. If the communication device receives information with the second data transmission rule—for example by means of an identically designed communication device as the communicant at the other end, it will switch to operate in accordance with the second data transmission rule. The communication device according to the invention is advantageously provided with a memory which is designed to store parameters of received second information elements. By way of example, the communication can thus be started straight away in accordance with the second data transmission rule at a later time, when this is stored, since the second data transmission rule was already relevant in a previous communication, and it can be assumed that the same communicant is still located in the vicinity. This therefore makes it possible initially to avoid the time for matching to the data transmission rule. One development provides for a memory to be arranged, which is designed to store parameters of the received first and second information elements. In consequence, the same method as that described above can also be used for the first data transmission rule. It is particularly advantageous to develop the communication device in such a way that a third or further data transmission rule or rules is or are implemented in the same way as the second data transmission rule. This also makes it possible to widen the backwards and forwards compatibility for other data transmission rules. BRIEF DESCRIPTION OF THE DRAWINGS Further features of the invention, its nature, and various advantages will be more apparent from the following detailed description and the accompanying drawings, wherein like reference characters represent like elements throughout, and in which: FIG. 1 is a schematic representation of an exemplary an information element design, in accordance with the principles of the present invention; and FIG. 2 is a block diagram of the data transmission processes in a wireless local area network, in accordance with the principles of the present invention. The following list is an index of the reference characters or numerals that are used in FIGS. 1 and 2 to identify drawing elements. LIST OF REFERENCE SYMBOLS 1. ERP Access point 2. Station 3. Data transmission test procedure 4. Test requirement 5. Test response 6. Radio beacon signal for the ERP access point 7. First authentication 8. Second authentication 9. Request for association 10. Association response 11. State of the successful association of the ERP access point 12. State of the successful association of the ERP station 13. Radio beacon signal transmission process 14. Element identification part 15. Length statement part 16. Information part 17. Information elements 18. Association process 19. Extended supported rates ID 20. Extended supported rates field DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION Communication devices and data transmission methods are provided for achieving high data transmission rates between heterogeneous communicants. An exemplary implementation of the invention is described herein with reference to a “critical case” according to the prior art of successful data transmission between an ERP access point 1 and a station 2 which is designed according to the prior art. FIG. 1 shows a basic configuration of an information element 17. The information element 17 comprises the element identification part 14, the length statement part 15, and the information part 16. The information element 17 therefore contains all the important data in order to implement the data transmission rule. FIG. 2 shows three possible options for data rate communication for the data transmission processes: data transmission test procedure 3 radio beacon signal transmission process 13 association process 18 An access point which operates on the basis of the second data transmission rule is referred to in the following text as an ERP access point (Extended Rate Phy access point 1). The data rate communication takes place between the ERP access point 1 and a station 2, which has the known data transmission rules according to the prior art. In the data transmission test procedure 3, the station 2 uses a test request 4 which contains the element identification part 14 to request the ERP access point 1 for identification. Since the ERP access point 1 has the data transmission rules according to the invention, it can respond with the test response 5 with the correct element identification part 14 which can be understood by the station 2, and can signal its information element 17. In the radio beacon signal transmission process 13, the ERP access point 1 transmits its radio beacon signal 6 at regular intervals, which signals to all of the stations in the radio cell the information element 17 according to the first data transmission rule and according to the second data transmission rule. The station 2 stores the information element according to the first data transmission rule, and ignores the information element according to the second data transmission rule. During the association process 18, the station 2 initiates a first authentication 7, which requests the ERP access point 1 to respond with a second authentication 8. Since the ERP access point 1 has the data transmission rules according to the invention, the communication from the station 2 can be continued with the request for association 9, and the ERP access point 1 responds with the association response 10. Both stations then assume the respective state of the successful association 11; 12. It will be understood that the foregoing is only illustrative of the principles of the invention, and that various modifications can be made by those skilled in the art without departing from the scope and spirit of the invention.
<SOH> BACKGROUND OF THE INVENTION <EOH>Data transfer in wireless local area networks between a first and second communicant may involve a first standardized data transmission rule or format and transmission and/or reception on electromagnetic signal paths of information elements with variant element formats. The information elements in this case may include an element identification part, a length statement part and an information part. The element identification part has a permissible value range from which a first standardized value of the element identification part identifies the information element as a first information element. The information part of the first information element contains parameters which relate to the data transmission of the communicant in accordance with a first data transmission rule as the transmitter. A receiving communicant stores the parameters which relate to the transmitting communicant in order to set the data transmission in the reply to the transmitting communicant. On identification of a value of the element identification part outside the permissible value range, each of the communicants, as the receiver determines the length of the information part from the length statement part, and jumps over the information part corresponding to the determined length. A communication device for data transmission in wireless networks may be connected as the first communicant in such networks to a second communicant via electromagnetic signal paths. The communication device has at least one transmitting unit. In this case, a first data transmission rule (which defines first information elements comprising an element identification part, a length statement part and an information part) is implemented in the communication device and defines a permissible value range for the element identification part. The importance of wireless networks has increased continuously in recent years. Their usage capabilities appear to be unlimited. The simplest option is to use two or more hosts (communicants) with wireless network cards in a so-called ad-hoc network. If it is intended to connect the wireless network (WLAN) to a wire-based local area network (LAN), an access point (AP) is required. A network structure such as this is also referred to as a distribution system (DS). An access point (first communicant) forms a radio cell with at least one individual station (second communicant). The increase in coverage is achieved by additional cells with two or more access points. Each access point acts like a traditional network bridge. One problem which has prevented wider use of WLANs was the inadequate standardization for a long time. This situation has now changed with an increasing tempo since the Institution of Electrical and Electronics Engineering (IEEE) has adopted WLAN Standards in recent years. See e.g., Publication XP002206839, IEEE standard for information technology telecommunication and information exchange between systems—local and metropolitan area networks—specific requirement, Part II: wireless LAN medium access control (MAC) and physical layer (PHY) specification, (ISO/IEC 8802-11, ANSI/IEEE Std. 802.11-1999), Aug. 20, 1999. One such disadvantage was also that wireless networks did not allow such high data transmission rates as wire-based networks. This was because the bandwidths provided by the regulators are limited and wireless networks have to introduce additional security mechanisms and expanded information in the data packets in order to make it possible to take account of the characteristic of a radio link. Since radio links are more susceptible to interference than cables, additional correction mechanisms have been introduced in the MAC layer in Standard 802.11. In the event of data transmission errors, these correction mechanisms ensure that the data packets are sent again, without any involvement of higher protocol layers in this process. This may now possibly lead to lengthened data transmission times in comparison to the quite error-free connection in a cable-based network. The IEEE Committee continued the further development of the already established WLAN Standard 802.11 by supplementing 802.11a for 5 Ghz and 802.11b for 2.4 Ghz. At the moment, a further increase in the data rate in the 2.4 Ghz band is being worked on in the IEEE 802.11g working group. One important feature of the new standard is the backwards compatibility with the established IEEE 802.11b Standard. The provider companies found out quite quickly that lack of compatibility detracts from the acceptance of their products for wireless local area network technology. In order to allow matching to different radio channels, the 802.11 Standard and its extensions 802.11a and b allow various data transmission rates. The data rates are coded in an information element which, in accordance with IEEE 802.11, allows a maximum number of 8 rates and is transmitted in the beacon signal. The IEEE 802.11g Standard provides for more than 8 data rates to be allowed. Intraoperability tests have shown that, when more than 8 data rates are notified in the conventional information element, backwards compatibility with existing solutions is no longer guaranteed. Consideration is now being given to improving communication devices and network data transmission methods. In particular attention is directed to communication devices and data transmission methods which can achieve a wide range of data transmission rates while remaining fully compatible with communicants operating in diverse modes including legacy modes.
<SOH> SUMMARY OF THE INVENTION <EOH>Communication devices and data transmission methods are provided for networked communications with diverse communicants. The data transmission methods may be implemented to achieve a wide range of data transmission rates which are fully compatible with the various operating modes of the diverse communicants. In an inventive data transmission method, at least in the case of one of the communicants, the first and a second data transmission rule are implemented, and the permissible value range is expanded in such a way that a second standardized value of the element identification part identifies the information element as a second information element whose information part contains parameters which relate to the data transmission of the transmitting communicant in accordance with the second data transmission rule. This makes it possible, in addition to the parameters for data transmission in accordance with the first data transmission rule, to also transmit parameters for data transmission in accordance with the second data transmission rule from the transmitting communicant to the receiving communicant. The second data transmission rule therefore allows a wider range of parameters than the first, for example. Parameters which relate to the second data transmission rule can thus be used alternatively or in addition to the parameters which relate to the first data transmission rules. The parameters which relate to the first and the second data transmission rules are expediently clearly separated in that the first information element contains only parameters which relate to the data transmission in accordance with the first data transmission rule, and the second information element contains only parameters which relate to the data transmission in accordance with the second data transmission rule. In conjunction with the fact that information elements whose element identification does not correspond to the range of values are jumped over by each communicant, the method is also backwards-compatible. The second information element is advantageously jumped over on reception of the second information element by a communicant in which only the first data transmission rule is implemented. If second information elements are sent in this case to communicants in which only the first data transmission rule is implemented, then the element identification of the second information element is outside the permissible value range, and the second information element is jumped over by the receiving communicant, and therefore does not cause any disturbance. The advantage of the greater variation of parameters which relate to data transmission is achieved in particular in that when a communicant in which both data transmission rules are implemented receives the second information element, the parameters which relate to the first and second information elements are stored. The method is advantageously carried out in such a way that the values in the information part of second information elements represent a set of data transmission rates which are supported by the transmitting communicant, in such a way that each value corresponds to one supported data transmission rate. A transmitting communicant thus informs the receiving communicant about all of the data transmission rates which it can process. The receiving communicant can then select a suitable data transmission rate in the acknowledgement. A refinement of the method according to the invention provides that the difference between a data transmission rate which corresponds to one value and the data transmission rate which corresponds to the next value is greater than or equal to 500 Kbit/s. A wide variation range of data transmission rates is thus available. In this case, it is particularly expedient for the difference to be 1 Mbit/s. A further refinement in the method provides that at most eight values correspond to the data transmission rates of the first data transmission rule, and all the other values correspond to the data transmission rates of the second data transmission rule. This corresponds to older standard requirements in which at most eight values were provided for the variation of the data transmission rates. For this purpose, it is also possible for the second information element additionally to contain values for data transmission rates which are equal to values for data transmission rates of the first data transmission rule. In this case, it is possible that when a communicant in which both data transmission rules are implemented receives the second information element, only the parameters which relate to the second information element are stored. The method according to the invention can also be expanded in a manner which corresponds to the first and second information elements in that, in addition to the second information element, a third or further information element or elements is or are also formed, which represents or represent third or further data transmission rules. One refinement of the method according to the invention provides that the data transmission rates are coded with the aid of value pairs instead of single values. In this case, the one value of the pair codes the data transmission rule itself and the other value codes the data rate. In this case, it is particularly expedient to make the coding of the data rate dependent on the data transmission rule. This allows very flexible extension for new data transmission rules. The object is also achieved by a communication device in which a second data transmission rule with an expanded value range of the element identification part is implemented. The transmitting unit can send two information elements which are defined by a second standardized value of the element identification part. In this case, its information part contains parameters which relate to the data transmission in accordance with the second data transmission rule. When the second communicant is unknown, this communication device makes it possible, for example, first of all to attempt to send information elements in accordance with the second data transmission rule. In this case, an element identification part is provided with the standardized value. At the receiver end, it is thus possible to identify a transmitter which can operate in accordance with the second data transmission rule. If the second communicant can likewise operate using the second data transmission rule, it can be set to the appropriate operating mode. If it can operate only in accordance with the first data transmission rule, it will not be able to “understand” the standardized value, since this is outside the permissible value range. This receiver will therefore jump over the information element. A communication device designed in this way does not interfere with second communicants which are implemented as communication devices in which only the first data transmission rule is implemented. In one embodiment of the invention, a receiving unit which is designed for reception of a first and of a second information element is arranged in the communication device. The communication device according to the invention is thus suitable not only for transmission but also for reception of information both in accordance with the first and the second data transmission rule. A further embodiment of the communication device according to the invention can be switched between first and second data transmission rules as a function of the reception of information elements during transmission. The communication device is thus both backwards and forwards compatible. Specifically, if information is received in accordance with the first data transmission rule, the communication device can switch to operate with the first data transmission rule, and both communicants then continue their communication on the basis of the first data transmission rule. If the communication device receives information with the second data transmission rule—for example by means of an identically designed communication device as the communicant at the other end, it will switch to operate in accordance with the second data transmission rule. The communication device according to the invention is advantageously provided with a memory which is designed to store parameters of received second information elements. By way of example, the communication can thus be started straight away in accordance with the second data transmission rule at a later time, when this is stored, since the second data transmission rule was already relevant in a previous communication, and it can be assumed that the same communicant is still located in the vicinity. This therefore makes it possible initially to avoid the time for matching to the data transmission rule. One development provides for a memory to be arranged, which is designed to store parameters of the received first and second information elements. In consequence, the same method as that described above can also be used for the first data transmission rule. It is particularly advantageous to develop the communication device in such a way that a third or further data transmission rule or rules is or are implemented in the same way as the second data transmission rule. This also makes it possible to widen the backwards and forwards compatibility for other data transmission rules.
20060125
20080212
20060622
74466.0
H04L2700
1
CASCA, FRED A
METHOD AND COMMUNICATION DEVICE FOR EXPANDING THE RANGE OF DATA TRANSMISSION RATES IN WIRELESS LOCAL AREA NETWORKS
UNDISCOUNTED
0
ACCEPTED
H04L
2,006
10,540,401
ACCEPTED
Radio communication apparatus and radio communication method
A CIR measuring section 307 measures CIRs of all blocks received and a block selection section 308 makes a threshold decision based on the CIR measurement result and threshold information according to an amount of traffic in the own cell and neighboring cells. As a result of the threshold decision, blocks whose CIRs exceed the threshold are regarded as usable blocks. A CIR averaging section 309 averages the CIRs of the usable blocks and a CQI generation section 310 generates a CQI based on the CIR average value. The CQI generated and selected block numbers are reported to a base station apparatus. This allows the throughput of the own cell and neighboring cells to be improved.
1. A radio communication apparatus comprising: a reception section that receives an OFDM signal; a reception quality measuring section that demodulates the received OFDM signal and measures reception quality of each subcarrier; a subcarrier selection section that selects subcarriers having top-ranking reception quality as subcarriers to be used based on a criterion notified from the other party of communication; an averaging section that averages the reception quality of the subcarriers selected by said subcarrier selection section; and a reporting section that generates a report value indicating the reception quality averaged by said averaging section and reports the report value generated and information indicating the subcarriers selected by said subcarrier selection section to the other party of communication. 2. The radio communication apparatus according to claim 1, wherein said subcarrier selection section selects subcarriers of reception quality equal to or higher than a threshold as subcarriers to be used based on reception quality and a threshold decision against a threshold notified from the other party of communication. 3. The radio communication apparatus according to claim 2, wherein said threshold is controlled adaptively according to an amount of traffic in the own cell and neighboring cells. 4. The radio communication apparatus according to claim 1, wherein said subcarrier selection section selects the same number of subcarriers as that notified from the other party of communication. 5. The radio communication apparatus according to claim 4, wherein said number of subcarriers is controlled adaptively according to an amount of traffic in the own cell and neighboring cells. 6. The radio communication apparatus according to claim 2, wherein said subcarrier selection section selects subcarriers to be used from among the subcarriers restricted beforehand out of all subcarriers. 7. A communication terminal apparatus comprising the radio communication apparatus according to claim 1. 8. A radio communication method comprising the steps of: selecting subcarriers having top-ranking reception quality as subcarriers to be used based on a criterion notified from the other party of communication; generating a report value indicating average reception quality of the selected subcarriers; and reporting the report value generated and information indicating the selected subcarriers to the other party of communication. 9. A radio communication system comprising: a base station apparatus that sends information which becomes a selection criterion of subcarriers according to an amount of traffic in the own cell and neighboring cells to a communication terminal apparatus; and a communication terminal apparatus that selects subcarriers having top-ranking reception quality as subcarriers to be used based on selection criterion information sent from said base station apparatus and reception quality of each subcarrier, and reports a report value indicating average reception quality of the selected subcarriers and information indicating the selected subcarriers to said base station apparatus.
TECHNICAL FIELD The present invention relates to a radio communication apparatus and radio communication method in a multicarrier transmission, and is suitable for use in, for example, an OFDM (Orthogonal Frequency Division Multiplex) communication terminal apparatus. BACKGROUND ART In a conventional W-CDMA (Wideband-Code Division Multiple Access) mobile communication system, a downlink high-speed packet transmission scheme (HSDPA: High Speed Downlink Packet Access) is being developed under which a high-speed, large-capacity downlink channel is shared among a plurality of communication terminal apparatuses and packet data is transmitted from a base station apparatus to a communication terminal apparatus at high speed. Here, HSDPA in a W-CDMA system will be explained briefly. A communication terminal apparatus measures a reception CIR (Carrier to Interference Ratio) and reports information (e.g., CQI: Channel Quality Indicator) indicating a downlink channel condition to a base station apparatus based on the measured CIR. The base station apparatus determines a communication terminal apparatus to which packet data is to be sent (transmission destination apparatus) based on CQIs reported from the respective communication terminal apparatuses. This is called “scheduling.” Furthermore, the base station apparatus determines according to what modulation scheme and what coding rate (MCS: Modulation and Coding Scheme) packet data to be sent to the transmission destination apparatus should be processed based on the downlink channel condition indicated by the CQI. This is called “MCS assignment.” The base station apparatus sends packet data to the determined transmission destination apparatus according to the determined MCS. As a specific example of MCS assignment, suppose a case where a fading variation as shown in FIG. 1 occurs. FIG. 1 illustrates a time variation of reception power due to fading. Suppose, the horizontal axis shows a time, the vertical axis shows reception power, and the reception power becomes a maximum at t1 and the reception power becomes a minimum at t2. It is decided that the propagation path is in a good condition at t1 and a high MCS level (e.g., 16QAM, coding rate ¾) is assigned. On the other hand, it is decided that the propagation path is in a poor condition at t2 and a low MCS level (e.g., QPSK, coding rate ¼) is assigned. That is, when the propagation path is in a good condition, high-speed transmission is possible. Therefore, if a communication terminal apparatus assigned a high MCS level is determined as the transmission destination, it is possible to send a large amount of data in a short time and thereby improve throughput of the system. Furthermore, a conventional W-CDMA system maintains reception quality per bit by controlling transmit power, while the HSDPA can maintain reception quality per bit by controlling the MCS as described above. The above described HSDPA is a technology based on the premise that it is used for a W-CDMA system, and the application of the HSDPA technology to an OFDM (Orthogonal Frequency Division Multiplexing) communication apparatus which is a promising next-generation communication scheme is under study. The following are examples of the HSDPA technology applied to OFDM. CONVENTIONAL EXAMPLE 1 A communication terminal apparatus measures reception CIRs of all subcarriers and reports a CQI to a base station apparatus based on the measured CIRs. Based on the CQIs reported from the respective communication terminal apparatuses, the base station apparatus performs scheduling and MCS assignment and carries out transmission using all the subcarriers. Furthermore, the base station apparatus distributes subcarriers uniformly over all frequencies and send the subcarriers. Furthermore, the base station apparatus also prepares subcarriers not to be used to reduce interference with neighboring cells. When the number of users of the neighboring cells increases, it is possible to prevent a lot of interference with the neighboring cells by increasing the number of subcarriers not to be used and improve the system throughput. FIG. 2 illustrates a frequency assignment method in conventional example 1. Here, assuming the number of users is 2, a situation in which frequencies are assigned to UE1 and UE2 is shown as an example. Suppose a frequency band used in the system is 5 MHz and the number of subcarriers is 512. In conventional example 1, as shown in FIG. 2, all subcarriers are assigned in order of UE1, UE2 and unassigned subcarrier (assigned to no target). Subcarriers assigned to no target are assigned between UE1 and UE2 subcarriers. CONVENTIONAL EXAMPLE 2 In conventional example 2, a communication terminal apparatus measures reception CIRs of all subcarriers and reports CQI to a base station apparatus based on the measured reception CIRs. The base station apparatus determines a communication terminal apparatus as the transmission destination (can also be plural), MCS and subcarriers based on the CQIs reported from the respective communication terminal apparatuses. From the next time of transmission on, the communication terminal apparatus generates a CQI based on the CIRs of the assigned subcarriers and reports this CQI to the base station apparatus. When the base station apparatus uses the same subcarriers for the communication terminal apparatus next time, it is possible to realize MCS assignment according to a more accurate CQI. FIG. 3 conceptually shows this method. FIG. 3 conceptually shows a communication method in conventional example 2. This figure assumes a case where Node B (base station apparatus) is communicating with UE1 to 3 (communication terminal apparatus 1 to 3). First, UE1 to 3 send CQIs about all subcarriers to Node B in the initial transmission ((1) in the figure). Node B carries out scheduling based on the transmitted CQIs and starts to transmit data ((2) in the figure). For the next time transmission, UE1 to 3 transmit CQIs about assigned frequencies (subcarriers) to Node B ((3) in the figure) Node B carries out scheduling for the next time transmission and transmits data to UE3 ((4) in the figure). In this example, in (2) in the figure, suppose Node B assigns frequencies (subcarriers) to UE1 to 3 as shown in FIG. 4. FIG. 4 illustrates a frequency assignment method in conventional example 2. Here, only parts different from FIG. 2 will be explained and assuming that the number of users is 3, a situation in which frequencies are assigned to UE1 to 3 is shown. In conventional example 2, neighboring subcarriers are collectively assigned to users and unassigned subcarriers (assigned to no target) are provided to reduce interference with neighboring cells. However, above described conventional examples 1 and 2 have a problem that subcarriers having low reception power may be assigned. This will be explained using FIG. 5 and FIG. 6. FIG. 5 conceptually shows reception power of subcarriers assigned in conventional example 1 at the communication terminal apparatus. Here, the state of reception power is shown as case 1 (FIG. 5A) and case 2 (FIG. 5B). As is seen from this figure, both subcarriers having high reception power (in a good propagation situation) and subcarriers having low reception power (in a bad propagation situation) are assigned. Furthermore, FIG. 6 conceptually shows reception power of subcarriers assigned in conventional example 2 at the communication terminal apparatus. FIG. 6 also shows states of reception power similar to those in FIG. 5 as case 1 (FIG. 6A) and case 2 (FIG. 6B). According to this method, it is possible to transmit data with an MCS according to a propagation situation of subcarriers, but as shown in FIG. 6, subcarriers having low reception power (in a bad propagation situation) are assigned, resulting in a low MCS level. Especially, in the situation of case 2, all the subcarrier assigned may have low reception power. In this way, data transmitted with subcarriers with reduced reception power cannot be decoded, retransmission of the data may be requested or data may be transmitted with a low MCS level, which causes throughput to be reduced. Furthermore, the communication terminal apparatus may also generate CQIs for all subcarriers separately and report them to the base station apparatus, but this may increase the number of transmission bits for reports and overweigh the uplink. Furthermore, for example, in a system of reuse 1 (frequency iteration 1) using the same frequency in neighboring cells as shown in FIG. 7, a signal transmitted by Node B#1 to a UE in the own cell becomes interference with neighboring cells (Nodes B#2 and #3). In such a system, the number of subcarriers used in the own cell determines interference with neighboring cells and a large amount of interference with neighboring cells will cause the throughput of the entire system to reduce. For this reason, it is necessary to carry out transmission with a limited number of subcarriers efficiently. DISCLOSURE OF INVENTION It is an object of the present invention to provide a radio communication apparatus and radio communication method that improve throughput of the own cell and neighboring cells. The present invention attains the above described object by selecting subcarriers of high reception quality as subcarriers to be used based on a criterion determined by amounts of traffic of the own cell and neighboring cells, creating a report value indicating average reception quality of the selected subcarriers and reporting the report value created and information indicating the subcarriers to be used to the other party of communication. BRIEF DESCRIPTION OF DRAWINGS FIG. 1 illustrates a time variation of reception power due to fading; FIG. 2 illustrates a frequency assignment method in conventional example 1; FIG. 3 conceptually illustrates a communication method in conventional example 2; FIG. 4 illustrates a frequency assignment method in conventional example 2; FIG. 5A conceptually illustrates reception power of subcarriers assigned in conventional example 1 at a communication terminal apparatus; FIG. 5B conceptually illustrates reception power of subcarriers assigned in conventional example 1 at the communication terminal apparatus; FIG. 6A conceptually illustrates reception power of subcarriers assigned in conventional example 2 at the communication terminal apparatus; FIG. 6B conceptually illustrates reception power of subcarriers assigned in conventional example 2 at the communication terminal apparatus; FIG. 7 illustrates a conceptual view showing a situation of interference with neighboring cells in a system of reuse 1; FIG. 8 is a schematic diagram conceptually illustrating subcarrier blocks; FIG. 9 is a block diagram illustrating the configuration of a transmission system of a base station apparatus according to Embodiment 1 of the present invention; FIG. 10 is a block diagram showing the configuration of a reception system of a communication terminal apparatus according to Embodiment 1 of the present invention; FIG. 11A illustrates a method of selecting usable blocks in Embodiment 1 of the present invention; FIG. 11B illustrates a method of selecting usable blocks in Embodiment 1 of the present invention; FIG. 12 illustrates an example of block assignment according to Embodiment 1 of the present invention; FIG. 13A illustrates a method of selecting usable blocks according to Embodiment 1 of the present invention; FIG. 13B illustrates a method of selecting usable blocks according to Embodiment 1 of the present invention; FIG. 14 illustrates a block assignment example according to Embodiment 1 of the present invention; FIG. 15 is a block diagram showing the configuration of a transmission system of a base station apparatus according to Embodiment 2 of the present invention; FIG. 16A illustrates a method of selecting usable blocks according to Embodiment 2 of the present invention; FIG. 16B illustrates a method of selecting usable blocks according to Embodiment 2 of the present invention; FIG. 17 illustrates a block assignment example according to Embodiment 2 of the present invention; FIG. 18 is a block diagram showing the configuration of a transmission system of a base station apparatus according to Embodiment 3 of the present invention; FIG. 19 is a block diagram showing the configuration of a reception system of a communication terminal apparatus according to Embodiment 3 of the present invention; FIG. 20A illustrates a method of selecting usable blocks according to Embodiment 3 of the present invention; and FIG. 20B illustrates a method of selecting usable blocks according to Embodiment 3 of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION With reference now to the attached drawings, embodiments of the present invention will be explained below. According to embodiments of the present invention, as shown in FIG. 8, suppose assignment is performed in block units assuming that the number of subcarriers to be used is 512, one subcarrier block (hereinafter simply referred to as “block”) consists of 32 subcarriers and a total of 16 blocks are used unless specified otherwise. Each block is assigned a number (block number) for identifying the block. EMBODIMENT 1 FIG. 9 is a block diagram showing the configuration of a transmission system of a base station apparatus according to Embodiment 1 of the present invention. In this figure, a scheduler section 201 determines (scheduling) to which communication terminal apparatus transmission in the next frame is carried out based on a CQI reported from each communication terminal apparatus in communication and outputs the determined scheduling information to a user selection section 202. As an algorithm of this scheduling, Max C/I, Proportional Fairness, etc., is available. Furthermore, when a user signal to be transmitted is determined through the scheduling, a modulation scheme and coding rate (MCS: Modulation and Coding Scheme) are assigned to the user signal and the assigned MCS is notified to coding sections 203-1, 203-2 and modulation sections 204-1, 204-2. Furthermore, at the same time the scheduler section 201 receives a report on usable block numbers from each communication terminal apparatus and determines which of the reported blocks is used for each communication terminal apparatus and notifies it to the subcarrier mapping sections 205-1, 205-2. The user selection section 202 temporarily stores transmission data to be sent to each communication terminal apparatus (assumed to be UE1 to UE3 in this figure as an example), selects data to be sent to the communication terminal apparatus which becomes the transmission destination according to the scheduling information output from the scheduler section 201 and outputs the data to the coding sections 203-1, 203-2. According to this embodiment, there are two lines of system that carry out coding, modulation and subcarrier mapping, the user selection section 202 can select two pieces of transmission data and perform processing of the same contents in parallel on the respective lines. Therefore, only one line of system will be explained. In addition, one more line of system is provided as a control data processing section 207 that carries out coding, modulation and subcarrier mapping on control data. The control data processing section 207 will be explained later. The coding section 203-1 carries out coding processing on transmission data output from the user selection section 202 using a turbo code, etc., at a coding rate notified from the scheduler section 201 and outputs the processed data to the modulation section 204-1. The modulation section 204-1 carries out modulation processing on the transmission data output from the coding section 203-1 according to the modulation scheme notified from the scheduler section 201 and outputs the modulated data to the subcarrier mapping section 205-1. The subcarrier mapping section 205-1 maps the modulated transmission data output from the modulation section 204-1 to a subcarrier determined by the scheduler section 201 and outputs the mapped data to the multiplexing section 208. A threshold calculation section 206 calculates a CIR threshold which is a selection criterion for selecting usable blocks at the communication terminal apparatus based on information on traffic in the own cell and neighboring cells. A CIR threshold (ThCIR) is calculated, for example, as ThCIR=S0-10 log (γ0/Σγi). At this time, S0 denotes a reference CIR and is, for example, −10 dB. γ0 denotes an amount of traffic in the own cell and 10 log (γ0/Σγi) is a ratio (dB) of the amount of traffic in the own cell to the total amount of traffic in the own cell and 6 neighboring cells. When S0=−10 dB, γ0/Σγi=1/10, the CIR threshold to be set is 0 dB. The threshold information calculated in this way is output to the control data processing section 207. The control data processing section 207 carries out coding processing (coding section 207-1) on the threshold information output from the threshold calculation section 206, modulation processing (modulation section 207-2) and mapping (subcarrier mapping section 207-3) to subcarriers and outputs the processing result to the multiplexing section 208. The multiplexing section 208 multiplexes the transmission data, control data including threshold information, a pilot line, output from the subcarrier mapping sections 205-1, 205-2, 207-3 respectively, and outputs the multiplexed data to an S/P conversion section 209. The S/P conversion section 209 converts the multiplexed signal output from the multiplexing section 208 to a plurality of lines of transmission data and outputs the lines of transmission data to an IFFT section 210. The IFFT section 210 carries out an inverse fast Fourier transform on the plurality of lines of transmission data output from the S/P conversion section 209, thereby forms an OFDM signal and outputs the OFDM signal to a GI insertion section 211. The GI insertion section 211 inserts a guard interval (GI) into the OFDM signal output from the IFFT section 210 and outputs the OFDM signal to a radio processing section 212. The radio processing section 212 carries out predetermined radio processing such as D/A conversion and up-conversion on the signal output from the GI insertion section 211 and transmits the signal subjected to the radio processing to a communication terminal apparatus through an antenna. FIG. 10 is a block diagram showing the configuration of a reception system of a communication terminal apparatus according to Embodiment 1 of the present invention. In this figure, a radio processing section 301 receives the signal sent from the base station apparatus through an antenna, carries out predetermined radio processing such as down-conversion and A/D conversion on the received signal and outputs the signal after the radio processing to a GI elimination section 302. The GI elimination section 302 removes the guard interval from the signal output from the radio processing section 301 and outputs the signal deprived of the guard interval to an FFT section 303. The FFT section 303 carries out a fast Fourier transform on the signal output from the GI elimination section 302 and thereby acquires signals transmitted through the respective blocks. The acquired signals in block units are output to a channel separation section 304. The channel separation section 304 separates the signals in block units (actually in subcarrier units) output from the FFT section 303 into user specific lines and extracts a data section, pilot section and control data section (including threshold information) directed to the own apparatus. The extracted data section is output to a demodulation section 305-1, subjected to demodulation processing by the demodulation section 305-1 and output to a decoding section 306-1. The decoding section 306-1 decodes the demodulated signal output from the demodulation section 305-1and extracts the user data. On the other hand, the control data section extracted by the channel separation section 304 is output to a demodulation section 305-2, subjected to demodulation processing by the demodulation section 305-2 and output to a decoding section 306-2. The decoding section 306-2 decodes the demodulated signal output from the demodulation section 305-2, extracts the control data and outputs the threshold information included in the control data to a block selection section 308. Furthermore, the pilot section extracted by the channel separation section 304 is output to a CIR measuring section 307 as a reception quality measuring section, where CIRs of all subcarriers are measured. The CIR measurement result is output to the block selection section 308. The block selection section 308 makes a decision on the CIR measurement result output from the CIR measuring section 307 against a threshold based on the threshold information output from the decoding section 306-2. That is, the block selection section 308 selects blocks equal to or greater than the threshold as usable blocks and outputs CIRs of the selected blocks to a CIR averaging section 309. Furthermore, the blocks numbers of the selected blocks are output to a transmission section (not shown). The CIR averaging section 309 averages the CIRs of the usable blocks output from the block selection section 308 and outputs the averaged value to a CQI generation section 310. The CQI generation section 310 includes a CQI table in which a CIR, modulation scheme (QPSK and 16QAM, etc.) coding rate are associated with each CQI, searches for a CQI from the CQI table based on the value averaged by the CIR averaging section 309 and generates a CQI. The CQI generated is output to the transmission section (not shown). That is, a CQI corresponding to the value obtained by averaging CIRs of blocks equal to or greater than the threshold is generated. The CQI output from the CQI generation section 310 and usable block numbers are sent to the base station apparatus through the uplink. The operations of the above described base station apparatus and communication terminal apparatus will be explained using FIG. 11 to FIG. 14 divided into two cases; one with a large amount of traffic in the own cell and neighboring cells and the other with a small amount of traffic. First, the case with a large amount of traffic will be explained using FIG. 11 and FIG. 12. The block selection section 308 in the communication terminal apparatus selects blocks as shown in FIG. 11. FIG. 11 illustrates a method of selecting usable blocks according to Embodiment 1 of the present invention. Here, two situations of CIR are shown as case 1 where there is a plurality of mountains having the same CIR level (FIG. 11A) and case 2 where there is only one mountain of a high CIR (FIG. 11B). The block selection section 308 of the communication terminal apparatus makes a threshold decision based on the CIRs measured in block units and the threshold information sent from the base station apparatus. This threshold reflects the fact that there is a large amount of traffic in the own cell and neighboring cells and is set to a relatively high value. For this reason, there are relatively fewer blocks which are equal to or greater than the threshold and it is possible to reduce interference with neighboring cells. As a result of the threshold decision by the block selection section 308, blocks whose measured CIRs are equal to or greater than the threshold are selected as usable blocks (blocks with shading in the figure), whereas blocks whose measured CIRs are smaller than the threshold (white blocks in the figure) are excluded as unusable blocks. Then, the CIRs of the blocks selected as usable blocks are output to the CIR averaging section 309 and the block numbers (information) of the selected blocks are output to the transmission section. The CIR averaging section 309 averages the CIRs output from the block selection section 308 to a CIR per block and the CQI generation section 310 generates a CQI corresponding to the averaged CIR. The CQI generated is output to the transmission section and sent to the base station apparatus together with the block numbers output from the block selection section 308. This eliminates the necessity for reporting CQIs of all blocks equal to or greater than the threshold to the base station apparatus and can thereby reduce amount of data transmitted over the uplink. At the base station apparatus, the scheduler section 201 assigns blocks based on CQIs reported from the respective communication terminal apparatuses and usable block numbers. FIG. 12 illustrates an example of block assignment according to Embodiment 1 of the present invention. Here, the number of communication terminal apparatuses to which blocks are assigned is assumed to be 2 and the communication terminal apparatuses are expressed as UE1 and UE2. As shown in FIG. 12, the base station apparatus assigns block numbers 14 and 15 to UE1 and block numbers 8 to 11 to UE2, which is assignment of a relatively small number of only blocks having good reception quality for the respective UEs. Thus, in the case with a large amount of traffic in the own cell and neighboring cells, assigning many blocks within the own cell by reducing a threshold would cause a large amount of interference with neighboring cells, preventing the neighboring cells from using most of blocks and thereby causing the throughput of the entire system to decrease. For this reason, by increasing a threshold and reducing the number of blocks to be used in the own cell, it is possible to reduce interference with the neighboring cells. This allows the throughput of the neighboring cells to be increased. On the other hand, setting too high a threshold extremely reduces the number of usable blocks in the own cells causing the throughput in the own cell to be reduced, and therefore it is necessary to increase the number of blocks to be used in the own cell within a range which will not cause a large amount of interference with neighboring cells. Next, the case with a small amount of traffic in the own cell and neighboring cells will be explained using FIG. 13 and FIG. 14. FIG. 13 illustrates a method of selecting usable blocks according to Embodiment 1 of the present invention. In this figure, conditions except the threshold are the same as those in FIG. 11. The threshold in the case with a small amount of traffic is set to a smaller value than in the case with a large amount of traffic. For this reason, the number of blocks exceeding the threshold is relatively large and it is possible to use more blocks, but in the case with a small amount of traffic, the channel usage rate with time in neighboring cells is low, and therefore interference with the neighboring cells is not a big problem. In the case with a small amount of traffic just like the case with a large amount of traffic, blocks exceeding the threshold are regarded as usable blocks, CQIs are generated based on a value obtained by averaging CIRs of the usable blocks and the CQIs and usable block numbers are sent from the transmission section to the base station apparatus. In the base station apparatus, the scheduler section 201 assigns blocks based on the CQIs and usable block numbers reported from the respective communication terminal apparatuses as in the case with a large amount of traffic. FIG. 14 illustrates an example of block assignment according to Embodiment 1 of the present invention. As shown in FIG. 14, the base station apparatus assigns block numbers 3 to 5 and 13 to 16 to UE1 and block numbers 6 to 12 to UE2, that is, the base station apparatus assigns more blocks compared to the case with a large amount of traffic. Thus, irrespective of whether the amount of traffic is large or small, only blocks with high reception quality are used, and therefore it is possible to assign a high MCS. For example, when transmission based on QPSK using 12 blocks including blocks of low quality is compared to transmission based on 64QAM using 6 blocks of high quality, the latter can obtain throughput 1.5 times that of the former and can also reduce interference with other cells by half. Irrespective of whether the amount of traffic is large or small, when a plurality of communication terminal apparatuses set the same block as a usable block simultaneously, the present invention may also be adapted so that the block is assigned to communication terminal apparatuses having higher CQIs. Furthermore, for a threshold decision made by the block selection section 308, it is also possible to use a difference obtained by subtracting an average CIR of all blocks from a CIR of each block, that is, (CIR of each block)−(average CIR). By so doing, it is possible for also the user in the center of the cell to use only blocks of relatively high quality and suppress interference with neighboring cells efficiently. Thus, according to this embodiment, it is possible to select only blocks of high reception quality exceeding a predetermined threshold as blocks to be used, and thereby improve throughput while suppressing interference with neighboring cells out of a limited number of blocks by carrying out transmission with a high MCS. Furthermore, changing a threshold used to select usable blocks according to an amount of traffic in the own cell and neighboring cells reflects an allowable amount of interference with other cells, and can thereby realize highly efficient transmission. EMBODIMENT 2 Embodiment 1 has described the case where usable blocks are selected based on a threshold decision on CIRs and the threshold is controlled according to an amount of traffic in the own cell and neighboring cells. Embodiment 2 of the present invention will describe a case where usable blocks are selected within a predetermined number of blocks and the number of blocks is determined according to an amount of traffic. FIG. 15 is a block diagram showing the configuration of a transmission system of a base station apparatus according to Embodiment 2 of the present invention. However, components in FIG. 15 common to those in FIG. 9 are assigned the same reference numerals as those in FIG. 9 and detailed explanations thereof will be omitted. What FIG. 15 differs from FIG. 9 is that the threshold calculation section 206 has been changed to an assignment block number calculation section 801. The assignment block number calculation section 801 calculates the number of blocks which is a selection criterion for selecting usable blocks in a communication terminal apparatus based on the amounts of traffic in the own cell and neighboring cells. The calculation of the number of blocks (assumed to be Nsb) can be expressed, for example, by the following expression: Nsb=└Nall×γ0/Σκ (1) Nall denotes the number of blocks of all subcarriers and is, for example, 64. γ0 denotes an amount of traffic of the own cell and γ0/Σγi denotes the ratio of the amount of traffic in the own cell to the total amount of traffic in the own cell and 6 neighboring cells. Furthermore, the symbol in the right side denotes a maximum integer that does not exceed the number enclosed therein and is expressed, for example, as follows: └2.4┘=2 (2) More specifically, when Nall=64, γ0/Σγi=1/10, Nsb=6. The information on the number of assigned blocks calculated in this way is output to the control data processing section 207. Reducing the number of selectable blocks in the assignment block number calculation section 801 can reduce interference with neighboring cells. Causing more interference with the neighboring cells prevents most of blocks from being used and reduces the system throughput. On the other hand, reducing the number of selectable blocks excessively will cause the throughput in the own cell to reduce. Therefore, this embodiment determines the number of selectable blocks in consideration of the amount of traffic in the own cell and neighboring cells, and can thereby avoid a large amount of interference with neighboring cells and prevent the throughput of the own cell from reducing. The configuration of the reception system of the communication terminal apparatus according to Embodiment 2 of the present invention is the same as that in FIG. 10 and only the function of the block selection section 308 is different, and therefore the reception system will be explained using FIG. 10 and detailed explanations of functional blocks common to FIG. 10 will be omitted. The decoding section 306-2 carries out decoding processing on the control data section output from the demodulation section 305-2, extracts control data and notifies the information on the number of selectable blocks included in the control data to the block selection section 308. The block selection section 308 selects usable blocks based on CIRs measured for all blocks by the CIR measuring section 307 and the number of selectable blocks (Nsb) output from the decoding section 306-2. More specifically, the block selection section 308 selects blocks corresponding to top-ranking Nsb CIRs as usable blocks. The CIRs of the selected usable blocks are averaged by the CIR averaging section 309, a CQI corresponding to the CIR average value is generated by the CQI generation section 310 and the CQI is output to the transmission section. The block numbers of the usable blocks selected by the block selection section 308 are output to the transmission section. The operations of the above described base station apparatus and communication terminal apparatus will be explained using FIG. 16 and FIG. 17. The block selection section 308 of the communication terminal apparatus selects blocks as shown in FIG. 16. FIG. 16 illustrates a method of selecting usable blocks according to Embodiment 2 of the present invention. Here, two situations of CIR are shown as case 1 where there is a plurality of mountain shaving the same CIR level (FIG. 16A) and case 2 where there is only one mountain of a high CIR (FIG. 16B) assuming that the number of usable blocks (Nsb) is 6. The block selection section 308 selects usable blocks based on a CIR measured for each block and information on the number of usable blocks sent from the base station apparatus. That is, blocks corresponding to top-ranking Nsb CIRs are selected as usable blocks and as shown in case 1 and case 2 in FIG. 16, 6 blocks are selected as specified usable blocks in both cases. Here, blocks are selected from those having top-ranking CIRs because it is thereby possible to prevent assignment of blocks of low quality, realize highly efficient transmission and reduce interference with neighboring cells. This allows the throughput of the entire system to be improved. Furthermore, when an MCS is assigned as in the case of this embodiment, use of blocks of higher quality makes it possible to assign a higher MCS, and thereby further improve the throughput. For example, when transmission based on QPSK using 12 blocks including blocks of low quality is compared to transmission based on 64QAM using only 6 blocks of high quality, the latter can obtain throughput 1.5 times that of the former and also reduce interference with other cells by half. The CIRs of the selected usable blocks are averaged by the CIR averaging section 309, a CQI corresponding to the CIR average value is generated by the CQI generation section 310 and the CQI is output to the transmission section. Furthermore, the block numbers of the usable blocks selected by the block selection section 308 are output to the transmission section. In the base station apparatus, the scheduler section 201 assigns blocks based on the CQI and usable block numbers reported from each communication terminal apparatus. FIG. 17 illustrates an example of block assignment according to Embodiment 2 of the present invention. Here, the figure illustrates a case where the usable blocks shown in case 1 in FIG. 16 are assigned to UE1. The base station apparatus assigns block numbers 4, 5, 9, 10, 14, 15 to UE1. Thus, this embodiment selects a predetermined number of blocks having high reception quality as blocks to be used, and can thereby improve throughput with a limited number of usable blocks through transmission at a high MCS while suppressing interference with neighboring cells. Furthermore, changing the number of usable blocks according to the amount of traffic in the own cell and neighboring cells reflects the allowable amount of interference with other cells, and can thereby carry out highly efficient transmission. EMBODIMENT 3 Embodiment 3 of the present invention will describe a case where blocks available to a communication terminal apparatus is predetermined according to an amount of traffic in the own cell and neighboring cells and blocks to be used are selected according to the CIR threshold explained in Embodiment 1. FIG. 18 is a block diagram showing the configuration of a transmission system of a base station apparatus according to Embodiment 3. However, the components in FIG. 18 common to those in FIG. 9 are assigned the same reference numerals as those in FIG. 9 and detailed explanations thereof will be omitted. What FIG. 18 differs from FIG. 9 is that a specified block determining section 1101 is added and the scheduler section 201 is changed to a scheduler section 1102. The threshold calculation section 206 calculates a CIR threshold for deciding usable blocks at a communication terminal apparatus based on information on the traffic in the own cell and neighboring cells. The calculated threshold is output to the control data processing section 207. The specified block determining section 1101 determines blocks (selectable blocks) to be specified to the communication terminal apparatus based on the amount of traffic in the own cell and neighboring cells. The information on the determined blocks to be specified (selection criterion information) is output to the scheduler section 1102 and control data processing section 207. The scheduler section 1102 determines to which communication terminal apparatus transmission should be performed in the next frame based on a CQI reported from each communication terminal apparatus in communication, usable block numbers and specified block information output from the specified block determining section 1101 and outputs the determined scheduling information to the user selection section 202. The rest of the processing is the same as that in Embodiment 1. FIG. 19 is a block diagram showing the configuration of a reception system of a communication terminal apparatus according to Embodiment 3 of the present invention. However, the components in FIG. 19 common to those in FIG. 10 are assigned the same reference numerals as those in FIG. 10 and detailed explanations thereof will be omitted. What FIG. 19 differs from FIG. 10 is that the CIR measuring section 307 is changed to a CIR measuring section 1201. The decoding section 306-2 carries out decoding processing on the control data section output from the demodulation section 305-2, extracts control data, outputs the information on specified blocks included in the control data to the CIR measuring section 1201 and outputs the threshold information also included in the control data to the block selection section 308. The CIR measuring section 1201 carries out CIR measurement on only the blocks specified by the pilot sections of the blocks indicated by the information on the blocks to be specified output from the decoding section 306-2 out of the pilot sections output from the channel separation section 304. Here, the CIR measuring section 1201 carries out CIR measurement on only the blocks specified by the base station apparatus, and therefore compared to the case where CIR measurement is performed on all blocks, it is possible to reduce an amount of processing required for CIR measurement and at the same time shorten the time required for processing. The measured CIR is output to the block selection section 308. The block selection section 308 makes a threshold decision on the CIR measurement result output from the CIR measuring section 1201 based on the threshold information output from the decoding section 306-2. The block selection section 308 needs to make a threshold decision on the CIR measurement result output from the CIR measuring section 1201 for only blocks specified by the base station apparatus instead of all blocks, and can thereby reduce the amount of processing and reduce the time required for processing. As a result of the threshold decision, blocks equal to or greater than the threshold are regarded as usable blocks and CIRs of these blocks are output to the CIR averaging section 309 and these block numbers are output to a transmission section (not shown). The operations of the above described base station apparatus and communication terminal apparatus will be explained using FIG. 20. FIG. 20 illustrates a method of selecting usable blocks in Embodiment 3 of the present invention. Here, two situations of CIR are shown as case 1 where there is a plurality of mountains having the same CIR level (FIG. 20A) and case 2 where there is only one mountain of a high CIR (FIG. 20B). The block selection section 308 of the communication terminal apparatus makes a threshold decision on CIRs measured about the blocks specified by the base station apparatus based on the threshold information sent from the base station apparatus. In case 1 in FIG. 20A, the blocks specified from the base station apparatus are five blocks from the left, but the blocks exceeding the threshold are up to the fourth block from the left. Furthermore, in case 2 in FIG. 20B, the block specified from the base station apparatus are five blocks from the left, but only the fifth block from the left is the block that exceeds the threshold. In this way, the usable blocks selected by the communication terminal apparatus are limited to blocks specified before hand, and therefore it is possible to reduce an amount of data of block numbers when the usable block numbers are reported to the base station apparatus. Thus, according to this embodiment, the base station apparatus specifies blocks to be assigned to the communication terminal apparatus beforehand according to the amount of traffic in the own cell and neighboring cells, and can thereby reduce an amount of processing and processing time required to select usable blocks at the communication terminal apparatus and also reduce an amount of information on block numbers used to be reported to the base station apparatus. The blocks specified by the base station apparatus may also be changed according to a predetermined pattern instead of being calculated and notified every time. Furthermore, this embodiment has explained the case where blocks to be assigned to a communication terminal apparatus are restricted and then applied to Embodiment 1, but blocks may also be applied to Embodiment 2. When applied to Embodiment 2, blocks corresponding to top-ranking Nsb CIRs are selected as usable blocks. The above described embodiments have explained the case where an MCS is assigned, but the present invention is also applicable to cases where no MCS is assigned. Furthermore, in the respective embodiments, the base station apparatus calculates a threshold, calculates the number of blocks assigned and determines blocks to be specified, but a higher-level control apparatus can also perform these calculation and determination. These calculation and determination are performed based on traffic information, but may also be performed based on the number of users. Furthermore, the respective embodiments assume that the number of subcarriers used is 512 and one block consists of 32 subcarriers, but the present invention is not limited to this and the number of subcarriers may also be set arbitrarily. As explained above, according to the present invention, subcarriers of high reception quality are selected as subcarriers to be used based on a criterion notified from the other party of communication, report values indicating average channel quality of the selected subcarriers are created, the report values created and information indicating the subcarriers to be used are reported to the other party of communication, and it is thereby possible to allow the other party of communication to carry out transmission using only subcarriers of high quality and thereby improve the throughput in the own cell and neighboring cells and improve the throughput of the entire system consequently. Furthermore, averaging and reporting the channel quality of the subcarriers to be used can reduce an amount of data required for reporting. This application is based on the Japanese Patent Application No. 2002-378076 filed on Dec. 26, 2002, entire content of which is expressly incorporated by reference herein. INDUSTRIAL APPLICABILITY The present invention is suitable for use in a radio communication apparatus and radio communication method in multicarrier transmission.
<SOH> BACKGROUND ART <EOH>In a conventional W-CDMA (Wideband-Code Division Multiple Access) mobile communication system, a downlink high-speed packet transmission scheme (HSDPA: High Speed Downlink Packet Access) is being developed under which a high-speed, large-capacity downlink channel is shared among a plurality of communication terminal apparatuses and packet data is transmitted from a base station apparatus to a communication terminal apparatus at high speed. Here, HSDPA in a W-CDMA system will be explained briefly. A communication terminal apparatus measures a reception CIR (Carrier to Interference Ratio) and reports information (e.g., CQI: Channel Quality Indicator) indicating a downlink channel condition to a base station apparatus based on the measured CIR. The base station apparatus determines a communication terminal apparatus to which packet data is to be sent (transmission destination apparatus) based on CQIs reported from the respective communication terminal apparatuses. This is called “scheduling.” Furthermore, the base station apparatus determines according to what modulation scheme and what coding rate (MCS: Modulation and Coding Scheme) packet data to be sent to the transmission destination apparatus should be processed based on the downlink channel condition indicated by the CQI. This is called “MCS assignment.” The base station apparatus sends packet data to the determined transmission destination apparatus according to the determined MCS. As a specific example of MCS assignment, suppose a case where a fading variation as shown in FIG. 1 occurs. FIG. 1 illustrates a time variation of reception power due to fading. Suppose, the horizontal axis shows a time, the vertical axis shows reception power, and the reception power becomes a maximum at t1 and the reception power becomes a minimum at t2. It is decided that the propagation path is in a good condition at t1 and a high MCS level (e.g., 16QAM, coding rate ¾) is assigned. On the other hand, it is decided that the propagation path is in a poor condition at t2 and a low MCS level (e.g., QPSK, coding rate ¼) is assigned. That is, when the propagation path is in a good condition, high-speed transmission is possible. Therefore, if a communication terminal apparatus assigned a high MCS level is determined as the transmission destination, it is possible to send a large amount of data in a short time and thereby improve throughput of the system. Furthermore, a conventional W-CDMA system maintains reception quality per bit by controlling transmit power, while the HSDPA can maintain reception quality per bit by controlling the MCS as described above. The above described HSDPA is a technology based on the premise that it is used for a W-CDMA system, and the application of the HSDPA technology to an OFDM (Orthogonal Frequency Division Multiplexing) communication apparatus which is a promising next-generation communication scheme is under study. The following are examples of the HSDPA technology applied to OFDM.
<SOH> BRIEF DESCRIPTION OF DRAWINGS <EOH>FIG. 1 illustrates a time variation of reception power due to fading; FIG. 2 illustrates a frequency assignment method in conventional example 1; FIG. 3 conceptually illustrates a communication method in conventional example 2; FIG. 4 illustrates a frequency assignment method in conventional example 2; FIG. 5A conceptually illustrates reception power of subcarriers assigned in conventional example 1 at a communication terminal apparatus; FIG. 5B conceptually illustrates reception power of subcarriers assigned in conventional example 1 at the communication terminal apparatus; FIG. 6A conceptually illustrates reception power of subcarriers assigned in conventional example 2 at the communication terminal apparatus; FIG. 6B conceptually illustrates reception power of subcarriers assigned in conventional example 2 at the communication terminal apparatus; FIG. 7 illustrates a conceptual view showing a situation of interference with neighboring cells in a system of reuse 1 ; FIG. 8 is a schematic diagram conceptually illustrating subcarrier blocks; FIG. 9 is a block diagram illustrating the configuration of a transmission system of a base station apparatus according to Embodiment 1 of the present invention; FIG. 10 is a block diagram showing the configuration of a reception system of a communication terminal apparatus according to Embodiment 1 of the present invention; FIG. 11A illustrates a method of selecting usable blocks in Embodiment 1 of the present invention; FIG. 11B illustrates a method of selecting usable blocks in Embodiment 1 of the present invention; FIG. 12 illustrates an example of block assignment according to Embodiment 1 of the present invention; FIG. 13A illustrates a method of selecting usable blocks according to Embodiment 1 of the present invention; FIG. 13B illustrates a method of selecting usable blocks according to Embodiment 1 of the present invention; FIG. 14 illustrates a block assignment example according to Embodiment 1 of the present invention; FIG. 15 is a block diagram showing the configuration of a transmission system of a base station apparatus according to Embodiment 2 of the present invention; FIG. 16A illustrates a method of selecting usable blocks according to Embodiment 2 of the present invention; FIG. 16B illustrates a method of selecting usable blocks according to Embodiment 2 of the present invention; FIG. 17 illustrates a block assignment example according to Embodiment 2 of the present invention; FIG. 18 is a block diagram showing the configuration of a transmission system of a base station apparatus according to Embodiment 3 of the present invention; FIG. 19 is a block diagram showing the configuration of a reception system of a communication terminal apparatus according to Embodiment 3 of the present invention; FIG. 20A illustrates a method of selecting usable blocks according to Embodiment 3 of the present invention; and FIG. 20B illustrates a method of selecting usable blocks according to Embodiment 3 of the present invention. detailed-description description="Detailed Description" end="lead"?
20050623
20120828
20060427
84122.0
H04B1700
2
KHAN, MEHMOOD B
RADIO COMMUNICATION APPARATUS AND RADIO COMMUNICATION METHOD
UNDISCOUNTED
0
ACCEPTED
H04B
2,005
10,540,535
ACCEPTED
Method of adding activated carbon in water purification and method of water purification
When a raw water to be filtered c is fed from a raw water tank 11 reservoiring a raw water (water to be treated) to a membrane module by a raw water pump P1, an activated carbon raw material supplied from an activated carbon tank is milled together with water to be mixed by a wet milling device, and added and mixed into the raw water tank as an aqueous suspension containing activated carbon fine particles having an average particle size of 0.1 μm to 10 μm, thus producing the raw water to be filtered (activated carbon-containing water to be treated). The raw water to be filtered (activated carbon-containing water to be treated) is filtered by the membrane module at a subsequent step, thereby obtaining a purified water.
1. A method of adding activated carbon in water purification treatment by adding activated carbon to water to be treated to purify water to be treated, characterized in that an aqueous suspension containing activated carbon fine particles having an average particle size of 0.1 μm to 10 μm obtainable by wet milling of the particles of the activated carbon is added to the water to be treated. 2. The addition method of activated carbon in the water purification treatment according to claim 1, wherein a concentration of the activated carbon in an aqueous suspension containing the activated carbon fine particles is 0.1 mass percent to 10 mass percents. 3. The addition method of activated carbon in the water treatment according to claim 1, wherein a milling machine is installed by attaching to a passage of the water to be treated or to a tank reservoiring water to be treated, so that the activated carbon particles are subjected to wet milling by the milling machine. 4. A water treatment method of purifying water to be treated by use of activated carbon, characterized by adding, to water to be treated, an aqueous suspension containing activated carbon fine particles having an average particle size of 0.1 μm to 10 μm obtainable by wet milling of the particles of the activated carbon, and by further subjecting an obtained activated carbon-containing water to be treated to a membrane separation treatment. 5. The water treatment method according to claim 4, wherein a concentration of activated carbon in the aqueous suspension containing the activated carbon fine particles is 0.1 mass percent to 10 mass percents. 6. The water treatment method according to claim 4, wherein milling machine is installed by attaching to a passage of water to be treated or to a tank reservoiring water to be treated, so that the activated carbon particles are subjected to wet milling by the milling machine. 7. The addition method of activated carbon in the water treatment according to claim 2, wherein a milling machine is installed by attaching to a passage of the water to be treated or to a tank reservoiring water to be treated, so that the activated carbon particles are subjected to wet milling by the milling machine. 8. The water treatment method according to claim 5, wherein milling machine is installed by attaching to a passage of water to be treated or to a tank reservoiring water to be treated, so that the activated carbon particles are subjected to wet milling by the milling machine.
TECHNICAL FIELD The present invention relates to a method of adding activated carbon in water purification and a method of water purification to improve quality of purified water by adsorption of the activated carbon. BACKGROUND ART A water treatment apparatus, for example, utilizing activated carbon as shown in FIG. 2 has been known as an apparatus to purify river water to obtain purified water of high quality. In a technique disclosed here, water to be treated is fed from a raw water tank 11 reservoiring a raw water (a) through passages 12, 13 by a raw water pump P1, a circulation pump P2 to a membrane module 14 where suspended solids (SS) are removed, thereby a purified water (b) is obtained. In case of the apparatus shown as example, the apparatus is configured to return water to be treated through a passage 15 for circulation. Furthermore, in the instance shown in this figure, organic substances such as abnormal taste and odor causing materials, coloring materials and the trihalomethane precursors in the raw water (a) is removed by adding, from powder activated carbon injection means 16, activated carbon of ultra-fine particle powder having a particle size of 0.01 μm to 10 μm, instead of activated carbon powder having a particle size of about 18 μm which has heretofore been used. However, in such a known method, there has been used activated carbon of ultra-fine particle powder having been milled in advance by a certain method to have a particle size of 0.01 μm to 10 μm, however, such activated carbon of ultra-fine particle powder in itself is apt to aggregate and easily forms a secondary aggregate; thus, there is a problem that effects of careful selection of ultra-fine particle powder are not sufficiently attained. Moreover, there is also such a disadvantage that fine particle powder causes dust in handling. The present invention has been made to solve the problems described above, and is intended to provide a method of adding activated carbon in a water purification treatment and method of water purification treatment, wherein secondary aggregation of the activated carbon ultra-fine particles can be suppressed to make full use of its adsorption performance and the dusting of activated carbon fine particles during handling can be prevented, in the water purification treatment by which the quality of purified water is improved by utilizing the adsorption of the activated carbon. DISCLOSURE OF THE INVENTION The present invention has been made to achieve the aforementioned objects, and there is provided according to the present invention a method of adding activated carbon in water purification treatment by adding activated carbon to water to be treated to purify the water to be treated, characterized in that an aqueous suspension containing activated carbon fine particles having an average particle size of 0.1 μm to 10 μm obtainable by wet milling of the particles of the activated carbon is added to water to be treated. Furthermore, according to the present invention, there is provided a water treatment method of purifying a water to be treated by use of activated carbon, characterized by adding, to water to be treated, an aqueous suspension containing the activated carbon fine particles having an average particle size of 0.1 μm to 10 μm obtainable by wet milling of the particles of the activated carbon, and by further subjecting the obtained activated carbon-containing water to be treated to a membrane separation treatment. In the present invention, a concentration of activated carbon in the aqueous suspension containing activated carbon fine particles is preferably 0.1 mass percent to 10 mass percents. Furthermore, a milling machine is preferably installed by attaching it to a passage of the water to be treated or to a tank reservoiring water to be treated, so that activated carbon particles are subjected to wet milling by the milling machine. The method of adding activated carbon in the water purification treatment and the method of water purification treatment according to the present invention are constructed as described above, so that the secondary aggregation of activated carbon fine particles can be suppressed, thereby its adsorption performance can be fully utilized and the dusting of activated carbon fine particles can be prevented. Further, a cheap activated carbon raw material can be used, and the cost reduction is attained therefore. Still further, a working environment can be improved. Thus, the present invention has a great industrial value as a method of adding activated carbon in the water purification treatment and the method of water purification treatment capable of solving the conventional problems. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow diagram of essential parts of a water treatment apparatus to explain an activated carbon addition method of the present invention; and FIG. 2 is a flow diagram of a conventional water treatment apparatus using activated carbon. BEST MODE FOR CARRYING OUT THE INVENTION A best mode for carrying out a method of adding activated carbon in water purification and a water treatment method of the present invention will hereinafter be described in detail referring to the drawings. As shown in FIG. 1, in the present invention, when a raw water to be filtered (c) is fed from a raw water tank 11 reservoiring a raw water (water to be treated) (a) such as river water to a membrane module (not shown) by a raw water pump P1, an activated carbon raw material supplied from an activated carbon tank 21 is put into a water to be mixed (d), and then milled by a wet milling device 22, and added and mixed into the raw water tank 11 as an aqueous suspension containing activated carbon fine particles having an average particle size of 0.1 μm to 10 μm, thus producing the raw water to be filtered (activated carbon-containing water to be treated) (c). The features of the present invention lies in the point that the activated carbon fine particles thus milled are used in a state co-existing with water without undergoing a dried state. Here, the average particle size of the activated carbon fine particles used in the present invention means a volume mean diameter, and is obtained by measurement using a laser diffraction scattering method. The raw water to be filtered (activated carbon-containing water to be treated) (c) to which such activated carbon fine particles are added is filtered by the membrane module at a subsequent step as in the case shown in FIG. 2, thereby allowing a purified water (b) to be obtained. In this case, the aqueous suspension containing activated carbon fine particles obtainable by the wet milling device 22 is added into the raw water tank 11, but may be injected directly into a supply passage of the raw water (water to be treated) (a) to produce the raw water to be filtered (activated carbon-containing water to be treated) (c). The average particle size of the activated carbon fine particles used in the present invention is within a range of 0.1 μm to 10 μm as described above, and is preferably in a range of 0.5 μm to 10 pn. When the average particle size is below 0.1 μm, for example, when a microfiltration (MF) membrane treatment is combined, the activated carbon fine particles are difficult to separate by the MF membrane treatment, and when the average particle size is above 10 μm, the full advantage of the present invention cannot be attained effectively since one may use commercially available products having an average particle size of above 10 μm. Moreover, when the average particle size is 0.5 μm or above, complete capture can be achieved by an MF membrane surface, so that the activated carbon fine particles do not penetrate into the membrane, thereby an efficient membrane filtration can be attained. According to the present invention, the activated carbon raw material is subjected to wet milling, and the obtained activated carbon fine particles are dispersed into the aqueous suspension and added in a state not to cause secondary aggregation, so that an adsorption effect of organic matters and the like in the raw water can be sufficiently displayed. Further, the commercially available products having an average particle size of above 10 μm can be used for the activated carbon raw material, which is an advantage in that it is easy to purchase and cheap in the raw material costs. Also, there is an advantage that no dusting problem occurs since the activated carbon fine particles are handled as the aqueous suspension in the present invention, and that the used activated carbon raw material has a large particle size to cause no powder dust and is thus easy to handle. The preferable particle size of the activated carbon fine particles used in the present invention has been as described above, but there is also an advantage that an adjustment can be properly made to have an optimum value for a particle size obtained by adjusting an operating condition of the wet milling device 22 in dependence upon a purification object and upon a filtration size of a filtration membrane of the membrane module at the subsequent step (e.g., an adjustment is made in dependence upon a use target and upon the purpose; for example, the particle size is reduced when adsorption properties are considered by priority, or the particle size is made larger when the efficiency of biological activated carbon is required). It is to be noted that the membrane separation treatment (membrane module) used in the present invention includes, for example, a monolith type ceramic membrane as a preferred example. Furthermore, the wet milling device used in the present invention is not specifically limited as long as it is of a type capable of milling activated carbon after putting it into water to be mixed (d) for dispersion, but the wet milling device can include, as a preferred example, a fine milling device such as a roll ball mill, an oscillating ball mill or an attriter mill having a ball or a rod as a milling medium. Still further, a concentration of the activated carbon in the aqueous suspension containing the activated carbon fine particles used in the present invention is preferably within a range of 0.1 mass percent to 10 mass percents. If it is below 0.1%, the raw water to be filtered (c) is diluted, and treatment efficiency in the membrane module at the subsequent step may decrease. If it is above 10%, the activated carbon fine particles may easily cause the secondary aggregation. EXAMPLES An example of the present invention and comparative examples are shown below in Table 1. In Table 1, activated carbon fine particles obtained by the present invention were used in the example. In the example of the present invention in which there was used a test solution containing organic impurities at a predetermined concentration, an addition amount of the activated carbon fine particles was regarded as 100 when the contained organic impurities could be removed therefrom, and in Comparative Examples 1 and 2, addition amounts of activated carbons which were required to obtain the same effect as the above level of 100 are shown as relative amounts in Table 1. According to these results, it was found that the present invention could provide a similar effect in addition amounts of 67% and 33% of the amounts of the activated carbons in Comparative Examples 1 and 2, respectively, and the present invention could sufficiently demonstrate an effect of milling of the activated carbon. TABLE 1 Addition amount Kind of activated carbon Example 100 Activated carbon wet milling: particle size (average) 1.0 μm Comparative 150 Power dried for 24 hours Example 1 after wet milling at a particle size 1.0 μm Comparative 300 Commercially available Example 2 product of particle size of 15 μm INDUSTRIAL APPLICABILITY The present invention is preferably utilized in various kinds of industrial fields where a water to be treated such as a river water or a certain industrial water needs to be efficiently purified to obtain purified water of high quality.
<SOH> BACKGROUND ART <EOH>A water treatment apparatus, for example, utilizing activated carbon as shown in FIG. 2 has been known as an apparatus to purify river water to obtain purified water of high quality. In a technique disclosed here, water to be treated is fed from a raw water tank 11 reservoiring a raw water (a) through passages 12 , 13 by a raw water pump P 1 , a circulation pump P 2 to a membrane module 14 where suspended solids (SS) are removed, thereby a purified water (b) is obtained. In case of the apparatus shown as example, the apparatus is configured to return water to be treated through a passage 15 for circulation. Furthermore, in the instance shown in this figure, organic substances such as abnormal taste and odor causing materials, coloring materials and the trihalomethane precursors in the raw water (a) is removed by adding, from powder activated carbon injection means 16 , activated carbon of ultra-fine particle powder having a particle size of 0.01 μm to 10 μm, instead of activated carbon powder having a particle size of about 18 μm which has heretofore been used. However, in such a known method, there has been used activated carbon of ultra-fine particle powder having been milled in advance by a certain method to have a particle size of 0.01 μm to 10 μm, however, such activated carbon of ultra-fine particle powder in itself is apt to aggregate and easily forms a secondary aggregate; thus, there is a problem that effects of careful selection of ultra-fine particle powder are not sufficiently attained. Moreover, there is also such a disadvantage that fine particle powder causes dust in handling. The present invention has been made to solve the problems described above, and is intended to provide a method of adding activated carbon in a water purification treatment and method of water purification treatment, wherein secondary aggregation of the activated carbon ultra-fine particles can be suppressed to make full use of its adsorption performance and the dusting of activated carbon fine particles during handling can be prevented, in the water purification treatment by which the quality of purified water is improved by utilizing the adsorption of the activated carbon.
<SOH> BRIEF DESCRIPTION OF THE DRAWINGS <EOH>FIG. 1 is a flow diagram of essential parts of a water treatment apparatus to explain an activated carbon addition method of the present invention; and FIG. 2 is a flow diagram of a conventional water treatment apparatus using activated carbon. detailed-description description="Detailed Description" end="lead"?
20050624
20071002
20060126
65892.0
C02F128
0
SAVAGE, MATTHEW O
METHOD OF ADDING ACTIVATED CARBON IN WATER PURIFICATION AND METHOD OF WATER PURIFICATION
UNDISCOUNTED
0
ACCEPTED
C02F
2,005
10,540,541
ACCEPTED
Printing device and cassette
The present invention relates to a cassette for a recording medium, comprising an upper casing and a lower casing, a spool for holding a roll of recording medium and disposed the upper and lower casings, and a side casing for enclosing the spool and joining the upper and lower casings, wherein the side casing is fitted to at least one of the upper and lower casings by means of press fit or snap-fit connections. Various embodiments of cassettes and printers are also disclosed.
1-109. (canceled) 110. A cassette for a recording medium, comprising an upper casing and a lower casing, a spool for holding a roll of recording medium and disposed between the upper and lower casings, and a side casing for enclosing the spool and joining the upper and lower casings, wherein the side casing is fitted to at least one of the upper and lower casings by press-fit or snap-fit connections. 111. A cassette according to claim 1, wherein the upper and lower casings comprise grooves and/or protrusions and the side casing comprises corresponding protrusions and/or grooves for effecting the press-fit or snap-fit connections. 112. A cassette according to claim 1, wherein the upper and lower casings and the side casing have a generally circular configuration, and comprise an exit area through which a recording medium disposed on the spool can exit. 113. A cassette for a recording medium comprising an exit region for recording medium, and first and second flanges disposed at the exit region, each flange comprising one or more grooves adapted to receive an edge of a recording medium and allow the said edge to pass along the grooves. 114. A cassette for a recording medium comprising a casing, wherein one region of the casing has a rib on its exterior surface, which rib is adapted to slide in a groove of a device in which the cassette can be inserted, the rib comprising a projection adapted to latch into a detent of a device in which the cassette can be inserted. 115. A printing device comprising a recording medium receiving bay adapted to receive a recording medium cassette, wherein the receiving bay comprises a groove along which a rib of a recording medium cassette can be slid during insertion of the cassette into the recording medium receiving bay, the groove comprising a detent into which a projection of a rib of a recording medium cassette can be latched. 116. In combination: a cassette for a recording medium comprising a casing, wherein one region of the casing has a rib on its exterior surface; and a printing device having a recording medium receiving bay adapted to receive a recording medium cassette, wherein the bay comprises a groove; wherein the said rib of the recording medium cassette is adapted to slide in the groove of the recording medium receiving bay of the printing device, and wherein the groove comprises a detent and the rib comprises a projection, the projection latching into the detent. 117. A printing device comprising a recording medium receiving bay adapted to receive a recording medium cassette, the receiving bay comprising first and second supports mounted in a moveably resiliently manner, the printing device further comprising a mechanism which is operable to allow separation of the supports for insertion of a recording medium cassette therebetween and is further operable to allow movement of the supports towards one another to retain an inserted recording medium cassette in a substantially fixed position with respect to the recording medium receiving bay. 118. A printing device adapted to receive a cassette therein, the printing device comprising one of a ramp and a resiliently moveable portion capable of interacting with the other of a ramp and a resiliently moveable portion of a cassette, such that during insertion of the cassette the ramp causes movement of the resiliently moveable portion from a position in which it would otherwise prevent insertion of the cassette into a position allowing insertion of the cassette. 119. A printing device according to claim 1 18, wherein the printing device comprises the ramp and further comprises a detent into which the resiliently moveable portion can latch following insertion of the cassette. 120. A printing device according to claim 119, wherein the detent is located such that when a resiliently moveable portion of a cassette has latched into the detent, the printing device is operable to print using the cassette. 121. A printing device according to claim 120, wherein the detent is configured such that the said resiliently moveable portion is moveable following insertion of a cassette into the printing device to allow removal of a cassette from the printing device. 122. A cassette adapted to be received in a printing device, the cassette comprising one of a ramp and a resiliently moveable portion capable of interacting with the other of a ramp and a resiliently moveable portion of a printing device, such that during insertion of the cassette the ramp causes movement of the resiliently moveable portion from a position in which it would otherwise prevent insertion of the cassette into a position allowing insertion of the cassette. 123. A cassette according to claim 122, wherein the cassette comprises the ramp and further comprises a detent into which the resiliently movable portion can latch following insertion of the cassette. 124. A cassette according to claim 123, wherein the detent is located such that when a resiliently movable portion of the printing device has latched into the detent, the printing device is operable to print using the cassette. 125. A cassette accordingly to claim 124, wherein the detent is configured such that the said resiliently movable portion is movable following insertion of the cassette into the printing device to allow removal of a cassette from the printing device. 126. In combination a printing device and a cassette adapted to be received in the printing device, the printing device comprising a resiliently moveable portion capable of interacting with a ramp of a cassette, such that during insertion of the cassette the ramp causes movement of the resiliently moveable portion from a position in which it would otherwise prevent insertion of the cassette into a position allowing insertion of the cassette. 127. A cassette comprising a hollow spool for holding a recording medium, and a sprocket disposed inside at least a part of the spool and driveable to rotate the spool for unwinding recording medium therefrom, wherein a surface of the sprocket in contact with an interior surface of the spool comprises a plurality of protrusions which bear on the inside surface of the spool. 128. A printer comprising a cassette receiving bay for receiving a cassette holding recording medium, the cassette receiving bay comprising a sprung portion which is openable to allow insertion of a cassette in the receiving bay and which is arranged to, following insertion of a cassette, close under a spring force, thereby locking an inserted cassette in the receiving bay. 129. A printer according to claim 128, wherein the sprung portion is arranged to open and close in a plane perpendicular to the direction of insertion of a cassette. 130. A cassette for use with a printer, the cassette comprising one or more ribs on an outside surface of the cassette, at least one of the ribs being substantially channel-shaped, wherein at least one of the legs of the channel-shape is disposed at an angle of greater than 90° to the base of the channel-shape. 131. In combination a printer and a cassette, the printer comprising a cassette receiving bay for receiving the cassette, the cassette receiving bay comprising a fixed portion and a sprung portion which is openable to allow insertion of the cassette in the receiving bay and which is arranged to, following insertion of the cassette, close under a spring force, thereby locking the inserted cassette in the receiving bay, wherein when the sprung portion is open, the sprung portion and the fixed portion together form one or more grooves through which a corresponding one or more ribs of the cassette can slide during insertion, thereby retaining the sprung portion in an open position during insertion. 132. A recording medium cassette comprising a casing and having a wound roll of recording medium disposed in the casing which roll can unwind such that an end of the recording medium can exit the casing, wherein the cassette further comprises a leaf spring disposed on the casing and oriented to act on the recording medium to exert a force in a direction towards the center of the roll of recording medium. 133. A set of cassettes for holding a recording medium, each cassette comprising an upper portion and a lower portion disposed apart a distance and joined together by attachment to a side portion having a width corresponding to the distance, thereby enabling a roll of recording medium to be held between the upper and lower portions with the width of the recording medium being oriented substantially parallel to the width of the side portion, wherein each cassette has a side portion of a different width. 134. A printer for use with a cassette holding recording medium, the printer comprising: a driver operable to drive in a forward direction to unwind recording medium of a cassette inserted in the printer and to drive in a reverse direction for rewinding recording medium; a detector operable to detect that an inserted cassette is to be removed from the printer and, when such a detection is made, generating a signal indicating that a cassette is to be removed, wherein the driver is arranged to receive the generated signal and in response thereto, drive in the reverse direction for rewinding a length of recording medium of an inserted cassette. 135. A printer for use with a cassette holding recording medium, the printer comprising: a printing zone comprising a platen and a printer device arranged to receive therebetween recording medium held in a cassette inserted in the printer, to thereby print an image on a length of the recording medium, the platen being rotatable to drive a length of recording medium through the printing zone; and a driver comprising a feed roller arranged to rotate to thereby unwind recording medium held in an inserted cassette to thereby feed recording medium to the printing zone, wherein the printer is arranged to, when a length of recording medium unwound by the driver reaches the printing zone, rotate the platen to drive the length of recording medium through the printing zone. 136. A printer comprising: a cassette receiving bay for receiving a cassette holding recording medium; a roller driver disposed in a region in which recording medium exits a cassette inserted in the cassette receiving bay; and a lever operable to move the roller driver from a position in which a cassette can be inserted to a position in which it will contact recording medium as the recording medium exits an inserted cassette. 137. An ink ribbon cassette comprising: a supply spool for holding a roll of ink ribbon; a take-up spool onto which ink ribbon unwound from the supply spool is wound; a driveable sprocket arranged to rotate the supply spool for rewinding unwound ribbon onto the supply spool; and a spring disposed to act axially on the sprocket for maintaining tension of the ink ribbon between the supply and take-up spools. 138. An ink ribbon cassette comprising: a hollow supply spool for holding a roll of ink ribbon; and a driveable sprocket at least part of which is disposed inside the supply spool to rotate the supply spool for rewinding unwound ribbon onto the supply spool, wherein the end of the sprocket that is not disposed inside the supply spool comprises an inner cylinder and an outer cylinder, the inner cylinder extending further in a direction away from the supply spool than the outer cylinder.
The present invention relates to a printing device and a cassette or cartridge, and also to a combination of a printing device and such a cassette or cartridge. One type of printing device that is widely known is a thermal tape printer. A thermal tape printer generally comprises a printing means comprising a thermally activatable printhead for printing onto an image receiving tape. Typically, the image receiving tape has an upper layer for receiving an image and a removable liner layer or backing layer secured to the upper layer by a layer of adhesive, such that after an image has been printed the liner layer or backing layer can be removed and the image receiving tape can be stuck down in the form of a label. Such thermal printers often include cutters for cutting off a length of image receiving tape after the image has been printed. Such thermal printers operate with a consumable in the form of image receiving tape, or any other image receiving substrate such as heat shrink tube, magnetic, iron-on labels, plastic strips, etc. The term “consumable” is used herein to denote any appropriate form of providing image receiving tape. The image receiving tape may comprise a continuous backing sheet whilst the image receiving layer has been pre-cut into labels, such that a label can be printed and then peeled off from the backing sheet. A printer intended to operate with such an image receiving tape does not need a cutter to cut the image receiving tape. A number of forms of consumables are known in the art, including cassettes or cartridges which comprise a housing in which is located a supply of image receiving tape. Cassettes are generally usable once only, such that once the image receiving tape has been consumed, the cassette (including the housing) is thrown away. A cassette can have a housing which substantially encloses the supply of image receiving tape or the housing can be simpler, for example a spool and two sides within which the tape is located. A simpler cassette is sometimes called an image receiving holder. Another type of consumable is a roll of tape without a permanent holder, for example wound on a paper core. These are termed “supplies”. In thermal printers, an image is generally generated by activation of a thermal printhead against an ink ribbon, such that ink from the ink ribbon is transferred onto the image receiving tape at a print zone. So-called direct thermal tapes are also available, in which an image is created directly onto the direct thermal tape without the interposition of an ink ribbon, If an ink ribbon is used in a thermal printer, it is generally provided held in a cassette having a housing, the housing being insertable into the printer. The ink ribbon is passed out of the cassette into overlap with the image receiving tape such that both the ink ribbon and the image receiving tape are fed past the printhead. Each length of ink ribbon is used for only one printing operation and is then rewound back into the ink ribbon cassette. The ink ribbon is therefore also a consumable. Known tape printing apparatus of the type with which the present invention is concerned are disclosed in EP-A-322918 and EP-A-322919 (Brother Kogyo Kabushiki Kaisha) and EP-A-267890 (Varitronic). The printers each include a printing device having a cassette receiving bay for receiving a cassette or tape holder. In EP-A-267890, the tape holder houses an ink ribbon and a substrate tape, the latter comprising an upper image receiving layer secured to a backing layer by an adhesive. In EP-A-322918 and EP-A-322919, the tape holding case houses an ink ribbon, a transparent image receiving tape and a double sided adhesive tape which is secured at one of its adhesive coated sides to the image tape after printing and which has a backing layer peelable from its other adhesive coated side. With both these apparatus, the image transfer medium (ink ribbon) and the image receiving tape (substrate) are in the same cartridge. It has also been proposed by the present applicants in, for example, EP-A-578372 to house the ink ribbon and the substrate tape in separate cassettes or cartridges. In all of these cases, the image receiving tape passes in overlap with the ink ribbon to a print zone consisting of a fixed print head and a platen against which the print head can be pressed to cause an image to transfer from the ink ribbon to the image receiving tape. There are many ways of doing this, including dry lettering or dry film impression, but the most usual way currently is by thermal printing where the print head is heated and the heat causes ink from the ink ribbon to be transferred to the image receiving tape. The devices of the type described above are provided with a keyboard which enables a user to enter characters, symbols and the like to form an image to be printed by the tape printer. The keyboard usually has text character keys and number keys for entering letters and number keys respectively, plus some function keys which, among other things, operate menus and allow printing attributes to be set. Cassettes are usually made from plastics material and for practical purposes are often formed from more than one moulded part. One problem with such cassettes is that they can be costly to manufacture because each moulded part is relatively complex in order to achieve correct placement and unwinding of the image receiving medium, and the parts need to be fitted together by a manufacturing process e.g. welding. It would be desirable to provide a cassette made from parts which can be press-fit or snap-fit together. Another problem with such cassettes is that excessive unwinding of the tape from the cassette can occur, and this is undesirable. This can happen during transportation of the cassette, but can also occur during operation of the printer when the tape is being driven. It would be desirable to provide a cassette with means for preventing excessive unwinding of the tape. During use of a cassette, image receiving tape contained therein must be unwound and must exit the cassette in order to be printed on. It is vital that the tape is properly aligned in the correct position relative to the printhead and, if used, the ink ribbon. Although this may be in part achieved by guiding elements within the printer, these may not be able to achieve accurate alignment if the tape is not correctly aligned when it arrives at the guiding elements. One problem with existing cassettes is that it is possible for the image receiving tape to move laterally during unwinding and exit from the cassette, and if enough lateral movement is accumulated over the unwinding and exit path, the image is not printed centrally on the tape or, in the worst case, does not even fit on the tape due to being printed in the wrong position or due to folds in the tape. It would therefore be desirable to provide a cassette which has means for ensuring correct alignment of exiting image receiving tape. A printer of the type previously described is often useable with different widths of tape. This enables the creation of many different sizes of labels. It is usual to size a cassette housing to correspond to the width of the tape contained in the cassette, thereby giving a visual indication of the tape size and avoiding use of unnecessarily bulky cassette housings. Having a suitably sized casing may also make it easier for tape to exit the cassette correctly aligned, depending on the design of the cassette and printer. One problem associated with the provision of multiple cassettes is the manufacturing cost for making the various designs. It would be desirable to mitigate these costs. As well has having different cassettes of different tape width available, it is also common to provide various cassettes of different colours and styles of tape. Another consequence of having different cassettes available for use with a printer is that a user or multiple users will want to use different cassettes but not use all the tape on one cassette at once. Therefore, one cassette will be removed by a user and another inserted. A problem associated with this is wastage of tape. This occurs because after creation of a label, a certain amount of further tape has exited from the cassette and is in the region between the cassette and the printer tape exit. It would be desirable to rewind this further tape prior to removal of a cassette so that it is available for use the next time the cassette is inserted into the printer. In order to achieve successful printing the image receiving cassette must be held firmly in place in the printer and must be inserted in the correct location. If the cassette can move about within the printer or is incorrectly positioned during insertion, images will not be correctly printed on the tape, or malfunction of the printer could be caused. It would therefore be desirable to provide means for ensuring accurate alignment and positioning of a cassette in a printer and means for retaining the cassette in the correct position after insertion. Most printers include a drive means which rotates a supply spool of a tape cassette, thus feeding tape to the printing area. It may be desirable to provide a further means of locally feeding the tape in the printing area. Another requirement for successful printing is that the ink ribbon cassette is correctly inserted in the printer and is retained in the correct location. If the ribbon cassette can move about within the printer it may result in incorrect feeding of the ink ribbon and hence a lack of proper transfer of ink to the image receiving tape during printing. It would therefore be desirable to facilitate correct insertion of the ink ribbon cassette and to ensure retention of the ink ribbon cassette in the correct position in the printer. According to a first aspect of the present invention, there is provided a cassette for a recording medium, comprising an upper casing and a lower casing, a spool for holding a roll of recording medium and disposed between the upper and lower casings, and a side casing for enclosing the spool and joining the upper and lower casings, wherein the side casing is fitted to at least one of the upper and lower casings by means of press-fit or snap-fit connections. According to a second aspect of the present invention, there is provided a cassette for a recording medium comprising an exit region for recording medium, and first and second flanges disposed at the exit region, each flange comprising one or more grooves adapted to receive an edge of a recording medium and allow the said edge to pass along the grooves. According to a third aspect of the present invention, there is provided a cassette for a recording medium comprising a casing, wherein one region of the casing has a rib on its exterior surface, which rib is adapted to slide in a groove of a device in which the cassette can be inserted, the rib comprising a projection adapted to latch into a detent of a device in which the cassette can be inserted. According to a fourth aspect of the present invention, there is provided a printing device having a recording medium receiving bay adapted to receive a recording medium cassette, wherein the receiving bay comprises a groove along which a rib of a recording medium cassette can be slid during insertion of the cassette into the recording medium receiving bay, the groove comprising a detent into which a projection of a rib of a recording medium cassette can be latched. According to a fifth aspect of the present invention, there is provided a printing device having a recording medium receiving bay adapted to receive a recording medium cassette, the receiving bay comprising first and second supports mounted in a moveably resiliently manner, the printing device further comprising a mechanism which is operable to allow separation of the supports for insertion of a recording medium cassette therebetween and is further operable to allow movement of the supports towards one another to retain an inserted recording medium cassette in a substantially fixed position with respect to the recording medium receiving bay. According to a sixth aspect of the present invention, there is provided a cassette adapted to be received in a printing device, the cassette comprising one of a ramp means and a resiliently moveable portion capable of interacting with the other of a ramp means and a resiliently moveable portion of a printing device, such that during insertion of the cassette the ramp means causes movement of the resiliently moveable portion from a position in which it would otherwise prevent insertion of the cassette into a position allowing insertion of the cassette. According to a seventh aspect of the present invention, there is provided in combination a printing device and a cassette adapted to be received in the printing device, the printing device comprising a resiliently moveable portion capable of interacting with a ramp means of a cassette, such that during insertion of the cassette the ramp means causes movement of the resiliently moveable portion from a position in which it would otherwise prevent insertion of the cassette into a position allowing insertion of the cassette. According to an eighth aspect of the present invention, there is provided a cassette comprising a hollow spool for holding a recording medium, and a sprocket disposed inside at least a part of the spool and driveable to rotate the spool for unwinding recording medium therefrom, wherein a surface of the sprocket in contact with an interior surface of the spool comprises a plurality of protrusions which bear on the inside surface of the spool. According to a ninth aspect of the present invention, there is provided a printer comprising a cassette receiving bay for receiving a cassette holding recording medium, the cassette receiving bay comprising a sprung portion which is openable to allow insertion of a cassette in the receiving bay and which is arranged to, following insertion of a cassette, close under a spring force, thereby locking an inserted cassette in the receiving bay. According to a tenth aspect of the present invention, there is provided a cassette for use with a printer, the cassette comprising one or more ribs on an outside surface of the cassette, at least one of the ribs being substantially channel-shaped, wherein at least one of the legs of the channel-shape is disposed at an angle of greater than 90° to the base of the channel-shape. According to an eleventh aspect of the present invention, there is provided a in combination a printer and a cassette, the printer comprising a cassette receiving bay for receiving the cassette, the cassette receiving bay comprising a fixed portion and a sprung portion which is openable to allow insertion of the cassette in the receiving bay and which is arranged to, following insertion of the cassette, close under a spring force, thereby locking the inserted cassette in the receiving bay, wherein when the sprung portion is open, the sprung portion and the fixed portion together form one or more grooves through which a corresponding one or more ribs of the cassette can slide during insertion, thereby retaining the sprung portion in an open position during insertion. According to a twelfth aspect of the present invention, there is provided a recording medium cassette comprising a casing and having a wound roll of recording medium disposed in the casing which roll can unwind such that an end of the recording medium can exit the casing, wherein the cassette further comprises a leaf spring disposed on the casing and oriented to act on the recording medium to exert a force in a direction towards the centre of the roll of recording medium. According to a thirteenth aspect of the present invention, there is provided a set of cassettes for holding a recording medium, each cassette comprising an upper portion and a lower portion disposed apart a distance and joined together by attachment to a side portion having a width corresponding to the distance, thereby enabling a roll of recording medium to be held between the upper and lower portions with the width of the recording medium being oriented substantially parallel to the width of the side portion, wherein each cassette has a side portion of a different width. According to a fourteenth aspect of the present invention, there is provided a printer for use with a cassette holding recording medium, the printer comprising: driving means able to drive in a forward direction to unwind recording medium of a cassette inserted in the printer and to drive in a reverse direction for rewinding recording medium; detection means for detecting that an inserted cassette is to be removed from the printer and, when such a detection is made, generating a signal indicating that a cassette is to be removed, wherein the driving means is arranged to receive the generated signal and in response thereto, drive in the reverse direction for rewinding a length of recording medium of an inserted cassette. According to a fifteenth aspect of the present invention, there is provided a printer for use with a cassette holding recording medium, the printer comprising: a printing zone comprising a platen and a print means arranged to receive therebetween recording medium held in a cassette inserted in the printer, to thereby print an image on a length of the recording medium, the platen being rotatable to drive a length of recording medium through the printing zone; and driving means comprising a feed roller arranged to rotate to thereby unwind recording medium held in an inserted cassette to thereby feed recording medium to the printing zone, wherein the printer is arranged to, when a length of recording medium unwound by the driving means reaches the printing zone, rotate the platen to drive the length of recording medium through the printing zone. According to a sixteenth aspect of the present invention, there is provided a printer comprising : a cassette receiving bay for receiving a cassette holding recording medium; a roller drive means disposed in a region in which recording medium exits a cassette inserted in the cassette receiving bay; and a lever means operable to move the roller drive means from a position in which a cassette can be inserted to a position in which it will contact recording medium as the recording medium exits an inserted cassette. According to a seventeenth aspect of the present invention, there is provided an ink ribbon cassette comprising: a supply spool for holding a roll of ink ribbon; a take-up spool onto which ink ribbon unwound from the supply spool is wound; a driveable sprocket arranged to rotate the supply spool for rewinding unwound ribbon onto the supply spool; and a spring disposed to act axially on the sprocket for maintaining tension of the ink ribbon between the supply and take-up spools. According to an eighteenth aspect of the present invention, there is provided a an ink ribbon cassette comprising: a hollow supply spool for holding a roll of ink ribbon; and a driveable sprocket at least part of which is disposed inside the supply spool to rotate the supply spool for rewinding unwound ribbon onto the supply spool, wherein the end of the sprocket that is not disposed inside the supply spool comprises an inner cylinder and an outer cylinder, the inner cylinder extending further in a direction away from the supply spool than the outer cylinder. Embodiments of the invention will now be described, by way of example only, with reference to the accompanying drawings in which FIG. 1 is a plan view of the mechanical arrangement of a printing apparatus; FIG. 2 is a side view of the mechanical arrangement of the printing apparatus; FIG. 3 is a front view of the mechanical arrangement of the printing apparatus; FIG. 4 is a cross-sectional view of the mechanical arrangement of the printing apparatus taken along line AA of FIG. 1; FIG. 5 is a schematic block diagram of control components of a printing apparatus; FIGS. 6a and 6b are perspective views from different angles of a tape cassette, FIG. 6b also showing a part of the printing apparatus which interacts with the tape cassette; FIG. 7a is a perspective view of a tape cassette housed in a receiving part of the printing apparatus and FIG. 7b is a perspective view of the receiving part of the printing apparatus without the tape cassette installed; FIGS. 8a and 8b are two perspective views of a ink ribbon cassette; FIG. 9 is a plan view of the printing apparatus showing a photo-sensor; FIG. 10 shows an exploded view of the tape cassette of FIG. 6; FIGS. 11a to 11i show views of the tape cassette being inserted into a cassette receiving part of the printer; FIGS. 12a-12d show views of a mechanism for aligning and holding the tape cassette in the cassette receiving part; FIG. 13 shows the fitting of leaf springs to the tape cassette; FIG. 14 shows a detail of a spool and sprocket of the tape cassette; FIG. 15 shows a tape cassette of a second embodiment; FIG. 16 shows a detail of a profile of the tape cassette of FIG. 15; FIG. 17 and b show a tape cassette receiving bay of a printer of the second embodiment; FIGS. 18a to 18c show the tape cassette of FIG. 15 inserted into the cassette receiving bay of FIG. 17; FIG. 19 shows an exploded view of the ink ribbon cassette of FIG. 8; FIG. 20 shows the interior of a bottom portion of the ink ribbon cassette; FIGS. 21a and 21b show two views of a sprocket of the ink ribbon cassette; FIGS. 22a and 22b show insertion of the ink ribbon cassette into the printer; and FIGS. 23a-c show a detail of a locking mechanism for locking the ink ribbon cassette in the printer; FIG. 24 shows an exploded view of an alternative ink ribbon cassette; FIGS. 25a and b show views of a bottom portion of the ink ribbon cassette of FIG. 24; and FIG. 26 shows a further view of a bottom portion of the ink ribbon cassette of FIG. 24 without an ink ribbon present. In the figures, like reference numerals indicate like parts. The mechanical arrangement of the printing apparatus will now be described with reference to FIGS. 1 to 4. A label substrate comprises a tape 2 onto which images can be printed by a printing apparatus into which the label substrate is inserted. The tape 2 is housed in a tape cassette 6, the details of which can most clearly be seen from FIGS. 4, 6a and 6b, together with the exploded view of FIG. 10. The tape cassette 6 comprises front and rear portions 60 (alternatively termed upper and lower portions) which are generally circular in shape and an inner spool 62 around which a supply of tape 2 is wound. The inner spool 62 may rotate within the tape cassette 6 when tape is unwound. Two leaf springs 64 are attached one to each portion 60 to prevent the tape from unwinding more than is required, as will be described in more detail below. Elongate ribs 58 are provided on one of the portions 60 of the tape cassette 6 which allow it to be housed in a first receiving part 66 of the printing apparatus, as will also be described in more detail below. The first receiving part 66 is shown in FIG. 7b and also in FIGS. 11a and 11b. The first receiving part 66 has side supports 86, 88. The side support (or flange) 86 has two grooves 67 designed to accept the corresponding ribs 58 of the rear portion 60 of the tape cassette 6. These ribs 58 can be seen on the front portion 60 of the cassette 6 in FIG. 10. The ribs 58 are generally elongate and extend across the portion 60. Two ribs 58 are provided, running parallel and spaced apart across a width of the portion 60 taken perpendicular to the ribs 58. There is one rib 58 either side of a central cut-out 60b of the portion 60. Thus neither of the ribs 58 passes through the centre of the portion 60. Each rib has a projection 96 shown as a detail in FIG. 11a, the projections 96 projecting towards the outer edge of the portion 60 and themselves being generally elongate in a direction along the length of the ribs 58, although relatively much shorter than the ribs 58. The projections 96 are shaped to latch into detents 87 in the grooves 67 (only one of which is visible in FIGS. 6b and 11). As discussed in the next paragraph, the user slideably inserts the cassette 6 so that the ribs 58 cooperate with one of the supports 86,88, while the opposing support moves in parallel. The opposing support has a sprocket 85 which is inserted into a sprocket 68 of the supply spool 62. The supports 86, 88 are adjustable to accommodate different width cassettes as will now be explained, also with reference to FIG. 12. The supports 86 and 88 of the first receiving part 66 are connected to teethed arms 80 and 82. The teeth of teethed arms 80 and 82 engage with opposite edges of a cog 84. In this way any movement of one of the supports 86 or 88 is mirrored by the other support, so that each support is always an equal distance from a centre line A (shown in FIG. 1). This ensures that the tape will always be fed centrally to the print head, regardless of the width of the tape. The supports 86, 88 can be separated by a user to insert a cassette 6, this being facilitated by handles 99. Then springs 74 (shown in FIGS. 1 and 12b) bring the supports 86, 88 together to grip the sides of the tape cassette 6. In order to assist the user in inserting the tape cassette 6 there is provided a position actuation lever 98 disposed at the outer edge of the support 86. This lever is shown particularly in FIGS. 11c, 11d, and 11g-i. This lever 98 acts as a lock to hold the supports 86, 88 firmly at a number of positions. The lever 98 can be pressed at its top end against the action of a spring 81 at its lower end and then the support 86 slid apart from the support 88 such that a secondary lever 87 also disposed at the lower end of the lever 98 can be detented into one of a number of slots 83. The slots 83 are disposed in the frame of the printer. Sliding of the support 86 is assisted by a guiding shaft 89 onto which the bottom of the support 86 is fitted. When the lever 98 is released, the secondary lever 87 is released from a slot 83 in which it is inserted and the springs 74 can act to draw the supports 86, 88 together. The above described ribs and grooves, and the support system can be used either together or separately to ensure good location and retention of the cassette 6 in the printer. The printing apparatus comprises a gear chain 12, powered by a motor 10, which drives a feed roller 14 which causes the tape from the tape cassette 6 to move towards a print zone 3 of the printing apparatus. At the print zone, a print head 16 is biased against a platen roller 18 by a spring 20. The spring 20 is held within a print head mounting block 19. As shown in FIG. 7a, the receiving part 66 is provided with a gear chain 72 powered by a motor 10 (shown in FIG. 1) that drives the feed roller 14 in order to rewind the tape onto the supply spool 62 to allow the cassette to be removed from the device. The printer is provided with a means of detecting when a cassette is to be removed. In this embodiment, a user can indicate at the keyboard 106 that a cassette is to be removed. This indication generates a signal which is received by the microprocessor 100 and then used to control the motor 10 to drive the spool 62 in a reverse direction. The microprocessor 100 controls the motor 10 to drive the feed roller 14 to rewind the tape 2 an amount corresponding to a predetermined distance range in the printer. The maximum distance is that from a cutting apparatus 40 (to be explained below) to where the tape 4 exits the cassette 6 when the cassette 6 is installed in the printer. The minimum distance is from the print zone 3 to where the tape 4 exits the cassette 6 when the cassette 6 is installed in the printer. Rewinding of the tape 2 onto the supply spool 62 can only be done when the printhead is in an open condition, away from the platen roller. The printhead can be opened either manually or automatically. An ink ribbon cassette 8 (shown in FIGS. 8a and 8b) holds an ink ribbon 4 and is mounted in a second receiving part of the printing apparatus. It is mounted on shafts 22 and 28 of the printing apparatus. The mounting block 19 may be moved by means of an actuator 21 to separate the printhead and the platen to allow the ink ribbon cassette 8 or the tape cassette 6 to be removed from the printer. Unused ink ribbon 26 is stored on a supply reel labelled generally as 24 and mounted on a printer shaft 22. Used ink ribbon 32 is stored on a take-up reel labelled generally as 30 and mounted on a printer shaft 28. A motor 34 powers a gear chain 36. When the motor 34 is driving forwards, a first set of gears 36c, 36d drive the shaft 28 to pull the ink ribbon 4 in a forward direction from the supply reel 24 to the take-up reel 30, and a slipping clutch (not shown) disengages the shaft 22 so that it is not driven, but is free to turn. When the motor 34 drives in reverse, a second set of gears 36a, 36b drive the shaft 22 to pull the ink ribbon 4 in a reverse direction from the take-up reel to the supply reel, and a slipping clutch (not shown) disengages the shaft 28 so that it is not driven, but is free to turn. The ink ribbon cassette 8 is located in the printing apparatus so that the ink ribbon 4 has a path which extends through the print zone 3, and in particular extends in overlap with the tape 2 between the printhead 16 and the platen 18. The platen 18 is driven by a platen motor 56, to drive the tape through the print zone. A cutting apparatus 40 is located downstream of the print zone 3. The cutting apparatus comprises a circular cutting blade or cutting wheel 44 mounted on a cutter holder 54. The cutting blade 44 cuts the tape 2 against an anvil 52. A cutter motor 42 drives the cutting wheel 44 from a rest position across the width of the tape. Once the cutting wheel 44 has traversed the entire width of the tape, the cutter motor 42 is reversed and drives the cutter holder 54 back to its rest position. The cutter holder 54 is slidably mounted on two sliders 46 which span the entire width of the tape 2. The cutter holder 54 is attached to a belt 48 which is supported by two rollers 50. One of the rollers 50 is driven by the cutter motor 42 to cause the cutter holder to move along the sliders 46. The mechanical function of the printing apparatus will now be described. During printing, the tape feed motor 10 and the ink ribbon motor 34 are activated to drive the tape 2 and the ink ribbon 4 respectively past the printhead 16 at an equal speed. Once the tape reaches the print zone, it is picked up by the platen 18, driven by the platen motor 56. In this embodiment the microprocessor 100 runs a timer which commences driving of the platen motor 56 a predetermined time after the motor 10 has begun to feed the tape. In other embodiments an end-of-tape detector is provided to detect when the leading edge of the tape 4 has been driven to the print zone 3. In both cases, driving of the platen motor 56 commences shortly before the leading edge of the tape actually reaches the platen 18 but it could be arranged to commence exactly as the leading edge reaches the platen. When the platen 18 starts to rotate, driving of the motor 10 is stopped so as not to feed excess tape to the print zone 3. An image is transferred onto the image receiving tape 2 by virtue of activation (heating) of particular printhead elements to transfer ink from the ink ribbon 4 to the substrate 2 in a known manner. Images are printed on a column by column basis as the tape 2 is moved past the printhead 16. This printing technique is known per se and so is not described further herein. When the printing on a label is finished, the tape feed motor 10 and the ink ribbon motor 34 continue to feed the tape and the ink ribbon a predetermined distance until the end of the label is at the required cutting position. The tape may then be cut by the cutting apparatus 40. If die-cut labels are used, a label can be peeled off at this position. Once cutting is complete, the tape 2 is reversed by reversing the platen motor 56 that drives the platen 18 in reverse until the tape 2 is in the correct position for printing the next label. Whilst the tape 2 is reversed, the ink ribbon 4 is also reversed at approximately the same speed by driving the ink ribbon motor 34 in reverse. This prevents the ink ribbon 4 rubbing against the tape 2 and becoming damaged. A photo-sensor 76 shown in FIG. 9 is mounted on the frame of the printing apparatus and detects the presence of tape 2. This prevents the printer printing if there is no tape present in the printer. FIG. 5 shows a schematic block diagram of the control components of the printing apparatus. A microprocessor 100 controls operation of the printing apparatus and is associated with a read only memory ROM 102, an electronically erasable programmable read only memory EEPROM 114 and a random access memory RAM 104. The printing apparatus includes a keyboard 106 for entering data (e.g. characters and symbols) and control commands for printing, and a display 108 for displaying to the user labels under edit, control commands, error messages, etc. The microprocessor 100 controls the printhead 16, tape drive motor 10, ink ribbon motor 34, cutter motor 42 and the platen motor 56. Various details of the tape cassette 6, an alternative tape cassette 100 and the ink ribbon cassette 8 will now be described. Reference is firstly made to FIG. 10, which shows an exploded view of the tape cassette 6. The tape cassette 6 is made from a number of component parts which can be put together manually or with a simple machine technique. No complex industrial processes such as welding are required. The tape cassette 6 is conveniently made from plastics material but other suitable materials could be used. The assembly process is as follows: (i) The spool 62 is placed in the centre of a roll of tape 2. In this embodiment the tape 2 is formed of a backing layer together with an upper layer which is to be printed, the upper layer being pre-cut into a series of labels. A continuous upper layer which can be cut with the cutting apparatus 40 is used in other embodiments. (ii) A profile 66 or side portion of the cassette 6 is press-fit into one of the portions 60. The profile 66 forms the side of the tape cassette 6, the portions 60 forming the front and rear or upper and lower parts of the case. The profile 66 is generally of open-ended cylindrical form but does not form a complete cylinder. When the tape cassette 6 is assembled, the absent part of the cylinder is located in the region where the tape exits the cassette 6. The profile 66 has four posts 63 formed on the inner surface of the profile 66 and running across the “length” of the part-cylinder of which the profile 66 is formed i.e. across the width of the profile 66. Each post 63 has a rounded protrusion 63a at each end which is for press-fitting into a corresponding groove 60a cut out of the outer edge of each portion 60. Thus the profile 66 is fitted into one of the portions 60, which in this embodiment we will call the rear portion. More or less than four protrusions and grooves could be used. The positions of the protrusions 63a and the corresponding positions of the grooves 60a ensure that the profile 66 is correctly fitted to the portion 60, such that the absent part of the cylinder from which the profile 66 is formed aligns with an exit area of the tape cassette 6. The exit area of the portions 60 is shown by the presence of a flange 59, which will be described in steps (iii) and (iv) below. (iii) The tape 2 on the spool 62 is placed into the joined profile 66 and rear portion 60. The end of the tape 2 is placed in the flange 59. FIG. 10 and FIG. 6a show that each flange 59 protrudes tangentially outwards from the generally cylindrical form of the tape cassette 6 and comprises two grooves 61 formed by upper 59a and lower 59b portions of the flange 59 and spaced apart along the length of the flange 59, one groove at the end nearest the body of the portion 60 and the other at the end distal from the body of the portion 60. Thus at this stage of the assembly procedure, one edge (the rear edge in FIG. 10) of the tape 2 is simply pushed into the grooves 61. (iv) The other portion, front portion 60 is press-fit to the free edge of the profile 66. The grooves 60a of the front portion are not visible in FIG. 10 but are aligned with the grooves 60a in the rear portion 60 and the protrusions 63 in the profile 66. Thus the tape 2 and the spool 62 are encased within the two portions 60 and the profile 66. The edge of the end of the tape 2 that is not already in the flange 59 of the rear portion 60 is pushed into the grooves 61 of the front portion 60. (v) The front and rear portions 60, although generally circular in shape, contain a central hole or cut-out portion 60b. A sprocket 68 is pushed into the hole 60b in the front portion 60 to form a press-fit in the spool 62, and a plug 70 is pushed into the hole 60b in the rear portion 60 to form a press-fit in the other end of the spool 62. The sprocket 68 has an inner cylindrical portion 68a with formations that can be picked up to drive the sprocket 68 and hence the spool 62 to rewind tape 2 onto the spool 62 during reverse feeding. The plug 70 also has an inner cylindrical portion 70a. The inner cylindrical portions of the sprocket 68 and the plug 70 are sized to be able to rotate in the holes 60b in the portions 60. The sprocket 68 and the plug 70 both have circular flanges 68b, 70b extending from the inner cylindrical portions 68a, 70a which fit inside curved ribs 60c on the portions 60. Only the ribs 60c on the front portion 60 are visible in FIG. 10. (vi) The leaf springs 64 are assembled onto the front and rear portions 60. This part of the procedure is shown more clearly in FIG. 13. Each leaf spring 64 has a substantially straight attachment portion 64a and a longer, curved drag portion 64b. The inner faces of the portions 60 each comprise a protrusion 60d aligned with the protrusion 59 but protruding from the region of the portion 60 at a position which substantially coincides with one end of the profile 66. Thus the protrusions 60d are located at the exit point of the tape 2 from the cassette 6. The protrusions 60d are widest where they emerge from the portions 60 and step down to a narrower portion at their distal ends. The attachment portion 64a of each leaf spring comprises a resilient curved portion 64c on its upper side, which is designed to be pushed over the narrower portion of a protrusion 60d and then abut on the end of the wider portion of the protrusion 60d. Arrows show the direction of fitting of the leaf springs 64 and FIG. 13b shows the protrusions 64d in detail. Once fitted, the longer portion 64b of the leaf springs 64 curves downwards so that it just touches the wound tape 2. The drag caused by the leaf springs 64 prevents excessive unwinding of the tape 2 when the cassette 6 is not being used for printing, but the drag force is overcome to unwind the tape during printing. The drag force nevertheless prevents excessive unwinding of the tape 4 during printing as well as when the cassette is not being used for printing. Due to the shape and attachment of the leaf springs 64, the drag force has a main component acting in a direction towards the centre of the spool (although some force may be exerted along the tape). Since there are two leaf springs, the drag force acts towards the outer edge of both sides of the tape. Two further features of the tape cassette 6 can be seen in FIG. 6. Firstly, the portions 60 each have an area cut-out of the edge which forms a finger grip 90. This is conveniently disposed some way round from the exit area of the cassette 60 so that the finger grip can be held in one hand and the tape 2 in the other. Another shaped cut-out disposed in between the edge and the centre cut-out 60b forms a viewing hole 92 which allows a user to view the type of labels or tape contained in the tape cassette 6. It should be noted that once the cassette 6 is assembled, the two flanges 59 form a sleeve for the tape 2 which holds the tape 2 on either edge. It can further be seen that the flanges 59 are disposed symmetrically across the width of the tape cassette 6 (i.e. along the “length” of the cylindrical form of the profile 66) and that therefore as a result of running through the grooves 61 the tape 2 is centred as it exits the tape cassette 60. This is an important feature because if the tape 2 were to exit the cassette off-centre, this deviation might not be correctable in the printer and hence the tape 2 would arrive at the printhead 16 off-centre, resulting in poor printing quality. It has been mentioned above with respect to the mechanism shown in FIG. 12 that the printer is designed to accommodate cassettes of different widths, carrying tapes of different widths. Cassettes 6 of different widths are achieved by varying the length dimension of the profile 66 in accordance with the tape 2 so that the cassette 6 is of a suitable width to accommodate a tape 2 without excessive space between the tape 2 and the portions 60. In other words, the tape width is generally just slightly less than that of the profile 66. The differently-dimensioned profiles are achieved by use of the same manufacturing tooling. The tooling is a plastic injection mould and includes an ejector plate in a mould for moulding the profile 66, and the differently-sized profiles are achieved by putting the ejector plate in different positions. Differently-sized profiles 66 can be used with the same portions 60 since they have the same press-fit attachments. Referring now to FIG. 14 as well as FIG. 10, another feature of the sprocket 68 will be described. It can be seen in FIG. 10 that the inner cylinder 68a of the sprocket 68 and the inner cylinder 70a of the plug 70 have a featured exterior surface. The features are ribs 94. These can be more clearly seen in FIG. 14b, which shows a close-up of the surface of the plug 70. FIG. 14a shows the spool 62 with the plug 70 fitted such that the circular flange 70b abuts on the edge of the spool 62. The ribs 94 are angled and are therefore triangular in cross-section, extending out of the inner cylinder 70a. The spool 62 is made of cardboard, hence in fitting the plug 70 through the cut-out portion 60b of the rear portion 60, the inner cylinder 70a slides into the spool 62 and the ribs 94 are pressed into the inside of the spool 62. The ribs 94 on the sprocket 68 are fitted in a similar manner at the other end of the spool 62. The ribs 94 bear on the inside surface of the spool 62, thus providing the advantage of preventing loosening of the spool 62 on the sprocket 68 and the plug 70. This prevents unwanted movement of the tape 2 away from its roll. Another advantage is that the tolerance on the spool diameter is less critical which reduces manufacturing and quality control costs. The particular configuration of the protrusions is not critical, as long as there is an interference fit between the protrusions and the inside surface of the spool 62. However, the serrated nature of the ribs 94 assists in preventing loosening of the spool 62 on the sprocket 68. A second embodiment of a cassette and printer will now be described. The features of the tape cassette which differ from those of the cassette 6 will be highlighted and the different insertion method of the cassette will also be explained. Thus the second printer is similar to the previously-described printer but differs in the cassette receiving bay. A cassette of the second embodiment is shown in FIG. 15, indicated generally by reference numeral 100. The cassette 100 is constructed in a similar manner as the cassette 6 from similar pieces, so the construction process is not being repeated here. One difference between the cassette 100 and the cassette 6 is the shape of the tape exit region of the cassette. In the cassette 100 the flanges 59′ are differently shaped from the flanges 59 of the cassette 6 such that the underside of the flanges 59′ forms a more pronounced recess 102 with the main body of the cassette 100. This recess is for receiving an idler roller 104 of the printer which the emerging tape moves against, as shown in FIG. 18. Another difference between the cassette 100 and the cassette 6 is in the design of the profile 66′. The profile 66′ is better shown in FIG. 16. On the outer edge of the profile 66′ are two positioning ribs 106 and three fixation ribs 108. The positioning ribs run across the width of the profile 66′ (i.e. along the “length” if the profile is considered to be a cylinder) and are elongate in shape and substantially straight. Their purpose is to prevent the cassette 100 turning in a radial direction when inserted in the printer. The purpose of the fixation ribs 108 is to prevent axial movement of the cassette 100 out of the printer once inserted. They are channel-shaped, having a long leg portion 108a similar to the positioning ribs, a middle portion or base 108b extending from one end of the long portion 108a around a small part of the circumference of the profile 66′ and a short leg portion 108c running back across the width of the profile 66′ from the end of the horizontal portion 108b distal from the long portion 108a. The leg portion 108c extends across approximately half the width of the profile 66′. The leg portion 108c forms an angle somewhat greater than a right angle with the horizontal portion 108b to facilitate smooth insertion of the cassette 100 into the printer. Insertion of the cassette 100 in the printer will now be described with reference to FIGS. 17 and 18. The cassette 100 is inserted differently from the cassette 6 in that it is pushed into a cassette receiving bay 110 of the printer, rather than being received between two supports. The cassette receiving bay 110 is shown in FIG. 17 without a cassette inserted. The cassette receiving bay 110 is generally cylindrical in shape, with a push-plate 112 at one end and open at the other end. Thus as shown in-figure 17 the cassette 100 is to be inserted downwards onto the push-plate 112. The side of the generally cylindrical shape is formed of a locking ring shown generally by reference numeral 114. The inside surface of the locking ring 114 is visible in FIG. 17 and there can be seen two grooves 116 for receiving the positioning ribs 106 and three grooves 118 for receiving the fixation ribs 108. A fixed part of the cassette receiving bay sits behind the locking ring 114. In order to insert the cassette 100, the ribs 106, 108 and the grooves 116, 118 are aligned and the cassette 100 is pushed downwards such that each rib slides along its respective groove. The push-plate 112 is moveable and is therefore pushed downwards in FIG. 17 as the cassette 100 is inserted. The locking ring 114 includes an exit slit for the tape 2 so that the tape 2 can exit the cassette receiving bay past the idler roller 104. This can be best seen in FIG. 18a, which shows an inserted cassette 100 which has pushed down the push-plate 112. In FIGS. 17a and b, the locking ring 114 is shown in an open position in which the cassette 100 can be inserted. FIG. 17b is similar to FIG. 17a but shows the locking ring 114 hatched to distinguish it from other parts of the cassette receiving bay 110. In this position the grooves 116, 118 are open. The push-plate 112 will be pushed down a variable distance in dependence on the tape width and hence the width of the cassette 100. The push-plate 112 is connected to the locking ring 114 (they are conveniently formed from a single piece) and the locking ring is spring-loaded in a radial direction by a spring 120. Thus as a cassette 100 is pushed into place, the spring 120 tries to close the grooves 116, 118 by turning the ring 114 clockwise in FIGS. 17 and 18 with respect to fixed parts of the cassette receiving bay 110. However, the ring 114 can not be turned and hence the grooves 116, 118 can not be closed until the cassette 100 is fully inserted. This is because during insertion, the fixation ribs 108 hold the grooves 118 open. The cassette 100 is inserted with the base portion 108b of the fixation ribs 108 turned towards the push-plate 112. The angle of the leg portion 108c facilitates smooth insertion. Once the cassette is fully inserted, the fixation ribs 108 have cleared the grooves 118 and hence the spring 120 can act to turn the locking ring 114 to close the grooves 116, 118. FIG. 18a shows a cassette 100 fully inserted and hence the grooves 116, 118 are no longer grooves because they have been closed. FIG. 18b shows the outside of the locking ring 114 and that one portion 114a of the locking ring 114 has slid over the top of the leg portion 108c of the fixation rib 108. Thus the leg portions 108c of the fixation ribs 108 abut on portions of the locking ring and hence prevent removal of the cassette 100 from the printer. This can be more clearly understood from FIG. 18c which is similar to FIG. 18b but shows the portions of the locking ring 114 hatched to distinguish them from other portions of the cassette receiving bay 110. When fully inserted, the cassette 100 is in the correct position for feeding of the tape 2 to the printhead. This is achieved for different widths of cassette because the push-plate 112 is moved different amounts for different cassettes by virtue of the fixation ribs 108 being correspondingly shorter or longer. Thus insertion of the cassette 100 using the ribs 106, 108 has ensured centring of the cassette 100 and hence the tape 2 with the printhead. The cassette receiving bay 110 has a door (not shown) which is closed after insertion of a cassette 100 to cover the otherwise exposed top surface of the cassette. Closing the door moves the idler roller 104 into its working position in contact with tape 2 exiting the cassette 100. In other embodiments, a separate lever is used to rotate the idler roller 104 into position. It is also possible for closure of the locking portion 114 to move the idler roller partially or fully into position. If it were only moved partially, a lever or the door could be used to complete the movement. Further discussion of the ink ribbon cassette 8 will now be made, firstly with reference to FIGS. 8a and 8b. The ribbon cassette 8 is suitable for use with either of the printers of the first and second embodiments described above. FIG. 8a shows a top perspective view of the ink ribbon cassette 8 and FIG. 8b shows a bottom perspective view. Further reference is made to FIG. 19, which shows an exploded view of the ink ribbon cassette 8 to assist in explaining its construction. The ink ribbon cassette 8 is constructed generally from a bottom part 120 and a cover part 122. Each of these parts comprises two half-cylinders joined together, so that when the parts 120, 122 are joined together, two cylinders are formed, one to house the supply reel 24 and the other to house the take-up reel 28. The supply reel 24 comprises a supply spool 124 and the take-up reel 28 comprises a take-up spool 126. The two half-cylinders of the cover part 122 are joined towards the widest part of the half-cylinders i.e. towards the bottom in FIGS. 8a and 19, such that when ink ribbon 4 emerges from the supply spool 124, it emerges from a slit 128 just above the join and is relatively protected by the two half-cylinders before it re-enters the cassette 8 through a second slit 130 to be taken up by the take-up spool 126. The ink ribbon 4 is used for printing as it passes through the region between the two cylinders. Other features of the ink ribbon cassette 8 that can be seen in FIG. 19 are a supply sprocket 132 and a take-up sprocket 134 which fit respectively inside the supply 124 and take-up 126 spools so as to enable driving of the spools, and a pair of spacers 136 either end of the supply spoof 124. A similar pair of spacers 138 is arranged to fit at either end of the take-up spool 126. There are also coil springs 140, 142 arranged respectively to act on the supply 132 and take-up 134 sprockets and having respective covers 144, 146 in which the springs are fitted. The purpose of the springs 140, 142 is to exert a constant force axially on the sprockets 132, 134, thereby maintaining ink ribbon tension. The end wall of the bottom portion 120 has flat or planar disc-shaped portions 152 onto which the other end of the springs 140, 142 bear. It would be possible to provide a single spring acting on only one of the sprockets but two springs provide better control over the ink ribbon tension. FIG. 20 shows in greater detail the bottom portion 120 of the ink ribbon cassette 8. Press fittings 148 for enabling press fitting of the bottom portion 120 with the cover 122 can be seen, and also a number of alignment ribs 150 to ensure accurate fitting with the cover. The flat spring supports 152 formed at one end of the bottom portion 120 are also visible. The ends of the springs 140, 142 rest on these supports to enable them to exert the necessary force on the sprockets 132, 134. Finally, two rewind brakes 154 can be seen in the region of the bottom portion 120 where the ends of the sprockets 132, 134 (where the springs make contact) reach to. These take the form of posts and there are two corresponding posts in the cover 122. Their purpose is to prevent unwinding of the ink ribbon 4 during transportation of the cassette 8. The action of the rewind brakes 154 can be better understood with reference to FIGS. 21a and 21b which show the unwind sprocket 132 (the rewind sprocket 134 is similar). It can be seen that the end of the sprocket 132 which contacts the spring 140 is formed of three cylinders, all of which have a greater diameter than the main body of the sprocket 132. The largest, inner cylinder 156 is a relatively flat disc and is located furthest from the spring contact point. This contains a series of openings 162 cut into the disc and arranged in a circular formation on the face which contacts the main body of the sprocket 132, located just outside the main body. The posts 154 fit into an opening 162, thereby holding the sprocket 132 such that it can not easily turn if the cassette 8 is subjected to vibration. An anti-turn rib 164 runs along much of the length of the sprocket 132 and can be picked up by a corresponding recess on the interior of the spool 124 for positive engagement with the spool for rewinding the ink ribbon 4. The other two cylinders, an outer cylinder 158 and an inner cylinder 160, form the end of the sprocket 132. The inner cylinder 160 sits inside the outer cylinder 158 but extends further out in the direction of the spring 140. This is to maintain a constant contact with the spring 140. The outer cylinder is used as a bearing surface onto the interior of the bottom portion 120 for the sprocket 132. Reference is now made once again to FIG. 8a, together with FIGS. 22 and 23. It can be seen in FIG. 8a that the ink ribbon cassette 8 has a ramp 166 cut out of the upper surface of the cover portion 122 at the end where the springs 140, 142 are disposed, and roughly centralised between the supply and take-up cylinders. The centralised position is for balancing the forces during insertion and removal of the ink ribbon cassette 8 from the printer. The ramp 166 slopes upwards towards the end of the cassette 8. FIG. 22a shows the ink ribbon cassette 8 partially inserted into the printer. It is inserted non-ramp end first into a suitably-shaped recess, and is pushed in in a direction along the length of the spools 124, 126. The printer includes release springs 168 acting on each sprocket (only one is visible in FIG. 22a) and as the cassette is inserted, the printer sprockets of the shafts 22, 28 slide into the sprockets 132, 134 (not visible). FIG. 22b shows an enlarged view of a lock 170 of the printer. This lock is designed to interact with the ramp 166. As can be seen in FIG. 23, the lock 170 includes a sprung button 172 which is resiliently moveable and which extends downwards in FIG. 22b so as to meet the ramp 166 as the cassette 8 is inserted. It can also be seen that as well as the ramp 166, the same face of the cassette 8 contains a slot 174 disposed just behind the ramp 166 (i.e. further away from the edge of the cassette 8) which is for receiving the button 172. It should be understood that the cassette 8 has a finite depth in the region of the ramp 166 and the slot 174, and that therefore the slot 174 extends through the material thickness of the cassette. However, this is not necessary because the button 172 is connected to a moveable centre portion 171 of the lock 170 which engages with the ink ribbon cassette 8 and which can conveniently be used to release the lock 170 as explained in the following paragraph. FIG. 23 shows three stages of insertion of the cassette 8 in the printer, and shows the lock 170 upside down as compared to FIG. 22. In FIG. 23a, the ramp 166 has not reached the lock and therefore the button 172 is sprung out. Thus if the cassette 8 did not have the ramp 166, it would not be possible to insert the cassette because the button 172 would prevent insertion. The centre portion 171 is in a position towards the front of the lock 170 i.e towards the exterior face of the printer. In FIG. 23b the cassette 8 is inserted in the direction of the arrow A and as the ramp 166 meets the button 172 it gradually pushes it upwards (downwards in the figure) until the button 172 reaches the flush position of FIG. 23b and the cassette clears the lock. The centre portion 171 has moved inwards with the button 172 i.e. towards the interior of the printer. In FIG. 23c, the cassette 8 is fully inserted and therefore the button 172 springs back out and enters the slot 174, such that it extends beyond the depth of the slot. The centre portion 171 has also returned to its original position. Thus the cassette 8 is locked in place in the printer. In order to remove the cassette 8 from the printer, the centre portion 171 is pushed inwards, and the springs 168 then release the cassette 8. It can be understood that the ramp and button mechanism would work equally well in reverse, i.e. with the printer bearing the ramp and slot and the cassette bearing the button. Reference is now made to FIGS. 24 to 26 which show an alternative embodiment of an ink ribbon cassette, labelled generally with reference numeral 200. This ink ribbon cassette can be used with either of the two printer embodiments described above. The exploded view of FIG. 24 shows that this cassette has similar components to the ink ribbon cassette 8. One difference is a spring 180. This is a single, generally flat elongate spring that is provided in place of the springs 140, 142 of the ink ribbon cassette 8. FIG. 25a shows insertion of this spring into the bottom of the cassette such that two curved portions 180a, one disposed towards either end of the spring 180 can act on the ends of the sprockets. FIG. 25b shows the spring 180 inserted in the cassette 200. This spring has a similar effect to the springs 140, 142 in that it maintains ink ribbon tension. An advantage of using the spring 180 is that it enables the cassette 200 to be more compact than the cassette 8. FIG. 26 shows the bottom portion of the cassette 200 without an ink ribbon present. It can be seen that towards one end of the bottom portion there are provided two sets of ribs 180 running across the bottom portion in the region of one end of where the ink ribbon and sprockets are to be located. These are for the outer cylinders 158 (see FIG. 21b with respect to the ink ribbon cassette 8) to bear on. Such ribs could be provided in the ink ribbon cassette 8. Although in the above embodiments the example of a tape as a recording medium has been used, the invention and the described embodiments would work equally well with other types of recording medium, for example die-cut labels. The applicant draws attention to the fact that the present invention may include any feature or combination of features disclosed herein either implicitly or explicitly or any generalisation thereof, without limitation to the scope of any of the present claims. In view of the foregoing description it will be evident to a person skilled in the art that various modifications may be made within the scope of the invention.
20060928
20130910
20070111
63579.0
B41J3528
0
LIANG, LEONARD S
PRINTING DEVICE AND CASSETTE
UNDISCOUNTED
0
ACCEPTED
B41J
2,006
10,540,626
ACCEPTED
Unfastening prevention device
An object of the present invention is to provide an unfastening prevention device which has nothing projecting outside, and can prevent unfastening at either head or distal end of a bolt. An unfastening prevention is attained by covering a cap (6, 16) to screwed up fastening means formed of a bolt (2) and a nut (3). In a groove (6a, 16a) formed on an inner surface of the cap (6, 16) an outer periphery of a spring ring (8) is engaged, an inner periphery of the spring ring being engaged in a groove (7a) of a holder (7), restricting axial direction (2a) and resulting in slip out prevention. Even when a torque is given on the cap (6, 16), the cap idles, fastening condition does not change and unfastening prevention is attained.
1. Unfastening prevention device attached to screwed up fastening means comprising: a cap covering at least torque-receiving portion from axially one side of the fastening means and being provided with a groove on its inner surface and a widened part on its inner surface close to its opening end of which inner diameter gradually increases as it goes to the opening end; a spring means biased outwardly so as to engage its outer periphery into the groove formed on the inner surface of the cap, being able to slide along the inner surface of the cap except for the groove area and being able to decrease its diameter due to compression from outside by the widened part and a restriction means for the spring means axially restricting the spring means to move. 2. Unfastening prevention device as claimed in claim 1, said cap is or is not provided with plural holes penetrating from outer surface to the groove formed on the inner surface. 3. Unfastening prevention device as claimed in claim 1 comprising, first elastic body biasing whole inner surface of the spring means radial outwardly located inside of the spring means restricted by the restriction means. 4. Unfastening prevention device as claimed in claim 1 comprising, second elastic body disposed between the fastening means and cap means, and compressed when the cap means is set.
TECHNICAL FIELD This invention relates to an unfastening prevention device for fastening means once screwed up by bolts and nuts etc. BACKGROUND ART Conventionally, fastening by bolts and nuts is widely known in mechanical fastening places such as fastening of a number plate to a bumper of automobiles, fastening of a pole base plate to anchor nuts or anchor bolts, fastening in construction sites of iron towers or buildings and fastening parts to railroads or some structures. According to screw up fastenings, it is easy to increase or decrease the fastening rigidity by adjusting fastening torque and it is also possible to readjust the fastening rigidity after the fastening process has been completed if necessary. General tools such as spanners may be utilized to screw up or release bolts and nuts for transmitting torque, and large fastening rigidity can be easily obtained by applying relatively small torque. On the fastened places, various proposed unfastening means may be applied to keep the fastened condition long. But recently, crimes such as breaking fastening places of number plates, iron towers for power transmission lines and connecting places of rail roads are committed by somebody unknown. Fastening places using bolts and nuts are possible to keep stable and long lasting fastened state by applying appropriate unfastening prevention means. But it is not possible to prevent some body with malicious intent break and loosen fastening means using general tools. The present applicant has proposed unfastening prevention devices each of which is covered on a fastened place of bolt and nut and is not released by general tools in patent application 2000-148383 (patent publication KOKAI 2001-330020) and patent application 2000-218455 (patent publication KOKAI 2002-39146). In the former patent application 2000-148383, a cylindrical cover member is fixed on a shank of a bolt by a pin. In the patent application 2000-218455, a cover member is fixed on a distal bolt shank projecting from a nut. But according to the patent application 2000-148383, the pin projects out of the cover member. According to the patent application 2000-218455, it is only applicable at distal end of the bolt shank, and it is not possible to prevent unfastening at head of the bolt. SUMMARY OF THE INVENTION (Technical Problem to be solved by the Invention) An object of the present invention is to provide an unfastening prevention device which has nothing projecting outside, and can prevent unfastening at either head or distal end of a bolt shank. (Solution for the Problem) The invention as claimed in claim 1 of the present invention is an unfastening prevention device attached to screwed up fastening means comprising: a cap covering at least torque-receiving portion from axially one side of the fastened parts and being provided with a groove on its inner surface and a widened part on its inner surface close to its opening end of which inner diameter gradually increases as it goes to the opening end; a spring means biased outwardly so as to engage its outer periphery into the groove formed on the inner surface of the cap, being able to slide along the inner surface of the cap except for the groove area and being able to decrease its diameter due to compression from outside by the widened part and a restriction means for the spring means axially restricting the spring means to move. According to the first invention, the unfastening prevention device is attached to a fastening place screwed up by a bolt and nut and provided with cover (cap) means, spring means and restriction means. The cover means covers at least torque-receiving portion, and is provided with a groove on its inner surface in which groove outer periphery of the spring means is engaged. The restriction means locates in the fastening place and restricts axial movement of the spring means. When the spring means is restricted in the fastened parts, cover means is attached from one axial side, and the cover means are hammered, the spring means is decreased in its diameter, slides on the inner surface especially on widened part near open end of the cover means, then meets with the groove and its outer periphery is engaged in the groove. The cover means together with restriction means prevents axial movement of the cover means and a possible removal of the cover means from fastened parts. Since the cover means covers at least torque-receiving portion of the fastening means, it is impossible to give any torque on the fastening means by a general tool, resulting in perfect unfastening prevention. On the outer surface of the cover means, there is no need to provide any portion protruding outside at all. The restriction means may be composed as a groove on head of bolt or nut as well as on outer surface of spacers so as to be able to engage the inner periphery of the spring means. The spring means may be used as a washer adjusting its axial position by another washer(s) or/and spacer(s), and its outer periphery is engaged in the inner groove of the cover means. Another invention 2 is characterized by that said cap means is or is not provided with plural holes penetrating from outer surface to the groove formed on the inner surface. According to the second invention, since the holes penetrate from outer surface to the inner groove, pins of special tool pressed into the holes are able to press the spring means inwardly. Resulting from decrease in diameter of the spring means, the outer periphery of the spring means is forced out from the inner groove of the cover means, causing not to restrict axial movement of the cover means so as to release the cover means from the fastened parts. After the removal of the cover means form the fastened parts, getting loosen or adjusting the fastening rigidity by general tool become possible. When the cover means is removed from the fastened parts, it is possible to loosen or readjust fastening condition by common spanners or like tools. Also when all said holes are abolished, the cover may be called as a dead-lock fit type, which is suitable when the cover must not be unfastened by all means, and its manufacturing cost can be decreased. Another invention 3 is characterized by that said unfastening prevention device comprising, first elastic body biasing whole inner surface of the spring means radial outwardly located inside of the spring means restricted by the restriction means. According to the third invention, since the spring means is biased by the first elastic body radial outwardly at the position of restriction in the groove by the restriction means, the spring means is kept at a certain position and all the peripheral portion projects uniformly and coaxially. When the cover means is put, the inner surface of the cover means slides smoothly on the outer surface of the spring means and causes uniform decrease of the spring means diameter. Another invention 4 is characterized by that said second elastic body disposed between the fastened parts and cap means, and compressed when the cap means is set. According to the forth invention, in case a fastened part, e.g. a number plate vibrates, vibration and noise of cover means are prevented by the second elastic body, and when the cover means is released by special tool, the cover means is popped out automatically. (Effects over Prior Arts) As described above, according to the present invention (first to forth inventions), the cover means is attached to a fastened place screwed up by a bolt and nut and the cover means covers at least torque-receiving portion. The cover means is not provided with anything projected outwardly. The cover is provided with a groove on its inner surface in which groove outer periphery of the spring means is engaged. Since once cover means is attached, the axial movement of the cover means is restricted by the spring means, cover means is prevented removing from the fastening place. Due to the presence of the cover means, it is not possible to give unfastening torque using general tools resulting in unfastening prevention. The restriction means may be composed as a groove on head of bolt or nut as well as on outer surface of spacers so as to be able to engage the inner periphery of the spring means. Further, according to the present invention, it is possible to release the cover means from the fastening place using holes formed on cover means and a special tool. After the removal of the cover means form the fastening place, getting loosen or adjusting the fastening rigidity become possible. Also when all said holes are abolished, the cover may be so called a dead-lock fit type, which is suitable when the cover must not be unfastened by all means, and its manufacturing cost can be decreased. Further, according to the present invention, since the cover means is kept coaxial, it slides and is fitted smoothly. Further, according to the present invention, in case a fastened part, e.g. a number plate vibrates, vibration and noise of cover means are prevented by the second elastic body, and when the cover means is released by special tool, the cover means is popped out automatically. BRIEF DESCRIPTION OF THE DRAWIMGS FIG. 1 is partially sectional vertical views showing first and second aspects of unfastening prevention devices according to the present invention. FIG. 2 shows a plan view and sectional vertical view of a cap of an embodiment of FIG. 1, a sectional vertical view of another embodiment corresponding to FIG. 2(b) and a sectional vertical view of another embodiment corresponding to d-d section of FIG. 2(b). FIG. 3 shows a plan view and front view of a holder shown in the embodiment of FIG. 1. FIG. 4 is a plan view of a spring ring shown in the embodiment of FIG. 1. FIG. 5 shows plan views of rubber rings (first and second elastic bodies) in the embodiment of FIG. 1. FIG. 6 is a front view of a bolt used in the 3rd embodiment of the present invention. FIG. 7 is a front view of a bolt used in the 4th embodiment of the present invention. FIG. 8 shows a plan view and front view of a bolt in the 5th embodiment of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION FIG. 1 shows schematic embodiments of unfastening prevention devices according to the present invention. FIG. 1(a) shows first aspect of the embodiment, and FIG. 1(b) shows second aspect. In the following drawings, like elements have like numbers and thereby eliminate duplicate explanations. As shown in FIG. 1(a), in the unfastening prevention device 1 which is first aspect embodiment of present invention, a fastening means (place) for fastened parts 4, 5 is composed by a bolt 2 and a nut 3, and a cover element i.e. cap 6 covers a head 2b of the bolt 2 from one (upper) end of axle line 2a extending upper and lower directions of the bolt 2, i.e. from the side of proximal end of the bolt 2. Inner surface of the cap 6 (cover element or cover means) opens downwardly via a widened part 6c of which diameter increases as it goes down axially downwardly along the axle line 2a to its one (lower) end (the widened part 6 being a quasi taper slightly projecting inwardly in ark as shown in the drawing or in perfect taper), and is closed at another (upper) end forming a bottom 6d. From the bottom 6d, nothing projects outside (upper side) axially along the axle line 2a. Once the cap 6 is fixed, a spanner or other general tool can not be approached and be actuated to the fastening torque receiving part, i.e. at least to the head 2b of the bolt 2. The cap 6 in the drawing is provided with an annular groove 6a on the inner surface. Between an outer surface of the cap 6 and groove 6a, there are provided plural, for example four pin insertion holes 6b apart equal in circumferential direction. When cap 6 is fully covered on the fastening means, groove 6a of the cap 6 opposes to an annular groove 7a formed on an outer surface of a holder 7. The holder 7 is disposed between head 2b of the bolt 2 and an upper surface of the fastened part 4 as if it is a common metal washer, and is provided with a tapered part 7c which functions as an introducing guide to secure centering posture of the widened part 6c when the cap 6 is being attached. Between groove 6a of the cap 6 and groove 7a of the holder 7, there is a spring ring 8 (resilient material). Between an inner surface of the spring ring 8 and groove 7a of the holder 7, an elastic rubber ring 9 (first elastic body) is disposed. In case of unfastening once attached cap 6 at an attaching factory, an exclusive special tool 10 is disposed as shown in FIG. 1(a), each pin 10b of four nail arms 10a is adjusted to enter the pin insertion hole 6b, diameter of the spring ring 8 is decreased by pins 10b from outside caused by turning a manipulation part 10c and the spring ring 8 is pushed out inside the groove 6a, thereby the cap 6 is automatically popped up by up to that time compressed elastic body 11 (second elastic body). As shown in FIG. 1(b), unfastening prevention device 11 as second aspect embodiment of the present invention, a cap 16 is engaged from distal end 2c of the bolt 2 under the condition that holder 7 is disposed between lower surface of the fastened part 5 and nut 3. An inner surface of the cap 16 is provided with an annular groove 16a, and spring ring 8 is put between the groove 16a and groove 7a of the holder 7 to effect fastening of the cap 16, above which is the same as the embodiment of FIG. 1(a). Cap 16 is also provided with same pin insertion holes 16b as pin insertion holes 6b of the cap 6. A bottom of the cap 16 in this embodiment is provided with a bolt insertion hole 16d through which distal end 2c of the bolt 2 is inserted. Even when distal end 2c of the bolt 2 is entered in the bolt hole 16d, distal end 2c is designed not to protrude outside the hole along axle line 2a. When axial height of the cap 16 is increased, or distal end 2c of the bolt 2 is shortened, cap 6 shown in FIG. 1(a) which is not provided with bolt hole 16d may be used instead of cap 16. Reference numeral 16c is a widened part. As shown in FIG. 1, when the caps 6, 16 are engaged on the fastening means, grooves 6a, 16a of the caps 6, 16 and groove 7a of the holder 7 are tightly connected by the spring ring 8, axial movement along axial line 2a of the caps 6, 16 are prevented thereby caps 6, 16 can not be taken out. Even when some torque around the axle line 2a is actuated outer surface of the caps 6, 16, slipping occurs between grooves 6a, 16a and outer surface of the spring ring 8 or between inner surface of the spring ring 8 and groove 7a of the holder 7, causing the caps 6, 16 run idle, and the torque is prevented to reach to the holder 7. If some torque is transmitted to the holder 7, it is not possible to transmit torque to head 2b of the bole 2 or nut 3, unfastening of the fastening means is effectively prevented. In the embodiments of FIG. 1, unfastening prevention is effected at one side, i.e. head 2b of the bolt 2 or distal end 2c, the unfastening prevention may be effected on both sides. FIG. 2, FIG. 3, FIG. 4 and FIG. 5 show the cap 6, holder 7, spring ring 8 and rubber ring 9, elastic body 11 of FIG. 1(a) respectively. In FIG. 2 and FIG. 3, (a) shows plan view and (b) shows sectional elevation view. FIG. 4 and FIG. 5 show plan views. As shown in FIGS. 2(a), 2(b), cap 6 is generally cylindrical and made of metal such as iron (ferrous material) and axially one side is open and other side is closed. In the inner surface close to the opening end, the annular groove 6a is formed. Plural pin insertion holes 6b are formed between the groove 6a and outer surface at regular circumferential intervals. The open end inner surface of the cap 6 is provided with a taper (widened part 6c) inner diameter of which increasing as it goes to the opening. In other words, since the inner diameter of the widened part 6c is largest at the open end, it is easily covered on the outer periphery of the spring ring 8 when the cap 6 is going to be covered. Under the condition that the outer periphery of the spring ring 8 is covered by the opening part (widened part 6c), when the bottom 6d is hammered, the widened part 6c slides on the outer periphery of the spring ring 8, then the outer diameter of the spring ring 8 is decreased and finally the spring ring 8 engages in the groove 6a. Outer periphery of the spring ring 8 engages in the groove 6a. When the spring ring 8 engages in the groove 6a, pins 10b (FIG. 1(a)) are pressed inside the pin insertion holes 6b against the outer surface of the spring ring 8 causing decrease of the diameter of the spring ring 8 and disengage the spring ring 8 from the groove 6a. As shown in FIG. 2(c), the cap 6 has no holes like pin insertion holes 6b of FIG. 2(b) thereby making it as a complete lock up type. This lock up type is suitable for a fastening means which is obliged not to be unfastened by all means. This type is able to decrease the manufacturing cost as low as possible. As shown in FIG. 2(b), outer surface (upper surface) of bottom 6d of the cap 6 is provided with a shallow recession 6e, round for example, in which recession 6e a seal 20 with for example logo mark is attached by means of both side adhesive tape. The seal is not able to be peeled off even using nails, so durability of the seal increases. Although the groove 6a in FIG. 2(b) is annular, as shown in FIG. 2(d), intermittent grooves 6a with short circumferential length disposed annularly at regular intervals and a spring ring 8 made of piano wire with ark projections 8b engaged in the grooves 6a may be used. As shown in FIG. 3, holder 7 is generally annular and made of metal such as iron. The holder 7 is provided with groove 7a on the outer surface, a central insertion hole 7b to be inserted by shank of the bolt 2, and tapered part 7c located at one end. Inner periphery of the spring ring 8 is engaged in the groove 7a. The spring ring 8 is designed to almost completely enter in the groove 7a when outer surface is compressed radially inwardly. Namely, groove 7a of the holder 7 functions as a restriction means to restrict the axial movement of the spring ring 8. When attachment of the cap 6 is completed, although widened part 6c of the cap 6 abuts or opposes with a small clearance left against the tapered part 7c, main object of the tapered part 7c is to stabilize the posture (keep centering position) of the cap 6 during the cap attaching procedure. As shown in FIG. 4, spring ring 8 is made of metal plate such as iron plate annually, and is provided with an opening 8a, a cut part in circumference. Diameter of the spring ring 8 is shortened by compression from radially outward positions (for example from four positions at regular intervals). Upon releasing the compression force, the spring ring 8 returns to its free condition. By widening the interval of the opening, inner periphery of spring ring 8 may be engaged in groove 7a of the holder 7. Once engaged in the groove 7a, interval of the opening 8a returns to its free condition. As shown in FIG. 5(a), rubber ring 9 is a sample of flexible ring made of elastic material. In the embodiments of FIG. 1(a) and FIG. 1(b), spring ring 8 is set after rubber ring 9 is set in groove 7a of the holder. According to the existence of rubber ring 9, spring ring 8 is set in an accurate center thereby equal radial amount of the outer peripheral portion of spring ring 8 is kept projecting. When spring ring 8 is compressed from outside and shrunk in diameter, rubber ring 9 is also compressed and shrunk, leaving room to spring ring 8 for deformation. Instead of rubber ring 9, other plastic elastomer ring may or may not be used. As an example, rubber like elastic body 11 is provided with a central small hall 11a, fixed on an inner surface of cap bottom 6d by for example both sides adhesive tape (not shown), kept slightly (for example 0.8 mm) compressed condition after the completion of cap 6 mounting procedure, urging the cap 6 upwardly thereby eliminating clearance between spring ring 8 and holder 7 and also preventing chattering and noise caused by vibration of cap 6. If the elastic body 11 is made of soft silicon rubber, long and stable elasticity is secured. By selecting diameter of small hole 11a, reaction force from elastic body 11 to the set cap 6 is adjusted at most suitable value thereby improve manufacturing efficiency. Among alternatives of elastic body 11, thin wave annular spring or plural dish shaped springs piled by turns may be employed. FIG. 6 shows a bolt 22 to be used in the third embodiment of the present invention. In this embodiment, bolt 22 is provided with a flange 22d in a head 22b integrally, and a groove 22e farmed around the flange 22d restricts spring ring 8 shown in FIG. 4. Namely, instead of using separate holder 7 of embodiment shown in FIG. 1, bolt 22 itself has a function of restricting means to restrict spring ring 8. In this kind of groove 22e of flange 22d, spring ring 8 is engaged, a nut is threaded on distal end 22c of the bolt 22, and cap 6 is attached on the bolt head 22b same as first embodiment shown in FIG. 1(a) to form unfastening prevention means. FIG. 7 shows a bolt 32 used in fourth embodiment of this invention. Top surface center of head 32b of the bolt 32 is provided with, for example, a hexagonal hole 32d through which torque may be applied to fasten or loosen by a hexagonal rod wrench. In this embodiment, a groove 32e directly formed on outer surface of head 32d of the bolt 32 restricts spring ring 8 shown in FIG. 4. Namely, same as the embodiment of FIG. 6, instead of using separate holder 7 of embodiment shown in FIG. 1, bolt 32 itself functions to restrict spring ring 8 and a nut is threaded on distal end 32c of the bolt 32, thereby attaining unfastening prevention by attaching cap 6, same as first embodiment shown in FIG. 1(a). FIG. 8 shows a nut 43 used for the fifth embodiment of this invention. The nut 43 of this embodiment comprises a head 43a and a hollow skirt 43b. Outer surface of the hollow skirt 43b is provided with a groove 43c, in which spring ring 8 shown in FIG. 4 is engaged. According to this construction, unfastening prevention is attained by covering the cap 16, same as second embodiment of FIG. 1(b). The idea of using nut as a restriction means can be utilized on the nut with flange by making a groove on the flange. Although in above embodiments, parts with peripheral groove for receiving inner periphery of the spring ring 8 are used, a washer and a spacer may be piled to make an annular space corresponding to the groove. INDUSTRIAL APPLICABILITY The present invention is applicable using bolts and nuts etc. in mechanical fastening places such as fastening of number plate to bumper of automobiles, fastening of pole base plate to anchor nuts or anchor bolts, fastening in construction sites of iron towers or buildings and fastening parts to railroads or some structures.
<SOH> BACKGROUND ART <EOH>Conventionally, fastening by bolts and nuts is widely known in mechanical fastening places such as fastening of a number plate to a bumper of automobiles, fastening of a pole base plate to anchor nuts or anchor bolts, fastening in construction sites of iron towers or buildings and fastening parts to railroads or some structures. According to screw up fastenings, it is easy to increase or decrease the fastening rigidity by adjusting fastening torque and it is also possible to readjust the fastening rigidity after the fastening process has been completed if necessary. General tools such as spanners may be utilized to screw up or release bolts and nuts for transmitting torque, and large fastening rigidity can be easily obtained by applying relatively small torque. On the fastened places, various proposed unfastening means may be applied to keep the fastened condition long. But recently, crimes such as breaking fastening places of number plates, iron towers for power transmission lines and connecting places of rail roads are committed by somebody unknown. Fastening places using bolts and nuts are possible to keep stable and long lasting fastened state by applying appropriate unfastening prevention means. But it is not possible to prevent some body with malicious intent break and loosen fastening means using general tools. The present applicant has proposed unfastening prevention devices each of which is covered on a fastened place of bolt and nut and is not released by general tools in patent application 2000-148383 (patent publication KOKAI 2001-330020) and patent application 2000-218455 (patent publication KOKAI 2002-39146). In the former patent application 2000-148383, a cylindrical cover member is fixed on a shank of a bolt by a pin. In the patent application 2000-218455, a cover member is fixed on a distal bolt shank projecting from a nut. But according to the patent application 2000-148383, the pin projects out of the cover member. According to the patent application 2000-218455, it is only applicable at distal end of the bolt shank, and it is not possible to prevent unfastening at head of the bolt.
<SOH> SUMMARY OF THE INVENTION <EOH>(Technical Problem to be solved by the Invention) An object of the present invention is to provide an unfastening prevention device which has nothing projecting outside, and can prevent unfastening at either head or distal end of a bolt shank. (Solution for the Problem) The invention as claimed in claim 1 of the present invention is an unfastening prevention device attached to screwed up fastening means comprising: a cap covering at least torque-receiving portion from axially one side of the fastened parts and being provided with a groove on its inner surface and a widened part on its inner surface close to its opening end of which inner diameter gradually increases as it goes to the opening end; a spring means biased outwardly so as to engage its outer periphery into the groove formed on the inner surface of the cap, being able to slide along the inner surface of the cap except for the groove area and being able to decrease its diameter due to compression from outside by the widened part and a restriction means for the spring means axially restricting the spring means to move. According to the first invention, the unfastening prevention device is attached to a fastening place screwed up by a bolt and nut and provided with cover (cap) means, spring means and restriction means. The cover means covers at least torque-receiving portion, and is provided with a groove on its inner surface in which groove outer periphery of the spring means is engaged. The restriction means locates in the fastening place and restricts axial movement of the spring means. When the spring means is restricted in the fastened parts, cover means is attached from one axial side, and the cover means are hammered, the spring means is decreased in its diameter, slides on the inner surface especially on widened part near open end of the cover means, then meets with the groove and its outer periphery is engaged in the groove. The cover means together with restriction means prevents axial movement of the cover means and a possible removal of the cover means from fastened parts. Since the cover means covers at least torque-receiving portion of the fastening means, it is impossible to give any torque on the fastening means by a general tool, resulting in perfect unfastening prevention. On the outer surface of the cover means, there is no need to provide any portion protruding outside at all. The restriction means may be composed as a groove on head of bolt or nut as well as on outer surface of spacers so as to be able to engage the inner periphery of the spring means. The spring means may be used as a washer adjusting its axial position by another washer(s) or/and spacer(s), and its outer periphery is engaged in the inner groove of the cover means. Another invention 2 is characterized by that said cap means is or is not provided with plural holes penetrating from outer surface to the groove formed on the inner surface. According to the second invention, since the holes penetrate from outer surface to the inner groove, pins of special tool pressed into the holes are able to press the spring means inwardly. Resulting from decrease in diameter of the spring means, the outer periphery of the spring means is forced out from the inner groove of the cover means, causing not to restrict axial movement of the cover means so as to release the cover means from the fastened parts. After the removal of the cover means form the fastened parts, getting loosen or adjusting the fastening rigidity by general tool become possible. When the cover means is removed from the fastened parts, it is possible to loosen or readjust fastening condition by common spanners or like tools. Also when all said holes are abolished, the cover may be called as a dead-lock fit type, which is suitable when the cover must not be unfastened by all means, and its manufacturing cost can be decreased. Another invention 3 is characterized by that said unfastening prevention device comprising, first elastic body biasing whole inner surface of the spring means radial outwardly located inside of the spring means restricted by the restriction means. According to the third invention, since the spring means is biased by the first elastic body radial outwardly at the position of restriction in the groove by the restriction means, the spring means is kept at a certain position and all the peripheral portion projects uniformly and coaxially. When the cover means is put, the inner surface of the cover means slides smoothly on the outer surface of the spring means and causes uniform decrease of the spring means diameter. Another invention 4 is characterized by that said second elastic body disposed between the fastened parts and cap means, and compressed when the cap means is set. According to the forth invention, in case a fastened part, e.g. a number plate vibrates, vibration and noise of cover means are prevented by the second elastic body, and when the cover means is released by special tool, the cover means is popped out automatically. (Effects over Prior Arts) As described above, according to the present invention (first to forth inventions), the cover means is attached to a fastened place screwed up by a bolt and nut and the cover means covers at least torque-receiving portion. The cover means is not provided with anything projected outwardly. The cover is provided with a groove on its inner surface in which groove outer periphery of the spring means is engaged. Since once cover means is attached, the axial movement of the cover means is restricted by the spring means, cover means is prevented removing from the fastening place. Due to the presence of the cover means, it is not possible to give unfastening torque using general tools resulting in unfastening prevention. The restriction means may be composed as a groove on head of bolt or nut as well as on outer surface of spacers so as to be able to engage the inner periphery of the spring means. Further, according to the present invention, it is possible to release the cover means from the fastening place using holes formed on cover means and a special tool. After the removal of the cover means form the fastening place, getting loosen or adjusting the fastening rigidity become possible. Also when all said holes are abolished, the cover may be so called a dead-lock fit type, which is suitable when the cover must not be unfastened by all means, and its manufacturing cost can be decreased. Further, according to the present invention, since the cover means is kept coaxial, it slides and is fitted smoothly. Further, according to the present invention, in case a fastened part, e.g. a number plate vibrates, vibration and noise of cover means are prevented by the second elastic body, and when the cover means is released by special tool, the cover means is popped out automatically.
20050624
20070206
20060608
57253.0
F16B3714
0
SAETHER, FLEMMING
UNFASTENING PREVENTION DEVICE
UNDISCOUNTED
0
ACCEPTED
F16B
2,005
10,540,651
ACCEPTED
Method and device for diagnosing the dynamic characteristics of a lambda probe used for the lambda regulation of individual cylinders
A method for diagnosing the dynamic characteristics of a lambda sensor, which is used at least intermittently for a cylinder-individual lambda closed-loop control, which provides for at least one actuating variable of the lambda closed-loop control to be detected and compared to a specifiable maximum threshold, and, if the maximum threshold is exceeded, the dynamic response of the lambda sensor is deemed insufficient with respect to the usability for the cylinder-individual lambda closed-loop control.
1-6. (canceled) 7. A method for diagnosing a dynamic characteristics of a lambda sensor, which is used at least intermittently for a cylinder-individual lambda control, the method comprising: detecting at least one actuating variable of the lambda control; comparing the at least one actual variable to a specifiable maximum threshold; and if the maximum threshold is exceeded, a dynamic response of the lambda sensor is deemed insufficient with respect to usability for the cylinder-individual lambda control. 8. The method of claim 7, wherein the value of lambda of at least one cylinder is detuned by a specifiable value and it is ascertained whether the detuning by the specifiable value is reflected as an offset or a factor in an actuating variable of a particular controller of the lambda control. 9. The method of claim 8, wherein it is ascertained whether a difference or an absolute value of the difference between detuning and offset is smaller than the specifiable maximum threshold. 10. The method of claim 8, wherein the value of lambda is detuned by variation of the cylinder-individual fuel metering. 11. The method of claim 9, wherein the value of lambda is detuned by variation of the cylinder-individual fuel metering. 12. The method of claim 9, further comprising: detecting a suitable operating range for the cylinder-individual lambda control; monitoring the actuating variables of the individual lambda controllers and, if at least one of the actuating variables exceeds its maximum amount, implementing the following: detecting a suitable instant for implementing the following: buffer-storing the actuating variables of the individual lambda controllers; detuning the value of lambda of at least one cylinder by the specifiable value; monitoring the actuating variables of the individual lambda controllers; determining whether the lambda controllers are able to compensate the detuning of the value of lambda, and if the lambda controllers are able to do so, cancellating the detuning, and re-initializing the individual lambda controllers by the buffer-stored actuating variables; and otherwise, outputting a fault signal. 13. A diagnosis device for diagnosing a dynamic characteristics of a lambda sensor, which is used at least intermittently for a cylinder-individual lambda control, comprising: a detecting arrangement to detect at least one actuating variable of the lambda control; a comparing arrangement to compare the at least one actual variable to a specifiable maximum threshold; and an arrangement to determine, if the maximum threshold is exceeded, that a dynamic response of the lambda sensor is deemed insufficient with respect to usability for the cylinder-individual lambda control.
FIELD OF THE INVENTION The exemplary embodiment and/or method of the present invention relates to a method and a device for diagnosing the dynamic characteristics of lambda sensors with respect to a cylinder-individual lambda closed-loop control. BACKGROUND INFORMATION For instance, a lambda closed-loop control in conjunction with a catalytic converter is currently the most effective exhaust-gas treatment method for the spark-ignition engine. Only in interaction with currently available ignition and injection systems is it possible to achieve very low exhaust values. Limit values for the engine exhaust gas are even mandated by law in most countries. The use of a three-way catalytic converter, or selective catalytic converter, is especially effective. This type of catalytic converter is able to break down up to more than 98% of hydrocarbons, carbon monoxides and nitrogen oxides provided the engine is operated within a range of approximately 1% around the stoichiometric air-fuel ratio at lambda=1. In this context, lambda specifies the degree to which the actually present air-fuel mixture deviates from the lambda=1 value, which corresponds to a mass ratio of 14.7 kg air to 1 kg of gasoline that is theoretically required for complete combustion, i.e., lambda is the quotient of the supplied air mass and the theoretical air requirement. As a general principle, lambda closed-loop control measures the particular exhaust gas, the supplied fuel quantity being immediately corrected according to the measuring result via the injection system, fox instance. Used as measuring probe is a lambda sensor, which is able to measure a steady lambda signal around lambda=1 and in this way supplies a signal that indicates whether the mixture is richer or leaner than lambda=1. As may be known, the effect of these lambda sensors is based on the principle of a galvanic oxygen concentration cell having a solid state electrolyte. Furthermore, a cylinder-individual lambda closed-loop control may be used to improve the exhaust gas if the lambda sensor, owing to its dynamic properties, is able to track lambda fluctuations in the exhaust-gas flow caused by cylinder-individual lambda differences at the installation location of the sensor. Due to a temporally high-resolution evaluation of the signal coming from the lambda sensor, it is possible to conclude from the composite lambda signal to the lambda of the individual engine cylinders whose exhaust gas is conveyed to the installation location of the sensor. In this way, cylinder-individual lambda differences may be corrected and the exhaust-gas result or, at the very least, the exhaust-gas stability be improved. The dynamic characteristics of a lambda sensor in new condition is in most cases adequate within a selected operating range. Nevertheless, in the event that the dynamic characteristics of the sensor change, to the effect that cylinder-individual lambda values are unable to be resolved since the response times of the sensor are increasing, the closed-loop lambda control will not intervene although lambda fluctuations are indeed present in the exhaust gas. Causes of a reduced dynamic performance of the sensor are, for instance, constrictions in the protective tube orifices of the sensor or contamination of function-controlling sensor ceramic parts of the solid state electrolyte as a result of deposits. In broad-band sensors, contamination of the diffusion barrier provided there may also play a part. In the worst case, a non-functioning cylinder-individual lambda closed-loop control will result in non-compliance with the mentioned exhaust-gas limit values mandated by law. In this case, the changed dynamic characteristics of the lambda sensor must be indicated by a control light, for example. SUMMARY OF THE INVENTION The exemplary embodiment and/or method of the present invention is therefore based on the objective of providing a method and a device of the type mentioned in the introduction, which allow a reliable diagnosis of the dynamic characteristics of a lambda sensor with respect to a cylinder-individual closed-loop lambda control. In a method and a device for diagnosis of the aforementioned type this objective is achieved by the features of the respective independent claims. The method according to the present invention in particular provides that at least one actuating variable of the closed-loop lambda control be detected and compared to a specifiable maximum threshold, and in the event that the maximum threshold is exceeded, that the dynamic performance of the lambda sensor be considered insufficient with respect to usability for the cylinder-individual closed-loop lambda control. In a first variant of the exemplary embodiment and/or method of the present invention, the dynamic characteristics of the lambda sensor are detected by the cylinder-individual control itself. This is based on the thought that the method of operation of individual cylinder-individual controllers diverges when the dynamic properties are insufficient and the associated actuating variables, namely one or more actuating variables, exceed a specifiable maximum threshold value. In a second variant according to the exemplary embodiment and/or method of the present invention, the dynamic response of the lambda sensor is detected with the aid of a test function, i.e., by an initiated interference or detuning of the instantaneous lambda value. The test function may be implemented on a one-time basis, on an intermittent periodical basis or in an event-triggered manner. The specifiable maximum threshold for a cylinder-individual controller may be exceeded, for instance, when the controller is active and the value of the respective actuating variable is higher than the specifiable amount or the actuating variable is unable to be increased further due to its structure. In this case, the dynamic properties of the lambda sensor will be deemed insufficient with respect to the usability for the cylinder-individual closed-loop lambda control. Furthermore, the exemplary embodiment and/or method of the present invention relates to a diagnostic device, which operates according to the method of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS The FIGURE shows an exemplary diagnosis method according to the present invention on the basis of a flow chart. DETAILED DESCRIPTION The following diagnostic routine for detecting the usability or non-usability of a lambda sensor of a spark-ignition engine, which is described in the following with the aid of the FIGURE, may be implemented only during the time when a cylinder-individual control having individual controllers is active. Depending on the strategy, the test function described hereinafter will be executed once or several times and the results of the tests analyzed only for as long as the test function is active. Following start 10 of the routine, the engine speed and/or the engine load and/or exhaust-gas mass flow 20 are/is ascertained first. On the basis of these data, it is determined in step 30 whether the engine is in an operating state that is suitable for the cylinder-individual control in the first place, and thus suitable for a detection of the dynamic properties of the lambda sensor. If this is not the case, a return to the beginning of the routine takes place in the form of a loop. In the other case, the actuating variables of the individual controllers are monitored 40 and, following detection of the actuating variables, it is also checked 50 whether the amount of at least one of the actuating variables exceeds a specifiable maximum threshold. If this is not the case, a return to step 40 takes place, possibly including a delay. If one or several actuating variable(s) of the individual controllers exceed(s) a specifiable maximum threshold in its/their amount, it is assumed that the dynamic characteristics of the lambda sensor are insufficient. In a next step 70 it is ascertained whether a suitable instant for activating the test function is present. If this is not the case, this test 70 will be repeated in a loop, possibly also by including a delay stage. Otherwise, the test routine begins in that the instantaneously present values of the actuating variables of the individual controllers are buffer-stored 80. Subsequently, an interference is applied 90 to the instantaneously ascertained lambda values and the actuating variables of the individual controllers monitored or recorded 100. It is then checked 110 whether the controller(s) is/are able to compensate for the interference. If this is the case, a positive signal will be output 120, if appropriate, to the effect that the dynamic response of the sensor is adequate. Otherwise, it will be assumed that the dynamic requirements are not met and a corresponding negative signal will be output 130. Finally, the interference is reversed 140 and a re-initialization 150 of the individual controllers takes place using the buffer-stored values. Then, another interference is applied, as indicated by return 160. The described procedure or routine is implemented repeatedly, if appropriate, so as to be able to optimize the actuating variables in an iterative manner, so to speak, or in a stepwise manner. The dynamic properties of the lambda sensor with respect to the cylinder-individual control are therefore ascertained with the aid of the controller function itself and/or the described active test function. In a suitable driving situation, the lambda of a cylinder is intentionally detuned by varying the cylinder-individual fuel metering by a previously defined amount x. When the cylinder-individual control is active, this cylinder detuning must be reflected in the associated cylinder-individual actuating variable of the cylinder-individual control as an additional offset of approximately the same magnitude as the detuning. If the resultant change in the actuating variable amounts only to a portion y of the stimulated cylinder detuning, this indicates that the lambda sensor is no longer able to fully follow the cylinder-individual fluctuations because of a reduced dynamic response. If portion y falls below a specifiable threshold z, i.e., an exhaust-gas relevant residual fault x-z can no longer be adjusted, a fault signal must be output. The resulting exhaust-gas loss is of no consequence in this case. In the case of a satisfactory test result, i.e., the sensor dynamics of the cylinder-individual lambda control are considered adequate since the detuning is completely or virtually completely compensated, the described test function has no detrimental effect on the exhaust gas. In addition, once a test has been concluded, the cylinder detuning will be set back to the initial state, as described. It should be noted that a possibly detected change in the dynamic characteristics of the lambda sensor is not relevant for the remaining functions of the engine control that evaluate the lambda sensor signal, and that these must therefore be monitored separately. The exemplary embodiment and/or method of the present invention may be implemented either as hardware or in the form of a control program as part of the engine control.
<SOH> BACKGROUND INFORMATION <EOH>For instance, a lambda closed-loop control in conjunction with a catalytic converter is currently the most effective exhaust-gas treatment method for the spark-ignition engine. Only in interaction with currently available ignition and injection systems is it possible to achieve very low exhaust values. Limit values for the engine exhaust gas are even mandated by law in most countries. The use of a three-way catalytic converter, or selective catalytic converter, is especially effective. This type of catalytic converter is able to break down up to more than 98% of hydrocarbons, carbon monoxides and nitrogen oxides provided the engine is operated within a range of approximately 1% around the stoichiometric air-fuel ratio at lambda=1. In this context, lambda specifies the degree to which the actually present air-fuel mixture deviates from the lambda=1 value, which corresponds to a mass ratio of 14.7 kg air to 1 kg of gasoline that is theoretically required for complete combustion, i.e., lambda is the quotient of the supplied air mass and the theoretical air requirement. As a general principle, lambda closed-loop control measures the particular exhaust gas, the supplied fuel quantity being immediately corrected according to the measuring result via the injection system, fox instance. Used as measuring probe is a lambda sensor, which is able to measure a steady lambda signal around lambda=1 and in this way supplies a signal that indicates whether the mixture is richer or leaner than lambda=1. As may be known, the effect of these lambda sensors is based on the principle of a galvanic oxygen concentration cell having a solid state electrolyte. Furthermore, a cylinder-individual lambda closed-loop control may be used to improve the exhaust gas if the lambda sensor, owing to its dynamic properties, is able to track lambda fluctuations in the exhaust-gas flow caused by cylinder-individual lambda differences at the installation location of the sensor. Due to a temporally high-resolution evaluation of the signal coming from the lambda sensor, it is possible to conclude from the composite lambda signal to the lambda of the individual engine cylinders whose exhaust gas is conveyed to the installation location of the sensor. In this way, cylinder-individual lambda differences may be corrected and the exhaust-gas result or, at the very least, the exhaust-gas stability be improved. The dynamic characteristics of a lambda sensor in new condition is in most cases adequate within a selected operating range. Nevertheless, in the event that the dynamic characteristics of the sensor change, to the effect that cylinder-individual lambda values are unable to be resolved since the response times of the sensor are increasing, the closed-loop lambda control will not intervene although lambda fluctuations are indeed present in the exhaust gas. Causes of a reduced dynamic performance of the sensor are, for instance, constrictions in the protective tube orifices of the sensor or contamination of function-controlling sensor ceramic parts of the solid state electrolyte as a result of deposits. In broad-band sensors, contamination of the diffusion barrier provided there may also play a part. In the worst case, a non-functioning cylinder-individual lambda closed-loop control will result in non-compliance with the mentioned exhaust-gas limit values mandated by law. In this case, the changed dynamic characteristics of the lambda sensor must be indicated by a control light, for example.
<SOH> SUMMARY OF THE INVENTION <EOH>The exemplary embodiment and/or method of the present invention is therefore based on the objective of providing a method and a device of the type mentioned in the introduction, which allow a reliable diagnosis of the dynamic characteristics of a lambda sensor with respect to a cylinder-individual closed-loop lambda control. In a method and a device for diagnosis of the aforementioned type this objective is achieved by the features of the respective independent claims. The method according to the present invention in particular provides that at least one actuating variable of the closed-loop lambda control be detected and compared to a specifiable maximum threshold, and in the event that the maximum threshold is exceeded, that the dynamic performance of the lambda sensor be considered insufficient with respect to usability for the cylinder-individual closed-loop lambda control. In a first variant of the exemplary embodiment and/or method of the present invention, the dynamic characteristics of the lambda sensor are detected by the cylinder-individual control itself. This is based on the thought that the method of operation of individual cylinder-individual controllers diverges when the dynamic properties are insufficient and the associated actuating variables, namely one or more actuating variables, exceed a specifiable maximum threshold value. In a second variant according to the exemplary embodiment and/or method of the present invention, the dynamic response of the lambda sensor is detected with the aid of a test function, i.e., by an initiated interference or detuning of the instantaneous lambda value. The test function may be implemented on a one-time basis, on an intermittent periodical basis or in an event-triggered manner. The specifiable maximum threshold for a cylinder-individual controller may be exceeded, for instance, when the controller is active and the value of the respective actuating variable is higher than the specifiable amount or the actuating variable is unable to be increased further due to its structure. In this case, the dynamic properties of the lambda sensor will be deemed insufficient with respect to the usability for the cylinder-individual closed-loop lambda control. Furthermore, the exemplary embodiment and/or method of the present invention relates to a diagnostic device, which operates according to the method of the present invention.
20060207
20090127
20060803
63125.0
B60Q100
0
MCCALL, ERIC SCOTT
METHOD AND DEVICE FOR DIAGNOSING THE DYNAMIC CHARACTERISTICS OF A LAMBDA PROBE USED FOR THE LAMBDA REGULATION OF INDIVIDUAL CYLINDERS
UNDISCOUNTED
0
ACCEPTED
B60Q
2,006
10,540,769
ACCEPTED
Novel herbicides
Compounds of formula (I), wherein the substituents are as defined in claim 1, and the agrochemically acceptable salts and all stereoisomers and tautomeric forms of the compounds of formula I are suitable for use as herbicides.
1. A compound of formula I wherein Y is oxygen, NR4a, sulfur, sulfonyl, sulfinyl, C(O), C(═NR4b), C(═CR6aR6b) or a C1-C4alkylene or C2-C4alkenylene chain, which may be interrupted by oxygen, NR5a, sulfur, sulfonyl, sulfinyl, C(O) or C(═NR5b) and/or mono- or poly-substituted by R6; A1 is nitrogen or CR7; A2 is nitrogen or CR8; R1, R2, R6, R7 and R8 are each independently of the others hydrogen, hydroxy, mercapto, NO2, cyano, halogen, formyl, oxyiminomethylene, C1-C6alkoxyiminomethylene, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, C3-C6oxacycloalkyl, C3-C6thiacycloalkyl, C3-C6dioxacycloalkyl, C3-C6dithiacycloalkyl, C3-C6oxathiacycloalkyl, C1-C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1-C6alkoxycarbonyloxy, C1-C6alkylcarbonyloxy, C1-C6alkylthio, C1-C6-alkylsulfonyl, C1-C6alkylsulfinyl, NR9R10, C3-C6cycloalkyl, tri(C1-C6alkyl)silyl, di(C1-C6alkyl)-phenylsilyl, tri(C1-C6alkyl)silyloxy, di(C1-C6alkyl)phenylsilyloxy or Ar1; or R1, R2, R6, R7, R8 are each independently of the others a C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl or C3-C6cycloalkyl group, which may be interrupted by oxygen, sulfur, sulfonyl, sulfinyl, —NR11— or —C(O)— and/or mono-, di- or tri-substituted by hydroxy, mercapto, NO2, cyano, halogen, formyl, C1-C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, C1-C6haloalkoxy, C1-C2alkoxy-C1-C2alkoxy, C1-C4alkoxycarbonyloxy, C1-C4alkylcarbonyloxy, C1-C4alkoxycarbonyl, C1-C4alkylcarbonyl, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, NR12R13, C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, tri(C1-C6alkyl)silyl, tri(C1-C6alkyl)silyloxy or Ar2; or two substituents R6 at the same carbon atom together form a —CH2O— or a C2-C5alkylene chain, which may be interrupted once or twice by oxygen, sulfur, sulfinyl or sulfonyl and/or mono- or poly-substituted by R6c, with the proviso that two hetero atoms may not be located next to one another; or two substituents R6 at different carbon atoms together form an oxygen bridge or a C1-C4alkylene chain, which may in turn be substituted by R6c; or R7 and R8 together form a —CH2CH═CH—, —OCH═CH— or —CH═CH—CH═CH— bridge or a C3-C4alkylene chain, which may be interrupted by oxygen or —S(O)n1— and/or mono- or poly-substituted by R6d; R3 is hydroxy, halogen, mercapto, C1-C8alkylthio, C1-C8alkylsulfinyl, C1-C8alkylsulfonyl, C1-C8haloalkylthio, C1-C8haloalkylsulfinyl, C1-C8haloalkylsulfonyl, C1-C4alkoxy-C1-C4alkylthio, C1-C4alkoxy-C1-C4alkylsulfinyl, C1-C4alkoxy-C1-C4alkylsulfonyl, C3-C8alkenylthio, C3-C8-alkynylthio, C1-C4alkylthio-C1-C4alkylthio, C3-C4alkenylthio-C1-C4alkylthio, C1-C4alkoxycarbonyl-C1-C4alkylthio, C1-C4alkoxycarbonyl-C1-C4alkylsulfinyl, C1-C4alkoxycarbonyl-C1-C4alkylsulfonyl, C3-C8cycloalkylthio, C3-C8cycloalkylsulfinyl, C3-C8cycloalkylsulfonyl, phenyl-C1-C4alkylthio, phenyl-C1-C4alkylsulfinyl, phenyl-C1-C4alkylsulfonyl, S(O)n1—Ar3, phenylthio, phenylsulfinyl, phenylsulfonyl, it being possible for the phenyl-containing groups to be substituted by one or more C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C1-C4alkoxycarbonyl, halogen, cyano, hydroxy or nitro groups; or R3 is O−M+, wherein M+ is an alkali metal cation or an ammonium cation; Q is a radical p1, p2 and p3 are 0 or 1; m1, m2 and m3 are 1, 2 or 3; X1, X2 and X3 are hydroxy, halogen, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylthio, C1-C6haloalkylsulfinyl or C1-C6haloalkylsulfonyl; Z1, Z2 and Z3 are C1-C6alkyl which is substituted by the following substituents: C3-C4cycloalkyl or C3-C4cycloalkyl substituted by halogen, C1-C6alkyl, C1-C3alkoxy or C1-C3alkoxy-C1-C3alkyl; oxiranyl or oxiranyl substituted by C1-C6alkyl or C1-C3alkoxy-C1-C3alkyl; 3-oxetanyl or 3-oxetanyl substituted by C1-C6alkyl, C1-C3alkoxy or C1-C3alkoxy-C1-C3alkyl; 3-oxetanyloxy or 3-oxetanyloxy substituted by C1-C6alkyl, C1-C3alkoxy or C1-C3alkoxy-C1-C3-alkyl; C3-C6cycloalkyloxy or C3-C4cycloalkyloxy substituted by halogen, C1-C6alkyl, C1-C3-alkoxy or C1-C3alkoxy-C1-C3alkyl; C1-C6haloalkoxy; C1-C6alkylsulfonyloxy; C1-C6haloalkylsulfonyloxy; phenylsulfonyloxy; benzylsulfonyloxy, benzoyloxy; phenoxy; phenylthio; phenyl-sulfinyl; phenylsulfonyl; Ar10; OAr12; tri(C1-C6alkyl)silyl or tri(C1-C6alkyl)silyloxy, it being possible for the phenyl-containing groups to be mono- or poly-substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano, hydroxy or nitro; or Z1, Z2 and Z3 are 3-oxetanyl; 3-oxetanyl substituted by C1-C3alkoxy, C1-C3alkoxy-C1-C3alkyl or C1-C6alkyl; C3-C6cycloalkyl substituted by halogen, C1-C3alkyl or C1-C3alkoxy-C1-C3alkyl; tri(C1-C6alkyl)silyl; tri(C1-C6alkyl)silyloxy or CH═P(phenyl)3; or Z1, Z2 and Z3 are a C1-C6alkyl, C2-C6alkenyl or C2-C6alkynyl group, which is interrupted by oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R14)O—, —ONR15—, sulfur, sulfinyl, sulfonyl, —SO2NR16—, —NR17SO2— or —NR18— and is mono- or poly-substituted by L1; it also being possible for L1 to be bonded at the terminal carbon atom of the C1-C6alkyl, C2-C6alkenyl or C2-C6alkynyl group; or Z1, Z2 and Z3 are hydrogen, hydroxy, mercapto, NO2, cyano, halogen, formyl, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1-C6alkylthio, C1-C6alkylsulfonyl, C1-C6alkylsulfinyl, NR22R23, phenyl which may be mono- or poly-substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano, hydroxy or nitro, C3-C6cycloalkyl, C5-C6cycloalkyl substituted by C1-C3alkoxy, C1-C3alkoxy-C1-C3alkyl or C1-C6alkyl, or Ar5, O—Ar6, N(R24)Ar7 or S(O)n6Ar8; L1 is hydrogen, halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, P(O)(OC1—C6alkyl)2, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkoxycarbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, halo-substituted C3-C6cycloalkyl, C3-C6alkenyloxy, C3-C6alkynyloxy, C3-C6haloalkenyloxy, cyano-C1-C6alkoxy, C1-C6alkoxy-C1-C6alkoxy, C1-C6alkylthio-C1-C6alkoxy, C1-C6alkylsulfinyl-C1-C6alkoxy, C1-C6-alkylsulfonyl-C1-C6alkoxy, C1-C6alkoxycarbonyl-C1-C6alkoxy, C1-C6alkylcarbonyloxy-C1-C6-alkylcarbonyl, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylthio, C1-C6haloalkylsulfinyl, C1-C6haloalkylsulfonyl or oxiranyl, which may in turn be substituted by C1-C6alkyl, C1-C3alkoxy or C1-C3alkoxy-C1-C3alkyl, or (3-oxetanyl)-oxy, which may in turn be substituted by C1-C6alkyl, C1-C3alkoxy or C1-C3alkoxy-C1-C3alkyl, or benzoyloxy, benzyloxy, benzylthio, benzylsulfinyl, benzylsulfonyl, C1-C6alkylamino, di(C1-C6alkyl)amino, R19S(O)2O—, R20N(R21)SO2—, rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, Ar4 or OAr11, it being possible for the phenyl-containing groups in turn to be substituted by one or more C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano, hydroxy or nitro groups; R4a and R5a are each independently of the other hydrogen, C1-C6alkyl, C1-C6haloalkyl, cyano, formyl, C1-C6alkylcarbonyl, C1-C6alkoxycarbonyl, carbamoyl, C1-C6alkylaminocarbonyl, di(C1-C6alkylamino)carbonyl, di(C1-C6alkylamino)sulfonyl, C3-C6cycloalkylcarbonyl, C1-C6-alkylsulfonyl, phenylcarbonyl, phenylaminocarbonyl or phenylsulfonyl, it being possible for the phenyl groups to be mono- or poly-substituted by C1-C6alkyl, C1-C6haloalkyl, C1-C6-alkoxy, C1-C6haloalkoxy, halogen, cyano, hydroxy or nitro; R4b and R5b are each independently of the other hydroxy, C1-C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy or benzyloxy, it being possible for the benzyl group to be mono- or poly-substituted by C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hydroxy or nitro; R9, R11, R13, R16, R17, R18, R20, R23 and R24 are each independently of the others hydrogen, C1-C6alkyl, Ar9, C1-C6haloalkyl, C1-C6alkylcarbonyl, C1-C6alkoxycarbonyl, C1-C6alkylsulfonyl, phenyl, it being possible for the phenyl group in turn to be mono- or poly-substituted by C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hydroxy or nitro; R6a is hydrogen, C1-C6alkyl or C1-C6alkylcarbonyl; or together with R6b is a C2-C5alkylene chain; R6b, R6d, R10, R12 and R22 are each independently of the others hydrogen or C1-C6alkyl; R6c, R14, R15, R19 and R21, are each independently of the others C1-C6alkyl or C1-C6haloalkyl; Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, Ar7, Ar8, Ar9, Ar10, Ar11 and Ar12 are each independently of the others a five- to ten-membered, monocyclic or fused bicyclic ring system, which may be aromatic, partially saturated or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen, sulfur, C(O) and C(═NR25), and each ring system may contain not more than two oxygen atoms, not more than two sulfur atoms, not more than two C(O) groups and not more than one C(═NR25) group, and each ring system may itself be mono- or poly-substituted by C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, amino, hydroxy, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6-haloalkenylthio, C3-C6alkynylthio, C1-C3alkoxy-C1-C3alkylthio, C1-C4alkylcarbonyl-C1-C3alkylthio, C1-C4alkoxycarbonyl-C1-C3alkylthio, cyano-C1-C3alkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, N,N-di(C1-C2alkyl)aminosulfonyl, di(C1-C4alkyl)amino, halogen, cyano, nitro or phenyl, it being possible for the phenyl group in turn to be substituted by hydroxy, C1-C6-alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C1-C3alkoxy-C1-C3alkylthio, C1-C4alkylcarbonyl-C1-C3alkylthio, C1-C4alkoxycarbonyl-C1-C3-alkylthio, cyano-C1-C3alkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, N,N-di(C1-C2alkyl)aminosulfonyl, di(C1-C4alkyl)amino, halogen, cyano or nitro, and the substituents at the nitrogen atom in the heterocyclic ring being other than halogen, and two oxygen atoms not being located next to one another; R25 is hydrogen, hydroxy, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6alkylcarbonyl, C1-C6alkoxycarbonyl or C1-C6alkylsulfonyl; and n1 is 0, 1 or 2; and n6 is 0, 1 or 2; or an agronomically acceptable salt/isomer/enantiomer/tautomer of such a compound. 2. A compound of formula Da wherein Y, R1, R2, A1 and A2 are as defined for formula I in claim 1. 3. A compound of formula Db wherein A1, A2, R1, R2 and Y are as defined for formula I in claim 1, Xa is hydrogen, chlorine or bromine and R3 is hydroxy or C1-C6alkoxy, with the exception of the compounds 3-chloro-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione; 3-chloro-bicyclo[3.2.1]oct-6-ene-2,4-dione; 3-chloro-4-hydroxy-bicyclo[3.2.1]octa-3,6-dien-2-one; 3,4-dibromo-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one; 3,4dibromo-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one; 3,4-dibromo-bicyclo[3.2.1]octa-3,6-dien-2-one; 3,4-dichloro-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one; 3,4-dichloro-bicyclo[3.2.1]octa-3,6-dien-2-one and 7,8-dibromo-5,9-dihydro-5,9-methano-benzo-cyclohepten-6-one. 4. A compound of formula VII wherein A1, A2, R1, R2, Y are as defined for formula I in claim 1, Xa is hydrogen, chlorine or bromine and R3a is C1-C6alkyl or two R3a together are —CH2CH2—. 5. A herbicidal and plant-growth-inhibiting composition, comprising a herbicidally effective amount of a compound of formula I according to claim 1 on an inert carrier. 6. A method of controlling undesired plant growth, which method comprises applying a compound of formula I according to claim 5, or a composition comprising such a compound, in a herbicidally effective amount to a plant or to the locus thereof. 7. A method of inhibiting plant growth, which method comprises applying a compound of formula I according to claim 5, or a composition comprising such a compound, in a herbicidally effective amount to a plant or to the locus thereof.
The present invention relates to novel, herbicidally active nicotinoyl derivatives, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants, or in inhibiting plant growth. Nicotinoyl derivatives having herbicidal action are described, for example, in WO 00/15615 and WO 01/94339. There have now been found novel nicotinoyl derivatives having herbicidal and growth-inhibiting properties, the structures of which are distinguished by a double bond in the 6,7-position of the bicyclo[3.2.1]oct-3-en-2-one, bicyclo[3.2.1]nona-3-en-2-one, 8-oxa-bicyclo-[3.2.1]octa-3-en-2-one, 8-aza-bicyclo[3.2.1]octa-3-en-2-one, 8-thia-bicyclo[3.2.1]octa-3-en-2-one and bicyclo[3.2.1]octa-3-ene-2,8-dione group. Some of the compounds of that kind are covered by WO 00/15615 but none of those compounds is specifically disclosed. WO 01/66522 includes pyridine ketones having bicyclo[3.2.1]oct-3-en-2-one groups as intermediates in the preparation of aroyl ketones. There is no mention therein of those compounds having a herbicidal action. The present invention accordingly relates to compounds of formula I wherein Y is oxygen, NR4a, sulfur, sulfonyl, sulfinyl, C(O), C(═NR4b), C(═CR6aR6b) or a C1-C4alkylene or C2-C4alkenylene chain, which may be interrupted by oxygen, NR5a, sulfur, sulfonyl, sulfinyl, C(O) or C(═NR5b) and/or mono- or poly-substituted by R6; A1 is nitrogen or CR7; A2 is nitrogen or CR8; R1, R2, R6, R7 and R8 are each independently of the others hydrogen, hydroxy, mercapto, NO2, cyano, halogen, formyl, oxyiminomethylene, C1-C6alkoxyiminomethylene, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, C3-C6oxacycloalkyl, C3-C6thiacycloalkyl, C3-C6dioxacycloalkyl, C3-C6dithiacycloalkyl, C3-C6oxathiacycloalkyl, C1-C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1-C6alkoxycarbonyloxy, C1-C6alkylcarbonyloxy, C1-C6alkylthio, C1-C6alkylsulfonyl, C1-C6alkylsulfinyl, NR9R10, C3-C6cycloalkyl, tri(C1-C6alkyl)silyl, di(C1-C6alkyl)phenylsilyl, tri(C1-C6alkyl)silyloxy, di(C1-C6alkyl)phenylsilyloxy or Ar1; or R1, R2, R6, R7, R8 are each independently of the others a C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl or C3-C6cycloalkyl group, which may be interrupted by oxygen, sulfur, sulfonyl, sulfinyl, —NR11— or —C(O)— and/or mono-, di- or tri-substituted by hydroxy, mercapto, NO2, cyano, halogen, formyl, C1-C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, C1-C6haloalkoxy, C1-C2alkoxy-C1-C2alkoxy, C1-C4alkoxycarbonyloxy, C1-C4alkylcarbonyloxy, C1-C4alkoxy-carbonyl, C1-C4alkylcarbonyl, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, NR12R13, C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, tri(C1-C6alkyl)silyl, tri(C1-C6alkyl)-silyloxy or Ar2; or two substituents R6 at the same carbon atom together form a —CH2O— or a C2-C5alkylene chain, which may be interrupted once or twice by oxygen, sulfur, sulfinyl or sulfonyl and/or mono- or poly-substituted by R6c, with the proviso that two hetero atoms may not be located next to one another; or two substituents R6 at different carbon atoms together form an oxygen bridge or a C1-C4alkylene chain, which may in turn be substituted by R6c; or R7 and R8 together form a —CH2CH═CH—, —OCH═CH— or —CH═CH—CH═CH— bridge or a C3-C4alkylene chain, which may be interrupted by oxygen or —S(O)n1— and/or mono- or poly-substituted by R6d; R3 is hydroxy, halogen, mercapto, C1-C8alkylthio, C1-C8alkylsulfinyl, C1-C8alkylsulfonyl, C1-C8haloalkylthio, C1-C8haloalkylsulfinyl, C1-C8haloalkylsulfonyl, C1-C4alkoxy-C1-C4alkylthio, C1-C4alkoxy-C1-C4alkylsulfinyl, C1-C4alkoxy-C1-C4alkylsulfonyl, C3-C8alkenylthio, C3-C8-alkynylthio, C1-C4alkylthio-C1-C4alkylthio, C3-C4alkenylthio-C1-C4alkylthio, C1-C4alkoxycarbonyl-C1-C4alkylthio, C1-C4alkoxycarbonyl-C1-C4alkylsulfinyl, C1-C4alkoxycarbonyl-C1-C4alkylsulfonyl, C3-C8cycloalkylthio, C3-C8cycloalkylsulfinyl, C3-C8cycloalkylsulfonyl, phenyl-C1-C4alkylthio, phenyl-C1-C4alkylsulfinyl, phenyl-C1-C4alkylsulfonyl, S(O)n1—Ar3, phenylthio, phenylsulfinyl, phenylsulfonyl, it being possible for the phenyl-containing groups to be substituted by one or more C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, C1-C4alkoxycarbonyl, halogen, cyano, hydroxy or nitro groups; or R3 is O−M+, wherein M+ is an alkali metal cation or an ammonium cation; Q is a radical p1, p2 and p3 are 0 or 1; m1, m2 and m3 are 1, 2 or 3; X1, X2 and X3 are hydroxy, halogen, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylthio, C1-C6haloalkylsulfinyl or C1-C6haloalkylsulfonyl; Z1, Z2 and Z3 are C1-C6alkyl which is substituted by the following substituents: C3-C4cycloalkyl or C3-C4cycloalkyl substituted by halogen, C1-C6alkyl, C1-C3alkoxy or C1-C3alkoxy-C1-C3alkyl; oxiranyl or oxiranyl substituted by C1-C6alkyl or C1-C3alkoxy-C1-C3alkyl; 3-oxetanyl or 3-oxetanyl substituted by C1-C6alkyl, C1-C3alkoxy or C1-C3alkoxy-C1-C3alkyl; 3-oxetanyloxy or 3-oxetanyloxy substituted by C1-C6alkyl, C1-C3alkoxy or C1-C3alkoxy-C1-C3alkyl; C3-C6cycloalkyloxy or C3-C4cycloalkyloxy substituted by halogen, C1-C6alkyl, C1-C3alkoxy or C1-C3alkoxy-C1-C3alkyl; C1-C6haloalkoxy; C1-C6alkylsulfonyloxy; C1-C6haloalkylsulfonyloxy; phenylsulfonyloxy; benzylsulfonyloxy; benzoyloxy; phenoxy; phenylthio; phenylsulfinyl; phenylsulfonyl; Ar10; OAr12; tri(C1-C6alkyl)silyl or tri(C1-C6alkyl)silyloxy, it being possible for the phenyl-containing groups to be mono- or poly-substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano, hydroxy or nitro; or Z1, Z2 and Z3 are 3-oxetanyl; 3-oxetanyl substituted by C1-C3alkoxy, C1-C3alkoxy-C1-C3-alkyl or C1-C6alkyl; C3-C6cycloalkyl substituted by halogen, C1-C3alkyl or C1-C3alkoxy-C1-C3-alkyl; tri(C1-C6alkyl)silyl; tri(C1-C6alkyl)silyloxy or CH═P(phenyl)3; or Z1, Z2 and Z3 are a C1-C6alkyl, C2-C6alkenyl or C2-C6alkynyl group, which is interrupted by oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R14)O—, —ONR15—, sulfur, sulfinyl, sulfonyl, —SO2NR16—, —NR17SO2— or —NR18— and is mono- or poly-substituted by L1; it also being possible for L1 to be bonded at the terminal carbon atom of the C1-C6alkyl, C2-C6alkenyl or C2-C6alkynyl group; or Z1, Z2 and Z3 are hydrogen, hydroxy, mercapto, NO2, cyano, halogen, formyl, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1-C6alkylthio, C1-C6alkylsulfonyl, C1-C6alkylsulfinyl, NR22R23, phenyl which may be mono- or poly-substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano, hydroxy or nitro, C3-C6cycloalkyl, C5-C6cycloalkyl substituted by C1-C3alkoxy, C1-C3alkoxy-C1-C3alkyl or C1-C6alkyl, or Ar5, O—Ar6, N(R24)Ar7 or S(O)n6Ar8; L1 is hydrogen, halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, P(O)(OC1-C6alkyl)2, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkoxycarbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, halo-substituted C3-C6cycloalkyl, C3-C6alkenyloxy, C3-C6alkynyloxy, C3-C6haloalkenyloxy, cyano-C1-C6alkoxy, C1-C6alkoxy-C1-C6alkoxy, C1-C6alkylthio-C1-C6alkoxy, C1-C6alkylsulfinyl-C1-C6alkoxy, C1-C6alkylsulfonyl-C1-C6alkoxy, C1-C6alkoxycarbonyl-C1-C6alkoxy, C1-C6alkylcarbonyloxy-C1-C6alkylcarbonyl, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylthio, C1-C6haloalkylsulfinyl, C1-C6haloalkylsulfonyl or oxiranyl, which may in turn be substituted by C1-C6alkyl, C1-C3alkoxy or C1-C3alkoxy-C1-C3alkyl, or (3-oxetanyl)-oxy, which may in turn be substituted by C1-C6alkyl, C1-C3alkoxy or C1-C3alkoxy-C1-C3alkyl, or benzoyloxy, benzyloxy, benzylthio, benzylsulfinyl, benzylsulfonyl, C1-C6alkylamino, di(C1-C6alkyl)amino, R19S(O)2O—, R20N(R21)SO2—, rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, Ar4 or OAr11, it being possible for the phenyl-containing groups in turn to be substituted by one or more C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano, hydroxy or nitro groups; R4a and R5a are each independently of the other hydrogen, C1-C6alkyl, C1-C6haloalkyl, cyano, formyl, C1-C6alkylcarbonyl, C1-C6alkoxycarbonyl, carbamoyl, C1-C6alkylaminocarbonyl, di(C1-C6alkylamino)carbonyl, di(C1-C6alkylamino)sulfonyl, C3-C6cycloalkylcarbonyl, C1-C6-alkylsulfonyl, phenylcarbonyl, phenylaminocarbonyl or phenylsulfonyl, it being possible for the phenyl groups to be mono- or poly-substituted by C1-C6alkyl, C1-C6haloalkyl, C1-C6-alkoxy, C1-C6haloalkoxy, halogen, cyano, hydroxy or nitro; R4b and R5b are each independently of the other hydroxy, C1-C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy or benzyloxy, it being possible for the benzyl group to be mono- or poly-substituted by C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hydroxy or nitro; R9, R11, R13, R16, R17, R18, R20, R23 and R24 are each independently of the others hydrogen, C1-C6alkyl, Ar9, C1-C6haloalkyl, C1-C6alkylcarbonyl, C1-C6alkoxycarbonyl, C1-C6alkylsulfonyl, phenyl, it being possible for the phenyl group in turn to be mono- or poly-substituted by C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hydroxy or nitro; R6a is hydrogen, C1-C6alkyl or C1-C6alkylcarbonyl; or together with R6b is a C2-C5alkylene chain; R6b, R6d, R10, R12 and R22 are each independently of the others hydrogen or C1-C6alkyl; R6c, R14, R15, R19 and R21 are each independently of the others C1-C6alkyl or C1-C6haloalkyl; Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, Ar7, Ar8, Ar9, Ar10, Ar11 and Ar12 are each independently of the others a five- to ten-membered, monocyclic or fused bicyclic ring system, which may be aromatic, partially saturated or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen, sulfur, C(O) and C(═NR25), and each ring system may contain not more than two oxygen atoms, not more than two sulfur atoms, not more than two C(O) groups and not more than one C(═NR25) group, and each ring system may itself be mono- or poly-substituted by C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, amino, hydroxy, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6-haloalkenylthio, C3-C6alkynylthio, C1-C3alkoxy-C1-C3alkylthio, C1-C4alkylcarbonyl-C1-C3alkylthio, C1-C4alkoxycarbonyl-C1-C3alkylthio, cyano-C1-C3alkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, N,N-di(C1-C2alkyl)aminosulfonyl, di(C1-C4alkyl)amino, halogen, cyano, nitro or phenyl, it being possible for the phenyl group in turn to be substituted by hydroxy, C1-C6-alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C1-C3alkoxy-C1-C3alkylthio, C1-C4alkylcarbonyl-C1-C3alkylthio, C1-C4alkoxycarbonyl-C1-C3-alkylthio, cyano-C1-C3alkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, N,N-di(C1-C2alkyl)aminosulfonyl, di(C1-C4alkyl)amino, halogen, cyano or nitro, and the substituents at the nitrogen atom in the heterocyclic ring being other than halogen, and two oxygen atoms not being located next to one another; R25 is hydrogen, hydroxy, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6alkylcarbonyl, C1-C6alkoxycarbonyl or C1-C6alkylsulfonyl; and n1 is 0, 1 or 2; and n6 is 0, 1 or 2; and agronomically acceptable salts/isomers/enantiomers/tautomers of those compounds. The alkyl groups appearing in the substituent definitions may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl and octyl and the branched isomers thereof. Alkoxy, alkenyl and alkynyl radicals are derived from the mentioned alkyl radicals. The alkenyl and alkynyl groups may be mono- or poly-unsaturated. C1-C4alkylene and C2-C4alkenylene chains may likewise be straight-chain or branched. Halogen is generally fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine. The same is true of halogen in conjunction with other meanings, such as haloalkyl or halophenyl. Haloalkyl groups preferably have a chain length of from 1 to 6 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl or 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl or dichlorofluoromethyl. In the context of the present invention, the term “mono- or poly-substituted” is generally to be understood as meaning mono- to penta-substituted, especially mono- to tri-substituted. As haloalkenyl there come into consideration alkenyl groups mono- or poly-substituted by halogen, halogen being fluorine, chlorine, bromine or iodine, and especially fluorine or chlorine, for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluoro-but-2-en-1-yl. Of the C3-C8alkenyl groups mono-, di- or tri-substituted by halogen preference is given to those having a chain length of from 3 to 5 carbon atoms. As haloalkynyl there come into consideration, for example, alkynyl groups mono- or poly-substituted by halogen, halogen being bromine, iodine and especially fluorine or chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4-trifluoro-but-2-yn-1-yl. Of the alkynyl groups mono- or poly-substituted by halogen preference is given to those having a chain length of from 3 to 5 carbon atoms. Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, Ar7, A8, A9, Ar10, Ar11 and Ar12 are, for example, phenyl, naphthyl or the following heterocyclic groups: (1-methyl-1H-pyrazol-3-yl)-; (1-ethyl-1H-pyrazol-3-yl)-; (1-propyl-1H-pyrazol-3-yl)-; (1H-pyrazol-3-yl)-; (1,5-dimethyl-1H-pyrazol-3-yl)-; (4-chloro-1-methyl-1H-pyrazol-3-yl)-; (1H-pyrazol-1-yl)-; (3-methyl-1H-pyrazol-1-yl)-; (3,5-dimethyl-1H-pyrazol-1-yl)-; (3-isoxazolyl)-; (5-methyl-3-isoxazolyl)-; (3-methyl-5-isoxazolyl)-; (5-isoxazolyl)-; (1H-pyrrol-2-yl)-; (1-methyl-1H-pyrrol-2-yl)-; (1H-pyrrol-1-yl)-; (1-methyl-1H-pyrrol-3-yl)-; (2-furanyl)-; (5-methyl-2-furanyl)-; (3-furanyl)-; (5-methyl-2-thienyl)-; (2-thienyl)-; (3-thienyl)-; (1-methyl-1H-imidazol-2-yl)-; (1H-imidazol-2-yl)-; (1-methyl-1H-imidazol-4-yl)-; (1-methyl-1H-imidazol-5-yl)-; (4-methyl-2-oxazolyl)-; (5-methyl-2oxazolyl)-; (2-oxazolyl)-; (2-methyl-5-oxazolyl)-; (2-methyl-4-oxazolyl)-; (4-methyl-2-thiazolyl)-; (5-methyl-2-thiazolyl)-; (2-thiazolyl)-; (2-methyl-5-thiazolyl)-; (2-methyl-4-thiazolyl)-; (3-methyl-4-isothiazolyl)-; (3-methyl-5-isothiazolyl)-; (5-methyl-3-isothiazolyl)-; (1-methyl-1H-1,2,3-triazol-4-yl)-; (2-methyl-2H-1,2,3-triazol-4-yl)-; (4-methyl-2H-1,2,3-triazol-2-yl)-; (1-methyl-1H-1,2,4-triazol-3-yl)-; (1,5-dimethyl-1H-1,2,4-triazol-3-yl)-; (3-methyl-1H-1,2,4-triazol-1-yl)-; (5-methyl-1H-1,2,4-triazol-1-yl)-; (4,5-dimethyl-4H-1,2,4-triazol-3-yl)-; (4-methyl-4H-1,2,4-triazol-3-yl)-; (4H-1,2,4-triazol-4-yl)-; (5-methyl-1,2,3-oxadiazol-4-yl)-; (1,2,3-oxadiazol-4-yl)-; (3-methyl-1,2,4-oxadiazol-5-yl)-; (5-methyl-1,2,4-oxadiazol-3-yl)-; (4-methyl-3-furazanyl)-; (3-furazanyl)-; (5-methyl-1,2,4-oxadiazol-2-yl)-; (5-methyl-1,2,3-thiadiazol-4-yl)-; (1,2,3-thiadiazol-4-yl)-; (3-methyl-1,2,4-thiadiazol-5-yl)-; (5-methyl-1,2,4-thiadiazol-3-yl)-; (4-methyl-1,2,5-thiadiazol-3-yl)-; (5-methyl-1,3,4-thiadiazol-2-yl)-; (1-methyl-1H-tetrazol-5-yl)-; (1H-tetrazol-5-yl)-; (5-methyl-1H-tetrazol-1-yl)-; (2-methyl-2H-tetrazol-5-yl)-; (2-ethyl-2H-tetrazol-5-yl)-; (5-methyl-2H-tetrazol-2-yl)-; (2H-tetrazol-2-yl)-; (2-pyridyl)-; (6-methyl-2-pyridyl)-; (4-pyridyl)-; (3-pyridyl)-; (6-methyl-3-pyridazinyl)-; (5-methyl-3-pyridazinyl)-; (3-pyridazinyl)-; (4,6-dimethyl-2-pyrimidinyl)-; (4-methyl-2-pyrimidinyl)-; (2-pyrimidinyl)-; (2-methyl-4-pyrimidinyl)-; (2-chloro-4-pyrimidinyl)-; (2,6-dimethyl-4-pyrimidinyl)-; (4-pyrimidinyl)-; (2-methyl-5-pyrimidinyl)-; (6-methyl-2-pyrazinyl)-; (2-pyrazinyl)-; (4,6-dimethyl-1,3,5-triazin-2-yl)-; (4,6-dichloro-1,3,5-triazin-2-yl)-; (1,3,5-triazin-2-yl)-; (4-methyl-1,3,5-triazin-2-yl)-; (3-methyl-1,2,4-triazin-5-yl)-; (3-methyl-1,2,4-triazin-6-yl)-; and Ar10 may also be, for example, a carbonyl-containing heterocyclic group wherein each R26 is methyl, each R27 and each R28 are independently hydrogen, C1-C3alkyl, C1-C3alkoxy, C1-C3alkylthio or trifluoromethyl, X4 is oxygen or sulfur and r=1, 2, 3 or 4. Where no free valency is indicated in those definitions of Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, Ar7, Ar8, A9, Ar10, Ar11 and Ar12, for example as in the linkage site is located at the carbon atom labelled “CH” or in a case such as, for example, at the bonding site indicated at the bottom left. The alkali metal cation M+ (for example in the meaning of O−M+ in R3) denotes in the context of the present invention preferably the sodium cation or the potassium cation. Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and the isomers of pentyloxy and hexyloxy; preferably methoxy and ethoxy. Alkylcarbonyl is preferably acetyl, propionyl or pivaloyl. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxycarbonyl or ethoxycarbonyl. Haloalkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Haloalkoxy is e.g. fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy. Alkylthio groups preferably have a chain length of from 1 to 8 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio and ethylthio. Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl; preferably methylsulfinyl and ethylsulfinyl. Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl. Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the isomers of butylamine. Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, di-butylamino and di-isopropylamino. Preference is given to alkylamino and dialkylamino groups—including as a component of (N-alkyl)sulfonylamino and N-(alkylamino)sulfonyl groups, such as (N,N-dimethyl)sulfonylamino and N,N-(dimethylamino)sulfonyl—each having a chain length of from 1 to 4 carbon atoms. Alkoxyalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms. Examples of alkoxyalkoxy are: methoxymethoxy, methoxyethoxy, methoxypropoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy and butoxybutoxy. Alkoxyalkyl groups have a chain length of preferably from 1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl. Alkylthioalkyl groups preferably have from 1 to 8 carbon atoms. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl. The cycloalkyl groups having up to 8 carbon atoms preferably have from 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. A cycloalkyl group having up to 8 carbon atoms also includes a C3-C6alkyl group bonded by way of a methylene or ethylene bridge, for example cyclopropylmethyl, cyclobutylmethyl and cyclopentylmethyl. Cycloalkyl groups, as well as, for example, the oxygen-containing oxiranyl, oxiranylmethyl, 3-oxetanyl, 2- and 3-tetrahydrofuranyl, 2-(2- and 3-tetrahydrofuranyl)methyl, 2-, 3- and 4-tetrahydropyranyl, 2-(2-tetrahydropyranyl)methyl, 1,3-dioxolanyl, 2-(1,3-dioxolanyl)methyl, 4-(1,3-dioxolanyl)methyl, 1,3-dioxanyl, 1,4-dioxanyl and similar saturated groups—especially as a component of Ar5 in L1—can also be mono- or poly-substituted by C1-C3alkyl, preferably mono- to tetra-substituted by methyl. Phenyl, including as a component of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl, may be in substituted form. The substituents may in that case be in the ortho-, meta- and/or para-position(s). Preferred substituent positions are the ortho- and para-positions relative to the ring linkage site. The phenyl groups are preferably unsubstituted or mono- or di-substituted, especially unsubstituted or mono-substituted. Z1, Z2 and Z3 as a C1-C6alkyl group which is interrupted by oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R14)O—, —ONR15—, sulfur, sulfinyl, sulfonyl, —SO2NR16—, —NR17SO2— or —NR18— and may be mono- or poly-substituted by a group L1 when that C1-C6alkyl group is interrupted by oxygen, —O(CO)O—, sulfur, sulfinyl or sulfonyl, is to be understood as meaning, for example, a bidentate bridging member —CH2OCH2—, —CH2CH2OCH2—, —CH2OCH2CH2—, —CH2OCH2CH2CH2—, —CH2OC(O)CH2—, —CH2(CO)OCH2—, —CH2O(CO)OCH2—, —CH2SCH2—, —CH2S(O)CH2—, —CH2SO2CH2—, —CH2SCH2CH2—, —CH2S(O)CH2CH2—, —CH2SO2CH2CH2—, —CH2N(CH3)SO2CH2—, —CH2N(SO2CH3)CH2—, —CH2N(C(O)CH3)CH2—, —CH2N(COOCH2CH3)CH2— or —CH2N(COOCH3)CH2—, the left-hand bonding site being bonded to the pyridine moiety and the right-hand side to the substituent L1. And Z1, Z2 and Z3 as a C2-C6alkenyl or C2-C6alkynyl group which is interrupted by oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R14)O—, —ONR15—, sulfur, sulfinyl, sulfonyl, —SO2NR16—, —NR17SO2— or —NR18— and may be mono- or poly-substituted by a group L1 is to be understood as meaning, for example, a bidentate bridging member —CH═CHCH2OCH2— or —C≡CCH2OCH2—. Such an unsubstituted or L1-substituted C1-C6alkyl, C2-C6alkenyl or C2-C6alkynyl group Z1, Z2 or Z3 which is interrupted by oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R14)O—, —ONR15—, sulfur, sulfinyl, sulfonyl, —SO2NR16—, —NR17OS2— or —NR18— can be either straight-chain or branched, for example as in the case of the bidentate bridging members —CH(CH3)OCH2— and —CH2OCH(CH3)CH2—. The compounds of formula I may occur in various tautomeric forms such as, for example, when R3 is hydroxy and Q is Q1, in formulae I′, I″, I′″ and I″″, preference being given to formulae I′ and I″. Since compounds of formula I may also contain asymmetric carbon atoms, for example in the case of R1, R2, A1, A2 and Y, their substituents R6, R7 and R8, and also in the case of carbon atoms carrying X1, X2, X3, Z1, Z2 and Z3, and accordingly in any sulfoxides, all the stereoisomers and all chiral <R> and <S> forms are also included. Also included are all constitutional isomeric <E> and <Z> forms in respect of any —C═C— and —C═N— double bonds. Since R1 and R2, like R7 and R8 in A1 and A2, may each independently of the other have the same or different meanings, the compound of formula I may also occur in various constitutional isomeric forms. The invention therefore relates also to all those constitutional isomeric forms in respect of the spatial arrangement of A1 and A2 and the substituents R1 and R2 in respect of the substituent R3 as shown in formulae D1 to D4. The same applies also to the spatial arrangement of the bridging member Y in respect of the carbon atoms carrying R1 and R2 when Y is a C1-C4alkylene or C2-C4alkenylene chain which may be interrupted by oxygen, NR5a, sulfur, sulfonyl, sulfinyl, C(O) or C(═NR5b) and/or mono- or poly-substituted by R6. The substituent R3 may also be located on the bridging member, as has already been shown above in formula I″ wherein R3 is hydroxy. The present invention relates also to those constitutional isomeric forms D5 of the compounds of formula I. That arrangement of A1, A2, Y and the substituents R1, R2, R4, R5, R6, R7 and R8 relates accordingly also to all possible tautomeric and stereoisomeric forms of the compounds used as intermediates. The present invention relates also to the salts which the compounds of formula I are able to form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Among the alkali metal and alkaline earth metal bases as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium, barium and calcium, but especially the hydroxides of sodium, barium and potassium. Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary C1-C18alkylamines, C1-C4hydroxyalkylamines and C2-C4-alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine. Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(RaRbRcRd)]OH wherein Ra, Rb, Rc and Rd are each independently of the others C1-C4alkyl. Further suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions. Preference is given to compounds of formula I wherein R1, R2, R6, R7 and R8 are each independently of the others hydrogen, hydroxy, mercapto, NO2, cyano, halogen, formyl, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, C3-C6oxacycloalkyl, C3-C6thiacycloalkyl, C3-C6dioxacycloalkyl, C3-C6dithiacycloalkyl, C3-C6oxathiacycloalkyl, C1-C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1-C6alkoxycarbonyloxy, C1-C6alkylcarbonyloxy, C1-C6alkylthio, C1-C6alkylsulfonyl, C1-C6alkylsulfinyl, NR9R10, C3-C6cycloalkyl, tri(C1-C6alkyl)silyl, tri(C1-C6alkyl)silyloxy or Ar1; or R1, R2, R6, R7, R8 are each independently of the others a C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl or C3-C6cycloalkyl group, which may be interrupted by oxygen, sulfur, sulfonyl, sulfinyl, —NR11— or —C(O)— and/or mono-, di- or tri-substituted by hydroxy, mercapto, NO2, cyano, halogen, formyl, C1-C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, C1-C6haloalkoxy, C1-C2alkoxy-C1-C2alkoxy, C1-C4alkoxycarbonyloxy, C1-C4alkylcarbonyloxy, C1-C4alkoxycarbonyl, C1-C4alkylcarbonyl, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, NR12R13, C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, tri(C1-C6alkyl)silyl, tri(C1-C6alkyl)silyloxy or Ar2; or two substituents R6 at the same carbon atom together form a —CH2O— or a C2-C5alkylene chain, which may be interrupted once or twice by oxygen, sulfur, sulfonyl or sulfinyl and/or mono- or poly-substituted by R6c, with the proviso that two hetero atoms may not be located next to one another; or two substituents R6 at different carbon atoms together form an oxygen bridge or a C1-C4alkylene chain, which may in turn be substituted by R6c; or R7 and R8 together form an oxygen bridge, a —CH═CH—CH═CH— bridge or a C3-C4alkylene chain, which may be interrupted by oxygen or —S(O)n1— and/or mono- or poly-substituted by R6d; Z1, Z2 and Z3 are each independently of the others C1-C3alkoxy-C1-C3alkyl-substituted C3-C6cycloalkyl, tri(C1-C6alkyl)silyl, tri(C1-C6alkyl)silyloxy or CH═P(phenyl)3; or Z1, Z2 and Z3 are a C1-C6alkyl, C2-C6alkenyl or C2-C6alkynyl group, which is interrupted by oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R14)—O—, —O—NR15—, sulfur, sulfinyl, sulfonyl, —SO2NR16—, —NR17SO2— or —NR18— and is mono- or poly-substituted by L1; L1 is halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, P(O)(OC1-C6alkyl)2, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkoxycarbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, halo-substituted C3-C6-cycloalkyl, C3-C6alkenyloxy, C3-C6alkynyloxy, C3-C6haloalkenyloxy, cyano-C1-C6alkoxy, C1-C6alkoxy-C1-C6alkoxy, C1-C6alkylthio-C1-C6alkoxy, C1-C6alkylsulfinyl-C1-C6alkoxy, C1-C6alkylsulfonyl-C1-C6alkoxy, C1-C6alkoxycarbonyl-C1-C6alkoxy, C1-C6alkylcarbonyloxy-C1-C6alkylcarbonyl, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylthio, C1-C6haloalkylsulfinyl, C1-C6haloalkylsulfonyl or oxiranyl, which may in turn be substituted by C1-C6alkyl, C1-C3alkoxy or C1-C3alkoxy-C1-C3alkyl, or (3-oxetanyl)-oxy, which may in turn be substituted by C1-C6alkyl, C1-C3alkoxy or C1-C3alkoxy-C1-C3alkyl, or benzoyloxy, benzyloxy, benzylthio, benzylsulfinyl, benzylsulfonyl, C1-C6alkylamino, di(C1-C6alkyl)amino, R19S(O)2O, R20N(R21)SO2—, rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl or Ar4, it being possible for the phenyl-containing groups in turn to be substituted by one or more C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano, hydroxy or nitro groups; or, when R1 and R2 are hydrogen, methyl, halogen or C1-C3alkoxycarbonyl and at the same time Y is other than C1-C2alkylene which may be substituted by hydrogen, halogen or methyl, or is other than oxygen, sulfur, sulfonyl, sulfinyl, C(O) or NR4a wherein R4a is hydrogen, C1-C4alkyl, formyl or C1-C4alkylcarbonyl, L1 may additionally be hydrogen and Z1, Z2 and Z3 may additionally be hydrogen, hydroxy, mercapto, NO2, cyano, halogen, formyl, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1-C6alkylthio, C1-C6alkylsulfonyl, C1-C6alkylsulfinyl, NR22R23, phenyl which may be mono- or poly-substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano, hydroxy or nitro, or C3-C6cycloalkyl, C3-C6cycloalkyl substituted by C1-C3alkoxy, C1-C3alkoxy-C1-C3alkyl or C1-C6alkyl, 3-oxetanyl, 3-oxetanyl substituted by C1-C3alkoxy, C1-C3alkoxy-C1-C3alkyl or C1-C6alkyl; or Ar5, O—Ar6, N(R24)Ar7 or S(O)n6Ar8; R9, R11, R13, R23, R16, R17, R18, R20 and R24 are each independently of the others hydrogen, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkylcarbonyl, C1-C6alkoxycarbonyl, C1-C6alkylsulfonyl, phenyl, it being possible for the phenyl group in turn to be mono- or poly-substituted by C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hydroxy or nitro, or Ar9; R6a and R6b are each independently of the other hydrogen or C1-C6alkyl; or R6a and R6b together are a C2-C5alkylene chain; R6c, R14, R15, R19 and R21 are each independently of the others C1-C6alkyl or C1-C6haloalkyl; R6d, R10, R12 and R22 are each independently of the others hydrogen or C1-C6alkyl; Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, Ar7, A8 and A9 are each independently of the others a five- to ten-membered, monocyclic or fused bicyclic ring system, which may be aromatic, partially saturated or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen, sulfur, C(O) and C(═NR25), and each ring system contains not more than two oxygen atoms and not more than two sulfur atoms, and each ring system may itself be mono- or poly-substituted by C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, amino, hydroxy, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6-haloalkenylthio, C3-C6alkynylthio, C1-C3alkoxy-C1-C3alkylthio, C1-C4alkylcarbonyl-C1-C3alkylthio, C1-C4alkoxycarbonyl-C1-C3alkylthio, cyano-C1-C3alkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, N,N-di(C1-C2alkyl)aminosulfonyl, di(C1-C4alkyl)amino, halogen, cyano, nitro or phenyl, it being possible for the phenyl group in turn to be substituted by hydroxy, C1-C6-alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C1-C3-alkoxy-C1-C3alkylthio, C1-C4alkylcarbonyl-C1-C3alkylthio, C1-C4alkoxycarbonyl-C1-C3alkylthio, cyano-C1-C3alkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, N,N-di(C1-C2alkyl)aminosulfonyl, di(C1-C4alkyl)amino, halogen, cyano or nitro, and the substituents at the nitrogen atom in the heterocyclic ring being other than halogen. Special mention should be made of compounds of formula I wherein L1 is hydrogen only when Z1, Z2 and Z3 are a C1-C6alkyl group which is interrupted by —O(CO)—, —(CO)O—, —N(R14)O—, —ONR15—, —SO2NR16—, —NR17SO2— or —NR18—, or is a C2-C6alkenyl or C2-C6alkynyl group which is interrupted by oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R14)O—, —ONR15—, sulfur, sulfinyl, sulfonyl, —SO2NR16—, —NR17SO2— or —NR18—; and when, further, either R1 and R2 are hydrogen or methyl, or R1 is halogen or R2 is C1-C3alkoxycarbonyl, and at the same time Y is other than C1-C2alkylene which may be substituted by halogen or methyl, or Y is other than oxygen, sulfur, sulfonyl, sulfinyl, C(O) or NR4a wherein R4a is hydrogen, C1-C4alkyl, formyl or C1-C4alkylcarbonyl. An outstanding group of compounds of formula I comprises those compounds wherein Z1, Z2, Z3 are C1-C3alkylene which is substituted by the following substituents: halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, P(O)(OC1-C6alkyl)2, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkoxycarbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6-haloalkynyl, C3-C6cycloalkyl, halo-substituted C3-C6cycloalkyl, C3-C6alkenyloxy, C3-C6alkynyloxy, C3-C6haloalkenyloxy, cyano-C1-C6alkoxy, C1-C6alkoxy-C1-C6alkoxy, C1-C6alkylthio-C1-C6alkoxy, C1-C6alkylsulfinyl-C1-C6alkoxy, C1-C6alkylsulfonyl-C1-C6alkoxy, C1-C6alkoxy-carbonyl-C1-C6alkoxy, C1-C6alkylcarbonyloxy, C1-C6alkylcarbonyl, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylthio, C1-C6haloalkylsulfinyl, C1-C6haloalkylsulfonyl or oxiranyl, which may in turn be substituted by C1-C3alkyl, C1-C3alkoxy or C1-C3alkoxy-C1-C3alkyl, or (3-oxetanyl)-oxy, which may in turn be substituted by C1-C6alkyl, C1-C3alkoxy or C1-C3alkoxy-C1-C3alkyl, or benzoyloxy, benzyloxy, benzylthio, benzylsulfinyl, benzylsulfonyl, C1-C6alkylamino, di(C1-C6alkyl)amino, R19S(O)2O, R20N(R21)SO2—, rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl or Ar4, it being possible for the phenyl-containing groups in turn to be substituted by one or more C1-C3alkyl, C1-C3haloalkyl, C1-C3-alkoxy, C1-C3haloalkoxy, halogen, cyano, hydroxy or nitro groups; or, when R1 and R2 are hydrogen, methyl, halogen or C1-C3alkoxycarbonyl and at the same time Y is other than C1-C2alkylene which may be substituted by halogen or methyl, or is other than oxygen, sulfur, sulfonyl, sulfinyl, C(O) or NR4a wherein R4a is hydrogen, C1-C4-alkyl, formyl or C1-C4alkylcarbonyl, L1 may additionally be hydrogen and Z1, Z2 and Z3 may additionally be hydrogen, hydroxy, mercapto, NO2, cyano, halogen, formyl, C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1-C6alkylthio, C1-C6alkylsulfonyl, C1-C6alkylsulfinyl, NR22R23, phenyl which may be mono- or poly-substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3-haloalkoxy, halogen, cyano, hydroxy or nitro, or C3-C6cycloalkyl, C3-C6cycloalkyl substituted by C1-C3alkoxy, C1-C3alkoxy-C1-C3alkyl or C1-C3alkyl, 3-oxetanyl, 3-oxetanyl substituted by C1-C3alkoxy, C1-C3alkoxy-C1-C3alkyl or C1-C6alkyl, or Ar5, O—Ar6, N(R24)Ar7 or S(O)n6Ar8. Preferred compounds of formula I are those wherein p is 0. Preferably at least one group Z1, Z2 or Z3 is in the ortho-position relative to the carbonyl group; in preferred compounds, in addition, m1, m2 and m3 are the number 1. Also preferred are compounds of formula I wherein Q is a group Q1 or Q2, especially the group Q1. Also preferred are those compounds of formula I wherein Y is oxygen, NCO2methyl, NSO2CH3, NC(O)CH3, sulfur, sulfinyl, sulfonyl, C(O) or a C1-C2alkylene chain. Outstanding compounds are those wherein Y is a C1-C2alkylene chain or oxygen, and wherein A1 is CR7, A2 is CR8 and R1, R2, R6, R7, R8 are each independently of the others hydrogen or methyl, especially Y is methylene or ethylene and R1, R2, R6, R7, R8 are each hydrogen. Especially interesting compounds of formula I are those wherein Z1 is C1-C3alkylene which may be interrupted by oxygen, especially a bidentate group of form —CH2—, —CH2CH2—, —OCH2—, —OCH2CH2—, —CH2O—, —CH2CH2O—, —CH2OCH2— or —CH2CH2CH2O—, and L1 is preferably hydrogen, halogen, cyano, C1-C6alkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkoxy-C1-C6alkoxy. Especially preferred are compounds of formula I wherein Z1 or Z1-L1 is CH3, CH2CH3, CH2CH2CH3, CHC(CH3)2, CH2OCH2CH2OCH3, CH2OCH2CH2OCH2CH3, CH2OCH3, CH2OCH2CH3, CH2OCH(CH3)2, CH2OCH2CF3, CH2OCH2CH═CH2, CH2OCH2CCH, CH2OCH2CCCH3, CH2OCH2CH2CCH, CH2OCH2CN, CH2OCH2C2CN, CH2OCH2CH2CH2OCH3, CH2OCH2CH2OCH2CH2OCH3, CH2OCH2CH2CH2OCF3, CH2CH2OCH3, CH2CH2OCH2CH3, CH2CH2CH2OCH3, CH2CH2CH2OCH2CH3 or CH2CH2OCH2CH2OCH3, more especially CH3, CH2CH2CH2OCH3 or CH2OCH2CH2OCH3, especially prominent compounds being those wherein Y is methylene, ethylene or oxygen, A1 is CR7, A2 is CR8 and R1, R2, R6, R7, R8 are each independently of the others hydrogen or methyl. Of that group, preference is given to those compounds wherein Q is Q1, p1 is 0 and m1 is 1, the group (Z1)m1 is in the ortho-position relative to the carbonyl group, and R3 is hydroxy. Special emphasis should also be given to compounds of formula I wherein Q is Q1, Z1 is C1-C3alkylene which may be interrupted by oxygen, Z1 being especially a bidentate group of form —CH2—, —CH2CH2—, —OCH2—, —OCH2CH2—, —CH2O—, —CH2CH2O—, —CH2OCH2— or —CH2CH2CH2O—, and L1 is preferably a monocyclic group wherein R26 is hydrogen or methyl, R27 is hydrogen, C1-C3alkyl, C1-C3alkoxy, C1-C3alkylthio or trifluoromethyl and X4 is oxygen or sulfur. Where no free valency is indicated in those preferred definitions of L1, for example as in the linkage site is located at the carbon atom labelled “CH” or in the case of at the carbon atom labelled “CH2” or in a case such as, for example, at the bonding site indicated at the bottom left. In a further preferred group of compounds of formula I, X1, X2 and X3 are C1-C3haloalkyl, especially CF3, CF2CF3, CF2Cl or CF2H, more especially CF3 or CF2H. An especially preferred group of compounds of formula I comprises those compounds wherein Y is oxygen, C(═CR6aR6b) or a C1-C4alkylene chain which may be mono- or poly-substituted by R6; A1 is CR7; A2 is CR8; R1, R2, R6, R6a, R6b, R7 and R8 are each independently of the others hydrogen, C1-C6alkyl or C1-C6alkoxycarbonyl; or two substituents R6 at the same carbon atom together form a C2-C5alkylene chain; R3 is hydroxy; Q is the radical Q1; p1 is 0; m1 is 1; X1 is C1-C6haloalkyl; Z1 is a C1-C6alkyl group which is interrupted by oxygen and is mono- or poly-substituted by L1; it also being possible for L1 to be bonded at the terminal carbon atom of the C1-C6alkyl group; or Z1 is C1-C6alkyl; and L1 is C1-C6alkoxy; and agronomically acceptable salts/isomers/enantiomers/tautomers of those compounds. The compounds of formula I can be prepared by means of processes known per se, e.g. as described in WO/0039094, as indicated below with reference to the examples of compounds of formula Ia wherein R1, R2, A1, A2, Y, X1, Z1, m1 and p1 are as defined above. In a preferred process, for example in the case of compounds of formula Ia wherein R1, R2, A1, A2 and Y are as defined above and Q is a group Q1, a) a compound of formula Q1a wherein Z1, m1, X1 and p1 are as defined above and E1 is a leaving group, for example halogen or cyano, is reacted in an inert organic solvent, in the presence of a base, with a compound of formula Da wherein Y, R1, R2, A2 and A1 are as defined for formula I, to form compound(s) of formula IIa and/or IIb and the latter is(are) then isomerised, for example in the presence of a base and a catalytic amount of an acylating agent, for example dimethylaminopyridine (DMAP), or a cyanide source, e.g. acetone cyanohydrin, potassium cyanide or trimethylsilyl cyanide; or b) a compound of formula Q1b wherein Z1, m1, p1 and X1 are as defined for formula I, is reacted with a compound of formula Da wherein Y, R1, R2, A1 and A2 are as defined for formula I, in an inert organic solvent, in the presence of a base and a coupling reagent, to form compound(s) of formula IIa and/or IIb and the latter is(are) then isomerised, for example as described under Route a). The intermediates of formulae Da, IIa and IIb are novel and have been developed especially for the preparation of the compounds of formula I. The present invention therefore relates also thereto. The novel intermediates of formulae Da, IIa, IIb correspond, in summary, to the general formulae IIIa and IIIb wherein R1, R2, Y, A1 and A2 are as defined above and R29 is OH or OC(O)Q wherein Q is as defined for formula I. The preparation of the compounds of formula I is illustrated in greater detail in the following Reaction Schemes. According to Reaction Scheme 1 it is preferable to prepare the compounds of formula I having the group Q1, Q2 and Q3 wherein R3 is hydroxy and p1, p2 and p3 are 0. Compounds of formula I wherein p1, p2 and p3 are 1, that is to say the corresponding N-oxides of formula I, can be prepared by reacting a compound of formula I wherein p1, p2 and p3 are 0 with a suitable oxidising agent, for example with the H2O2-urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride. Such oxidations are known in the literature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 or WO 00/15615. For the preparation of the compounds of formula I wherein Q is the groups Q1, Q2 and Q3 and R3 is hydroxy, for example in accordance with Reaction Scheme 1, Route a), the carboxylic acid derivatives of formula Q1a wherein E1 is a leaving group, e.g. halogen, for example iodine, bromine and especially chlorine, N-oxyphthalimide or N,O-dimethylhydroxylamino, or part of an activated ester, e.g. (formed from dicyclohexylcarbodiimide (DCC) and the corresponding carboxylic acid) or (formed from N-ethyl-N′-(3-dimethylaminopropyl)-carbodiimide (EDC) and the corresponding carboxylic acid) are used as starting materials. They are reacted in an inert, organic solvent, e.g. a halogenated hydrocarbon, for example dichloromethane, a nitrile, for example acetonitrile, or an aromatic hydrocarbon, for example toluene, and in the presence of a base, e.g. an alkylamine, for example triethylamine, an aromatic amine, for example pyridine or 4-dimethylaminopyridine (DMAP), with the dione derivatives of formula Da to form the isomeric enol esters of formula IIa or IIb. That esterification can be carried out at temperatures of from 0° C. to 110° C. The isomerisation of the enol ester derivatives of formulae IIa and IIb to form the derivatives of formula I wherein R3 is hydroxy can be carried out, for example, analogously to EP-A-0 353 187, EP-A-0 316 491 or WO 97/46530 in the presence of a base. e.g. an alkylamine, for example triethylamine, a carbonate, for example potassium carbonate, and a catalytic amount of DMAP or a catalytic amount of a cyanide source, for example acetone cyano-hydrin, potassium cyanide or trimethylsilyl cyanide. The two reaction steps can be carried out in situ, especially when a cyanide compound of formula Q1a (E1=cyano) is used, or in the presence of a catalytic amount of acetone cyanohydrin or potassium cyanide, without isolation of the intermediates IIa and IIb. According to Reaction Scheme 1, Route b), the desired derivatives of formula I wherein R3 is hydroxy can be obtained e.g. analogously to E. Haslem, Tetrahedron, 2409-2433, 36, 1980 by first preparing enol esters of formula IIa and/or IIb by means of esterification of the carboxylic acids of formula Q1b with the dione derivatives of formula Da in an inert solvent, for example a halogenated hydrocarbon, for example dichloromethane, a nitrile, for example acetonitrile, or an aromatic hydrocarbon, for example toluene, in the presence of a base, e.g. an alkylamine, for example triethylamine, and a coupling agent, for example 2-chloro-1-methyl-pyridinium iodide, which enol esters are then converted in situ or in a second step into the compounds of formula I. That reaction takes place, depending upon the solvent used, at temperatures of from 0° C. to 110° C. and yields first, as described under Route a), the isomeric esters of formulae IIa and IIb, which can be isomerised to the desired derivatives of formula I (R3=hydroxy) as described under Route a), for example in the presence of a base and a catalytic amount of DMAP, or a cyanide source, e.g. acetone cyanohydrin. The activated carboxylic acid derivatives of formula Q1a in Reaction Scheme 1 (Route a) wherein E1 is a leaving group, e.g. halogen, for example bromine, iodine or especially chlorine, can be prepared according to known standard methods, as described e.g. in C. Ferri “Reaktionen der organischen Synthese”, Georg Thieme Verlag, Stuttgart, 1978, page 460 ff. Such reactions are generally known and various variations in respect of the leaving group E1 are described in the literature. Compounds of formula I wherein R3 is other than hydroxy or halogen can be prepared in accordance with conversion reactions generally known from the literature by nucleophilic substitution reactions on chlorides of formula I wherein R3 is chlorine, which are readily obtainable from compounds of formula I wherein R3 is hydroxy, likewise in accordance with known processes, by reaction with a chlorinating agent, such as phosgene, thionyl chloride or oxalyl chloride. In such a reaction there are used, for example, mercaptans, thiophenols or heterocyclic thiols in the presence of a base, for example 5-ethyl-2-methylpyridine, diisopropyl-ethylamine, triethylamine, sodium hydrogen carbonate, sodium acetate or potassium carbonate. Compounds of formula I wherein the substituent R3 contains thio groups can be oxidised to the corresponding sulfones and sulfoxides of formula I analogously to known standard methods, e.g. with peracids, for example meta-chloroperbenzoic acid (m-CPBA) or peracetic acid. In that reaction the degree of oxidation at the sulfur atom (SO— or SO2—) can be controlled by the amount of oxidising agent. Other sulfur-containing groups, for example those in the meanings of R1, R2, R6, R7, R8, L1, X1, X2, X3 or Y, or in alkyl groups and chains interrupted by sulfur, as may occur, for example, in Z1, Z2 and Z3, can be oxidised with a suitable oxidising agent, such as m-CPBA or sodium periodate, to the corresponding sulfone and sulfine (sulfoxido) groups directly in compounds of formula I, as well as in intermediates of formulae IIa, IIb, Da and Db (hereinbelow). The derivatives of formula I so obtained wherein R3 is other than hydroxy can also be in various isomeric forms, which can optionally be isolated in pure form. The invention therefore includes all those stereoisomeric forms. Examples of those isomeric forms are the following formulae I′, I″ and I″′, as shown with reference to compounds of formula I wherein Q is group Q1. The compounds of formula Da used as starting materials can be prepared, for example, by treating a compound of formula Db wherein A1, A2, R1, R2 and Y are as defined for formula I, Xa is chlorine or bromine and R3 is hydroxy or C1-C6alkoxy, in the presence of a suitable reducing agent, e.g. tributyltin hydride, or zinc in acetic acid, optionally followed, when R3 is C1-C6alkoxy, by aftertreatment in the presence of a hydrolysing agent, e.g. dilute hydrochloric acid or aqueous p-toluenesulfonic acid. Specifically the compounds of formula Db above wherein R1 and R2 are each hydrogen or methyl, A1 and A2 are each methylene, Y is oxygen, methylene or ethylene, R3 is chlorine, bromine or hydroxy and Xa is chlorine or bromine are known from Organic Letters 2002, 4, 1997; Archiv der Pharmazie 1987, 320, 1138; J. Amer. Chem. Soc. 1968, 90 2376 and from U.S. Pat. No. 3,538,117 and can be prepared in accordance with the methods described therein. The compounds of formula Da used as starting materials can accordingly also be prepared very generally in accordance with those known methods, by reacting a dienophilic compound of formula IV wherein A1, A2, R1, R2 and Y are as defined above, in an inert solvent, such as dichloromethane, 1,2-dichloroethane, toluene or chlorobenzene, optionally at elevated temperature or under elevated pressure, in a reaction similar to a Diels-Alder reaction, with a tetrahalocyclopropene of formula V wherein Xa is chlorine or bromine, and then hydrolysing the resulting bicyclic compound of formula VI wherein A1, A2, R1, R2, Xa and Y are as defined above, optionally in the presence of a suitable catalyst, for example silver nitrate or the silver tetrafluoroborate salt, or an acid, such as 90-98% sulfuric acid, 90% trifluoroacetic acid or p-toluenesulfonic acid, or reacting it with an alcoholate, for example sodium methanolate, potassium ethanolate or lithium isopropanolate, in order thus to obtain a compound of formula Db wherein A1, A2, R1, R2, Xa and Y are as defined above, and R3 depending upon the reaction conditions is either hydroxy, C1-C6alkoxy, chlorine or bromine, which is then further reduced and/or hydrolysed to form a novel compound of formula Da wherein A1, A2, R1, R2 and Y are as defined above. Compounds of formula VI can thus be reacted further, for example in the presence of 90-98% sulfuric acid at elevated temperature of about 80-100° C., to form compounds of formula Db wherein R3 is hydroxy and Xa is chlorine or bromine, as described in greater detail in J. Amer. Chem. Soc. 1968, 90, 2376. It is also possible for compounds of formula VI to be converted into compounds of formula Db wherein R3 and Xa are both chlorine or bromine, for example in the presence of 90% trifluoroacetic acid at boiling temperature or in the presence of aqueous silver nitrate at ambient temperature, as described in Archiv der Pharmazie 1987, 320, 1138 and in Organic Letters 2002, 4, 1997. On the other hand, compounds of formula VI can be converted into compounds of formula Db wherein R3 is C1-C6alkoxy and Xa is chlorine or bromine in good yields at ambient temperature in the presence of alcoholates of formula R3aO−M+ wherein R3a is accordingly C1-C6alkyl and M+ is an alkali metal salt, in a solvent, such as an alcohol R3aOH, toluene or ether, e.g. tetrahydrofuran, dimethoxyethane. It is also possible for compounds of formula Db wherein Xa is chlorine or bromine and R3 is hydroxy or C1-C6alkoxy to be reduced in the presence of reducing agents, e.g. tributyltin hydride, in an organic solvent, such as toluene or tetrahydrofuran, to form compounds of formula Db wherein Xa is hydrogen, as is well known according to general methods from the literature for the reduction of a halogen in a position adjacent to a carbonyl group (see e.g. Comprehensive Org. Funct. Group, Transformations, Vol. 1. ed. S. M. Roberts, Pergamon Press Oxford, 1995, pages 1-11). Finally, compounds of formula Db wherein R3 is C1-C6alkoxy, chlorine or bromine and Xa is hydrogen can be hydrolysed to compounds of formula Da in the presence of acids, e.g. dilute hydrochloric acid, dilute sulfuric acid or p-toluenesulfonic acid. The general reaction sequences for the preparation of compounds of formulae Da and Db from compounds of formulae IV and V via intermediates of formula VI are shown in the following Scheme. In the reaction of compounds of formula VI and/or Db wherein A1, A2, R1, R2, Xa and Y are as defined above and R3 is C1-C6alkoxy with alcoholates of formula R3aO−M+, it is also possible for compounds of formula VII to be formed wherein A1, A2, R1, R2, Xa and Y are as defined above and R3a is C1-C6alkyl or, when glycol is used, two R3a together are —CH2CH2—. Those compounds too can be reacted under the reduction conditions mentioned above, for example with tributyltin hydride or with zinc in the presence of acetic acid, by way of a compound of formula VIIa wherein A1, A2, R1, R2, R3a and Y are as defined above, and subsequent hydrolysis, for example with dilute hydrochloric acid or a catalytic amount of p-toluenesulfonic acid in water, to form the compounds of formulae Da and Db wherein A1, A2, R1, R2 and Y are as defined above and R3 is hydroxy and Xa is hydrogen, as is shown generally in the following Scheme. In a further process, compounds of formula Da can also be prepared either by conversion of a compound of formula VIII wherein R1, R2, A1, A2, Y are as defined above and Ra is C1-C6alkyl or, when glycol is used, two R3a together are —CH2CH2—, by hydrolysis, e.g. by treatment with an aqueous acid, Route c), or by conversion of a compound of formula IX wherein R1, R2, A1, A2, Y are as defined above, by means of oxidation, e.g. with selenium dioxide, Route d), first into a diketo compound of formula X wherein R1, R2, A1, A2, Y are as defined above, and subsequent conversion of that compound by carbene insertion, e.g. with diazomethane or with trimethylsilyl-diazomethane, into the 1,3-dione compound Da. Those processes are also known per se to the person skilled in the art; the compounds can be prepared, depending upon the functionality of the groups R1, R2, A1, A2 and Y, by general reaction routes shown in the following Scheme: Using such routes it is readily possible to obtain, in particular, those compounds of formula VIII wherein Y is a C2alkylene chain substituted by R6, wherein R6 is for example alkoxy, benzyloxy, alkylcarbonyl, alkoxycarbonyl, alkylthio or alkylsulfonyl. Methods of obtaining the starting compounds of formula VII used in the above-mentioned process are known, for example, from Acc. Chem. Res. 2002, 856; J.O.C. 2002, 67, 6493; Organic Letters 2002, 2477; Synlett, 2002,1520; Chem. Commun. 2001, 1624; Synlett, 2000, 421; Tetrahedron Letters, 1999, 8431; J.O.C. 1999, 64, 4102; J.A.C.S. 1998, 129, 13254; Tetrahedron Letters, 1998, 659; Synlett, 1997, 1351. Methods of obtaining the starting compounds of formula IX are described, for example, in Org. Lettr. 2002, 2063; Synthetic Commun. 2001, 707; J.A.C.S. 2001, 123, 1569; Synlett, 1999, 225; Synlett, 1997, 786; Tetrahedron Letters, 1996, 7295; Synthesis, 1995, 845. Compounds of formula X are known, for example, from Synthesis, 2000, 850. The transformations according to Route d) are likewise known, for example from Tetr. 1986, 42, 3491. Oxidation is preferably carried out with selenium dioxide in a solvent, such as acetic acid, at temperatures of from about 20° C. to about 120° C. and the carbene insertion with diazomethane is preferably effected at from about −40° C. to about 50° C. in a solvent, such as dichloromethane or diethyl ether. The carbene insertion can also be carried out with trimethylsilyldiazomethane, it having proved advantageous to work in the presence of a Lewis acid catalyst, such as boron trifluoride etherate, for example at temperatures of from about −15° C. to about +25° C. In principle, however, the compounds of formulae Da, Db, VII, VIIa, VIII, IX and X used as starting materials and as intermediates can be prepared, in dependence upon the substituent pattern A1, A2, R1, R2 and Y and also in dependence upon the availability of the starting materials, according to any desired methods and reaction routes, there being no limitation in respect of the process variants indicated above. The compounds of formula Da wherein R1, R2, A1, A2 and Y are as defined above, and also compounds of formula Db wherein R1, R2, A1, A2 and Y are as defined above and R3 is chlorine, bromine, hydroxy or C1-C6alkoxy and Xa is hydrogen, chlorine or bromine, with the exception of the compounds 3-chloro-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione; 3-chloro-bicyclo[3.2.1]oct-6-ene-2,4-dione; 3-chloro-4-hydroxy-bicyclo[3.2.1]octa-3,6-dien-2-one; 3,4-dibromo-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one; 3,4-dibromo-1,5-dimethyl-8-oxa-bicyclo-[3.2.1]octa-3,6-dien-2-one; 3,4-dibromo-bicyclo[3.2.1]octa-3,6-dien-2-one; 3,4-dichloro-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one; 3,4-dichloro-bicyclo[3.2.1]octa-3,6-dien-2-one and 7,8-dibromo-5,9-dihydro-5,9-methano-benzocyclohepten-6-one, and also the compounds of formula VII are novel and constitute valuable intermediates for the preparation of compounds of formula I. The present invention accordingly relates likewise thereto. The compounds of formulae Q1a, Q2a and Q3a used as starting materials and their corresponding acids Q1b, Q2b and Q3b are known from the publications WO 00/15615 and WO 01/94339 or can be prepared in accordance with the methods described therein. The compounds of formula V used as starting material are likewise known, for example from Synthesis 1987, 260 and from J. Amer. Chem. Soc. 1968, 90 2376. A large number of known standard methods are available for the preparation of all further compounds of formula I functionalised in accordance with the definition of A1, A2, R1, R2, Y and Q, for example alkylation, halogenation, acylation, amidation, oximation, oxidation and reduction, the choice of a suitable preparation process being governed by the properties (reactivities) of the substituents in question in the respective intermediates of formulae I, Da, Db, VI, VII and VIIa, and especially the starting materials of formulae IV and V and Q1b, Q2b and Q3b. The reactions to form compounds of formula I are advantageously carried out in aprotic, inert organic solvents. Such solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, such as acetonitrile or propionitrile, amides, such as N,N-dimethylformamide, diethylformamide or N-methylpyrrolidinone. The reaction temperatures are preferably from −20° C. to +120° C. The reactions generally proceed slightly exothermically and can generally be carried out at room temperature. In order to shorten the reaction time or to initiate the reaction, brief heating, up to the boiling point of the reaction mixture, can be carried out. The reaction times can likewise be shortened by the addition of a few drops of base as reaction catalyst. Suitable bases are especially tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,5-diazabicyclo[5.4.0]undec-7-ene. It is also possible, however, to use as bases inorganic bases, such as hydrides, e.g. sodium or calcium hydride, hydroxides, e.g. sodium or potassium hydroxide, carbonates, e.g. sodium or potassium carbonate, or hydrogen carbonates, e.g. potassium or sodium hydrogen carbonate. The bases can be used as such or alternatively with catalytic amounts of a phase transfer catalyst, e.g. crown ethers, especially 18-crown-6, or tetraalkylammonium salts. The end products of formula I can be isolated in conventional manner by concentration or evaporation of the solvent and purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, by distillation or by means of column chromatography or by means of the HPLC technique using a suitable eluant. The sequence in which the reactions should be carried out in order as far as possible to avoid secondary reactions will be familiar to the person skilled in the art. Unless the synthesis is specifically aimed at the isolation of pure isomers, the product may be obtained in the form of a mixture of two or more isomers, for example chiral centres in the case of alkyl groups or cis/trans isomerism in the case of alkenyl groups or <E> or <Z> forms. All such isomers can be separated by methods known per se, for example chromatography, crystallisation, or produced in the desired form by means of a specific reaction procedure. For the use according to the invention of the compounds of formula I, or of compositions comprising them, there come into consideration all methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques such as, for example, the controlled release of active ingredient. For that purpose a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If required, it is additionally possible to apply a coating (coated granules), which allows the active ingredient to be released in metered amounts over a specific period of time. The invention therefore relates also to a herbicidal and plant-growth-inhibiting composition comprising a herbicidally effective amount of a compound of formula I according to claim 1 on an inert carrier. The compounds of formula I can be used as herbicides in unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, suspensions, mixtures of a suspension and an emulsion (suspoemulsions), wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, on pages 9 to 13 of WO 97/34485. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are selected in accordance with the intended objectives and the prevailing circumstances. The formulations, that is to say the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers. Surface-active compounds (surfactants) may also be used in addition in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, on page 6 of WO 97/34485. Depending upon the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485. In addition, the surfactants conventionally employed in formulation technology, which are described, inter alia, in “McCutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood N.J., 1981, Stache, H., “Tensid-Taschenbuch”, Carl Hanser Verlag, Munich/Vienna 1981, and M. and J. Ash, “Encyclopedia of Surfactants”, Vol. I-III, Chemical Publishing Co., New York, 1980-81, are also suitable for the preparation of the herbicidal compositions according to the invention. The compositions according to the invention can additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters thereof or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 2%, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® obtainable from Rhône-Poulenc Canada Inc., alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. A preferred additive contains as active components essentially 80% by weight alkyl esters of fish oils and 15% by weight methylated rapeseed oil, and also 5% by weight of customary emulsifiers and pH modifiers. Especially preferred oil additives comprise alkyl esters of higher fatty acids (C8-C22), especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). A preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Henkel subsidiary Cognis GMBH, DE). The application and action of the oil additives can be improved by combining them with surface-active substances, such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485. Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C12-C22 fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available, preferred surfactants are the Genapol types (Clariant AG, Muttenz, Switzerland). Also preferred for use as surface-active substances are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltrisiloxanes, such as are commercially available as e.g. Silwet L-77®, and also perfluorinated surfactants. The concentration of surface-active substances in relation to the total additive is generally from 1 to 30% by weight. Examples of oil additives that consist of mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Zeneca Agro, Stoney Creek, Ontario, Calif.) and Actipron® (BP Oil UK Limited, GB). The addition of an organic solvent to the oil additive/surfactant mixture can also bring about a further enhancement of action. Suitable solvents are, for example, Solvesso® (ESSO) and Aromatic Solvent® (Exxon Corporation) types. The concentration of such solvents can be from 10 to 80% by weight of the total weight. Such oil additives, which are also described, for example, in U.S. Pat. No. 4,834,908, are suitable for the composition according to the invention. A commercially available oil additive is known by the name MERGE®, is obtainable from the BASF Corporation and is essentially described, for example, in U.S. Pat. No. 4,834,908 in col. 5, as Example COC-1. A further oil additive that is preferred according to the invention is SCORE® (Novartis Crop Protection Canada.) In addition to the oil additives listed above, in order to enhance the action of the compositions according to the invention it is also possible for formulations of alkyl pyrrolidones, such as are commercially available e.g. as Agrimax®, to be added to the spray mixture. Formulations of synthetic latices, such as, for example, polyacrylamide, polyvinyl compounds or poly-1-p-menthene, such as are commercially available as e.g. Bond®, Courier® or Emerald®, can also be used to enhance action. Solutions that contain propionic acid, for example Eurogkem Pen-e-trate®, can also be added as action-enhancing agent to the spray mixture. The herbicidal formulations generally contain from 0.1 to 99% by weight, especially from 0.1 to 95% by weight, of herbicide, from 1 to 99.9% by weight, especially from 5 to 99.8% by weight, of a solid or liquid formulation adjuvant, and from 0 to 25% by weight, especially from 0.1 to 25% by weight, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients. The compounds of formula I are generally applied to the plant or to the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent upon the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters. The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control. The term “crops” is to be understood as including also crops that have been rendered tolerant to herbicides or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®. Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to the Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to synthesise such toxins, are described in EP-A-0 451 878, EP-A-0 374 753, WO 93/07278, WO 95/34656 and EP-A-0 427 529. Plant crops or seed material thereof can be both herbicide-tolerant and at the same time resistant to insect feeding (“stacked” transgenic events). The weeds to be controlled may be both monocotyledonous and dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica. The compositions according to the invention may additionally comprise growth regulators, for example trinexapac (744), chlormequat chloride (129), clofencet (148), cyclanilide (170), ethephon (281), flurprimidol (355), gibberellic acid (379), inabenfide (421), maleic hydrazide (449), mefluidide (463), mepiquat chloride (465), paclobutrazol (548), prohexadione-calcium (595), uniconazole (746) or thidiazuron (703). It is also possible for a composition according to the invention to comprise fungicides, for example azoxystrobin (43), epoxiconazole (48), benomyl (60), bromuconazole (89), bitertanol (77), carbendazim (107), cyproconazole (189), cyprodinil (190), diclomezine (220), difenoconazole (228), diniconazole (247), epoxiconazole (48), ethirimol (284), etridiazole (294), fenarimol (300), fenbuconazole (302), fenpiclonil (311), fenpropidin (313), fenpropimorph (314), ferimzone (321), fludioxonil (334), fluquinconazole (349), flutolanil (360), flutriafol (361), imazalil (410), ipconazole (426), iprodione (428), isoprothiolane (432), kasugamycin (438), kresoxim-methyl (439), spiroxamine (441), mepronil (466), myclobutanil (505), nuarimol (528), pefurazoate (554), pencycuron (556), phthalide (576), probenazole (590), prochloraz (591), propiconazole (607), pyrazophos (619), pyroquilone (633), quinoxyfen (638), quintozene (639), tebuconazole (678), tetraconazole (695), thiabendazole (701), thifluzamide (705), triadimefon (720), triadimenol (721), tricyclazole (734), tridemorph (736), triflumizole (738), triforine (742), triticonazole (745) or vinclozolin (751). The number in brackets after each active ingredient refers to the entry number of that active ingredient in the Pesticide Manual, eleventh ed., British Crop Protection Council, 1997. The following Examples further illustrate the invention but do not limit the invention. PREPARATION EXAMPLE 1 Preparation of 2,3,4,4-tetrachloro-1,5-dimethyl-8-oxa-bicyclo-[3.2.1]octa-2,6-diene 6.49 g (67.48 mmol) of 2,5-dimethylfuran and 10 g (56.23 mmol) of tetrachlorocyclopropene are heated at boiling temperature in 70 ml of toluene for 16 hours. The toluene and excess 2,5-dimethylfuran are then removed under reduced pressure. The product, 14.77 g (95.9% of theory) of 2,3,4,4-tetrachloro-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-2,6-diene, which remains behind in the form of an oil, can be transferred to the next reaction step without further purification (1H NMR). 1H NMR (300 MHz; CDCl3) δ 6.50 (d, 1H); 6.15 (d, 1H); 1.82 (s, 3H); 1.63 (s, 3H). PREPARATION EXAMPLE P2 Preparation of 3,4-dichloro-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one 14 g (51.1 mmol) of unpurified 2,3,4,4-tetrachloro-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-2,6-diene and 17.36 g (102.2 mmol) of silver nitrate are dissolved in 500 ml of acetone/water 1:1 mixture and heated for 15 hours at a temperature of 65-70° C. until the reaction of the reactants is complete (thin-layer chromatography (TLC) monitoring (mobile phase hexane/ethyl acetate 4:1)). After the reaction mixture has cooled to ambient temperature, solid sodium hydrogen carbonate is then stirred into the mixture in portions in order to neutralise the nitric acid. The precipitated silver bromide is filtered off and most of the acetone is distilled off under reduced pressure. The aqueous phase that remains behind is extracted three times with ethyl acetate. The organic extract is washed with water, dried over sodium sulfate and concentrated by evaporation. The oily residue is purified by means of silica gel chromatography (eluant gradient: 3-50% ethyl acetate in hexane). 6.1 g (54%) of pure 3,4-dichloro-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one are obtained in the form of a pale yellow solid. 1H NMR (300 MHz; CDCl3) δ 6.65 (d, 1H); 6.23 (d, 1H); 1.72 (s, 3H); 1.61 (s, 3H). PREPARATION EXAMPLE P3 Preparation of 3-chloro-1,5-dimethyl-4-methoxy-8-oxa-bicyclo-[3.2.1]octa-3,6-dien-2-one and 3-chloro-4,4-dimethoxy-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one 6.0 g (27.39 mmol) of 3,4-dichloro-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one is introduced into 39 ml of anhydrous methanol. At a temperature of 0° C., the reaction mixture is further diluted dropwise with a solution of 15.2 ml of 5.4M sodium methanolate (82.17 mmol) and treated with 10 ml of absolute methanol. The reaction mixture is then heated to ambient temperature with 35 minutes' stirring. Using thin-layer chromatography (hexane/ethyl acetate 8:2) it can be established that reaction of the starting material is complete. The reaction solution is then concentrated under reduced pressure. The residue is then extracted by means of carbon tetrachloride against water. The aqueous phase is extracted a further three times using fresh carbon tetrachloride. The combined organic extracts are dried over sodium sulfate and concentrated by evaporation under reduced pressure; with ice-cooling, the oily product that remains behind crystallises out in the form of a ˜1:1 mixture. The mixture is separated by means of column chromatography on silica gel (eluant: gradient from 1-5% ethyl acetate/hexane). 3.1 g (52.9%) of pure 3-chloro-1,5-dimethyl-4-methoxy-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one are isolated. 1H NMR (300 MHz; CDCl3) δ 6.48 (d, 1H); 6.24 (d, 1H); 4.24 (s, 3H); 1.60 (s, 3H); 1.56 (s, 3H). A second fraction yields 3.17 g (46.9%) of pure 3-chloro-4,4-dimethoxy-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one. 1H NMR (300 MHz; CDCl3) δ 6.25 (d, 1H); 6.05 (d, 1H); 5.15 (s, 1H); 3.48 (s, 3H); 3.46 (s, 3H); 1.53 (s, 3H); 1.51 (s, 3H). PREPARATION EXAMPLE P4 Preparation of 4,4-dimethoxy-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one 2.2 g (8.92 mmol) of 3-chloro-4,4-dimethoxy-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one in 240 ml of toluene are degassed, with heating at reflux temperature, and a catalytic amount of 66 mg of azaisobutyronitrile (AIBN) and a solution of 5.9 ml (22.3 mmol) of tributyltin hydride are added in succession. The reaction mixture is maintained at reflux temperature for a further 20 minutes to complete the reaction (TLC monitoring: hexane/ethyl acetate 4:1). The reaction mixture is then concentrated by evaporation under reduced pressure. The residue is then taken up in acetonitrile and the tin-containing residues are extracted by means of hexane. The acetonitrile phase is concentrated by evaporation in vacuo, 1.56 g (82.4% of theory) of 4,4-dimethoxy-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one remaining behind in the form of a yellow oil, which can be used for the next reaction step without further purification. 1H NMR (300 MHz; CDCl3) δ 6.22 (d, 1H); 5.90 (d, 1H); 3.41 (s, 3H); 3.25 (s, 3H); 2.92 and 2.84 (AB syst., 2H, J=16.5 Hz); 1.55 (s, 3H); 1.45 (s, 3H). PREPARATION EXAMPLE P5 Preparation of 1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione 1.61 g (7.59 mmol) of 4,4-dimethoxy-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one and 0.432 g (2.28 mmol) of p-toluenesulfonic acid are dissolved in a 2:1 mixture of acetone and water and heated for 50 minutes at a temperature of 70° C. (TLC monitoring: hexane/ethyl acetate 9:1). The acetone is then removed under reduced pressure. The aqueous phase is then adjusted to pH 9 with saturated sodium hydrogen carbonate solution and extracted three times with ethyl acetate to remove neutral components. The aqueous phase is then adjusted to pH 5 with dilute hydrochloric acid and extracted three times with fresh ethyl acetate. The organic phase is dried over sodium sulfate and concentrated by evaporation under reduced pressure, there being obtained 1.04 g (82.5%) of technically pure 1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione in the form of a yellowish product, which can be used without further purification in the next reaction step to form compounds of formula I. 1H NMR (300 MHz; CDCl3) δ 6.46 (d, 1H); 6.23 (d, 1H); 5.54 (hept., 1H); 1.58 (d, 6H); 1.40 (d, 3H); 1.25 (d, 3H). PREPARATION EXAMPLE P6 Preparation of 3-bromo-1,5-dimethyl-4-isopropoxy-8-oxa-bicyclo-[3.2.1]octa-3,6-dien-2-one A solution of 2.74 g (8.9 mmol) of 3,4-dibromo-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one (prepared according to Organic Lett. 4(12), 1997 (2002)) dissolved in 10 ml of tetrahydrofuran is added dropwise at ambient temperature to a solution of 5.4 ml (10.7 mmol) of 2M lithium isopropanolate diluted with 10 ml of tetrahydrofuran. The mixture is stirred for 3 hours at ambient temperature until the starting material has reacted completely (TLC monitoring: hexane/ethyl acetate/hexane 4:1). The reaction solution is then treated at a temperature of 0° C. with a 10% sodium dihydrogen phosphate solution (20 ml) and water (30 ml) and extracted three times with ethyl acetate. Drying over sodium sulfate and concentration by evaporation are carried out. For further purification, the dark oil so obtained is purified by chromatography over silica gel with 5% ethyl acetate in hexane. 1.73 g (68% of theory) of pure 3-bromo-1,5-dimethyl-4-isopropoxy-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one are isolated. 1H NMR (300 MHz; CDCl3) δ 6.46 (d, 1H); 6.23 (d, 1H); 5.54 (hept., 1H); 1.58 (d, 6H); 1.40 (d, 3H); 1.25 (d, 3H). PREPARATION EXAMPLE P7 Preparation of 3-bromo-4,4-(1′,2′-ethylenedioxy)-bicyclo[3.2.1]oct-6-en-2-one A sodium glycolate solution is prepared by stirring 124 mg (5.4 mmol) of metallic sodium into 2.7 ml (42.42 mmol) of anhydrous ethylene glycol at ambient temperature and, when the sodium has completely dissolved, 1.5 ml of tetrahydrofuran are added. To the resulting monosodium glycolate solution there is then added dropwise a solution of 1 g (3.6 mmol) of 3,4-dibromo-bicyclo[3.2.1]octa-3,6-dien-2-one (prepared according to Organic Lett. 4(12), 1997 (2002)) dissolved in 5 ml of tetrahydrofuran. The reaction mixture is then stirred at ambient temperature for 90 minutes with TLC monitoring (mobile phase hexane/ethyl acetate 4:1). The reaction mixture is then treated with 8 ml of 10% sodium dihydrogen phosphate solution and extracted with ethyl acetate (3×). The organic phase is washed with water to remove ethylene glycol, then dried and concentrated by evaporation. 930 mg (˜100%) of 3-bromo-4,4-ethylenedioxy-bicyclo[3.2.1]oct-6-en-2-one are obtained in the form of a white solid. 1H NMR (300 MHz; CDCl3) δ 6.38 (m, 1H); 6.25 (m, 1H); 5.46 (s, 1H); 4.25 (m, 2H); 4.04 (m, 2H); 3.38 (m, 1H); 2.98 (m, 1H); 2.40 (m, 1H); 2.25 (m, 1H). PREPARATION EXAMPLE P8 Preparation of 4,4-(1′,2′-ethylenedioxy)-bicyclo[3.2.1]oct-6-en-2-one A degassed solution of 920 mg (3.55 mmol) of 3-bromo-4,4-(1′,2′-ethylenedioxy)-bicyclo-[3.2.1]oct-6-en-2-one in 90 ml of toluene is treated at boiling temperature in succession with a catalytic amount (30 mg) of AIBN and with 2.35 ml (8.88 mmol) of tributyltin hydride. To complete the reaction, the reaction mixture is maintained at reflux for a further 20 minutes, with TLC monitoring (mobile phase hexane/ethyl acetate 1:1). The reaction mixture is then concentrated by evaporation under reduced pressure. The residue is taken up in a small amount of acetonitrile and extracted five times with a small amount of hexane in order to remove tin-containing secondary products. The acetonitrile phase is then again concentrated by evaporation. 800 mg of 4,4-(1′,2′-ethylenedioxy)-bicyclo[3.2.1]oct-6-en-2-one are obtained in the form of a yellow oil, which can be transferred directly to the next reaction step without further purification. 1H NMR (300 MHz; CDCl3) δ 6.30 (m, 1H); 6.12 (m, 1H); 4.02-3.90 (m, 2×2H); 3.10 (m, 1H); 3.06 (d, 1H); 2.83 (m, 1H); 2.45 (d, 1H); 2.40-2.25 (m, 2×1H). PREPARATION EXAMPLE P9 Bicyclo[3.2.1]oct-6-ene-2,4-dione a) 640 mg (3.55 mmol) of 4,4-(1′,2′-ethylenedioxy)-bicyclo[3.2.1]oct-6-en-2-one are heated for 16 hours at a temperature of 70° C. in the presence of 200 mg of p-toluenesulfonic acid in a 2:1 mixture of acetone and water. After hydrolysis is complete (TLC monitoring: ethyl acetate/hexane 1:1), the acetone is distilled off under reduced pressure and the aqueous phase is adjusted to pH 9 with saturated sodium hydrogen carbonate solution. After extraction of the aqueous phase three times with ethyl acetate, it is acidified to pH 5 with dilute hydrochloric acid. Extraction is carried out three times with fresh ethyl acetate, followed by drying over sodium sulfate and concentration by evaporation in vacuo. 364 mg (75%) of pure bicyclo[3.2.1]oct-6-ene-2,4-dione are obtained in the form of a yellow oil for further reaction to form compounds of formula I. 1H NMR (300 MHz; CDCl3) δ 6.22 (m, 2H); 3.50 (d, 1H); 3.45 (m, 2H); 3.22 (d, 1H); 2.60-2.45 (m, 2×1H). b) One-pot process: 100 mg (0.39 mmol) of 3-bromo-4,4-(1′,2′-ethylenedioxy)-bicyclo[3.2.1]-oct-6-en-2-one are taken up in concentrated acetic acid and treated at ambient temperature with 80 mg (1.16 mmol) of zinc powder. The progress of the reaction is monitored by means of thin-layer chromatography (mobile phase: hexane/ethyl acetate 1:1). When after 2 hours brominated starting material can no longer be detected, the reaction mixture is heated continuously at a temperature of 95° C. After a further 2 hours, according to thin-layer chromatography all the reference material 4,4-(1′,2′-ethylenedioxy)-bicyclo[3.2.1]oct-6-en-2-one has reacted. The reaction mixture is filtered and concentrated in vacuo. The residue is treated with saturated sodium hydrogen carbonate solution and extracted three times with ethyl acetate. The alkaline aqueous phase is adjusted to pH 3-4 with dilute hydrochloric acid and extracted three times with fresh ethyl acetate. After drying of the organic phase over sodium sulfate and subsequent concentration by evaporation, 45 mg (85% of theory) of technically pure bicyclo[3.2.1]oct-6-ene-2,4-dione are obtained. PREPARATION EXAMPLE P10 Preparation of 3-[2-(2-methoxy-ethoxymethyl)-6-trifluoromethyl-pyridine-3-carbonyl]-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione 146 mg (0.879 mmol) of 1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione and 245 mg (0.879 mmol) of 2-(2-methoxy-ethoxymethyl)-6-trifluoromethyl-nicotinic acid (preparation as described in WO 01/94339) are dissolved in 29 ml of acetonitrile and treated at ambient temperature with 199 mg (0.966 mmol) of dicyclohexylcarbodiimide. The reaction mixture is stirred for 2 hours and then 0.184 ml (1.318 mmol) of triethylamine and 0.08 ml (0.879 mmol) of acetone cyanohydrin are added. Stirring is carried out for a further 16 hours at ambient temperature, followed by concentration under reduced pressure. The residue that remains behind is chromatographed over silica gel (eluant: toluene/ethanol/dioxane/triethylamine/water 20:8:4:4:1). The product-containing fraction is concentrated. The oily residue is again dissolved in fresh ethyl acetate and washed with 10 ml of dilute hydrochloric acid (pH 1), and then with water (2×) and sodium chloride solution (2×). After the solution has been dried over sodium sulfate and concentrated by evaporation under reduced pressure, 128 mg (34%) of 3-[2-(2-methoxy-ethoxymethyl)-6-trifluoromethyl-pyridine-3-carbonyl]-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione are obtained in the form of a yellow oil. 1H NMR (300 MHz; CDCl3) δ 16.1 (br. s, 1H); 7.68 (m, 2×1H); 6.29 (d, 1H); 6.22 (d, 1H); 4.72 (m, 2H); 3.48 (m, 2H); 3.37 (m, 2H); 3.32 (s, 3H); 1.68 (s, 3H); 1.48 (s, 3H). PREPARATION EXAMPLE P11 3-Chloro-bicyclo[3.2.2]non-6-ene-2,4-dione 0.7 g (2.7 mmol) of 2,3,4,4-tetrachloro-bicyclo[3.2.2]nona-2,6-diene (known from U.S. Pat. No. 3,538,117) is heated in a mixture of 1 ml of trifluoroacetic acid, 4 ml of acetic acid and 1 ml of water for 18 hours at a temperature of 70° C. The cooled reaction solution is then taken up in diethyl ether and extracted first with water and then with saturated sodium chloride solution. After chromatographic purification (ethyl acetate/hexane 1:4), 0.33 g of 3-chloro-bicyclo-[3.2.2]non-6-ene-2,4-dione is obtained as a tautomeric mixture of the forms Da and Db. 1H-NMR (300 MHz; CDCl3) δ 8.58 (b, 1H); 6.38 (m, 2H); 3.78 (m, 2H); 2.05 to 1.80 (m, 4H); tautomeric form Db. PREPARATION EXAMPLE P12 Bicyclo[3.2.2]non-6ene-2,4-dione 0.19 g (1 mmol) of 3-chloro-bicyclo[3.2.2]non-6-ene-2,4-dione is treated in the presence of 4 ml of acetic acid with 0.27 g (4 mmol) of zinc and the mixture is heated for 3 hours at a temperature of 95° C. The cooled reaction mixture is then extracted with ethyl acetate against water and then washed again with saturated sodium chloride solution. 0.14 g of amorphous bicyclo[3.2.2]non-6-ene-2,4-dione is obtained as tautomeric form Da. 1H-NMR (300 MHz; CDCl3) δ 6.22 (m, 2H); 3.58 to 3.51 (m, 2H); 2.12 (m, 2H); 1.92 (m, 2H). PREPARATION EXAMPLE P13 5-Bromo-7,8-dioxo-bicyclo[2.2.2]oct-5-ene-2-carboxylic acid methyl ester 3 g (9.4 mmol) of 5-bromo-8,8-dimethoxy-7-oxo-bicyclo[2.2.2]oct-5-ene-2-carboxylic acid methyl ester (J.O.C. (202), 67, 6493) are stirred in a mixture of 15 ml of trifluoroacetic acid and 1 ml of water for 12 hours at room temperature. Extraction is then carried out with dichloromethane against water. The organic phase is dried over sodium sulfate and yields, after removal of the solvent, the 5-bromo-7,8-dioxo-bicyclo[2.2.2]oct-5-ene-2-carboxylic acid methyl ester in the form of an orange-coloured oil and as a pure isomer. 1H-NMR (300 MHz; CDCl3) δ 6.62 (d, 1H); 3.97 (d, 1H); 3.80 (s, 3H); 3.70 (m, 1H); 3.20 (d, 1H); 2.63 (m, 1H); 2.40 (m, 1H). PREPARATION EXAMPLE P14 8-Bromo-2,4-dioxo-bicyclo[3.2.2]non-8-ene-6-carboxylic acid methyl ester 4.2 ml of trimethylsilyl-diazomethane are added dropwise at a temperature of −10° C. to a solution of 1.91 g (7 mmol) of 5-bromo-7,8-dioxo-bicyclo[2.2.2]oct-5-ene-2-carboxylic acid methyl ester in 20 ml of dichloromethane and 0.089 ml (0.7 mmol) of boron trifluoride etherate. The cooling is removed and the reaction mixture is stirred for 4 hours at a temperature of 20° C. The reaction solution is then extracted with water, the organic phase is dried over sodium sulfate and concentrated by evaporation using a rotary evaporator, and the residue is purified by silica gel chromatography. An isomer of 8-bromo-2,4-dioxo-bicyclo[3.2.2]non-8-ene-6-carboxylic acid methyl ester is obtained. 1H-NMR (300 MHz; CDCl3) δ 6.42 (d, 1H); 3.86 (d, 1H); 3.75 (d, 1H); 3.68 (s, 3H); 3.65 (m, 1H); 3.43 (d, 1H); 3.10 (m, 1H); 2.52 (m, 1H); 2.34 (m, 1H); tautomeric form Da. PREPARATION EXAMPLE P15 3-(2-Methyl-6-difluoromethyl-pyridine-3-carbonyl)-2,4-dioxo-bicyclo[3.2.2]non-8-ene-6-carboxylic acid methyl ester Catalytic amounts (10 mg) of azaisobutyronitrile are added to a solution of 0.10 g (0.24 mmol) of 8-bromo-3-(2-methyl-6-difluoromethyl-pyridine-3-carbonyl)-2,4-dioxo-bicyclo-[3.2.2]non-8-ene-6-carboxylic acid methyl ester (Example 1.1155) and 0.149 ml (0.48 mmol) of tris(trimethylsilyl)silane in 3.5 ml of toluene and the reaction mixture is stirred at a temperature of 80° C. 5 mg portions of fresh azaisobutyronitrile dissolved in a small amount of toluene are then added four times until, after 6 days, the reaction has come to a complete standstill (LC-MS monitoring). The solvent is then removed under reduced pressure and the residue is purified by silica gel chromatography (eluant: gradient mixture of ethyl acetate/tetrahydrofuran/hexane and 3% triethylamine). After removal of the solvents the triethyl-ammonium salt of 3-(2-methyl-6-difluoromethyl-pyridine-3-carbonyl)-2,4-dioxo-bicyclo-[3.2.2]non-8-ene-6-carboxylic acid methyl ester is obtained. 1H-NMR (300 MHz; CDCl3) δ 7.30 (m, 2H); 6.51 (t, 1H); 6.35 (m, 1H); 6.18 (m, 1H); 3.68 (m, 1H); 3.52 (s, 3H); 3.35 (m, 1H); 3.24 (m, 1H); 3.00 (q, 6H); 2.40 (s, 3H); 2.38 (m, 1H); 2.14 (m, 1H); 1.18 (t, 9H). The following Tables 1 to 3 list preferred compounds of formula I. The linkage site of the substituent Z1 to the pyridine ring is the unsaturated valency; the free bonds represent methyl groups. For example, in the group the —CH2 group at the nitrogen atom adjacent to the keto group is the linkage site; the free bond at the nitrogen atom represents methyl. That group can also be depicted as follows: TABLE 1 Compounds of formula Ib: (Ib) No. R1 R2 Z1 R30 X Y p Physical data 1.0000 H H CH3 H F NSO2CH3 0 1.0001 H H CH3 H Cl NSO2CH3 0 1.0002 H H CH3 H H NSO2CH3 0 1.0003 H H CH3 CH3 F NSO2CH3 0 1.0004 H H CH3 CH3 Cl NSO2CH3 0 1.0005 H H CH3 CH3 H NSO2CH3 0 1.0006 H H CH2CH3 H F NSO2CH3 0 1.0007 H H CH2CH3 H Cl NSO2CH3 0 1.0008 H H CH2CH3 H H NSO2CH3 0 1.0009 H H CH2CH2CH3 H F NSO2CH3 0 1.0010 H H CH2CH2CH3 H Cl NSO2CH3 0 1.0011 H H CH2CH2CH3 H H NSO2CH3 0 1.0012 H H CH2OCH3 H F NSO2CH3 0 1.0013 H H CH2OCH3 H Cl NSO2CH3 0 1.0014 H H CH2OCH3 H H NSO2CH3 0 1.0015 H H CH2OCH2CH3 H F NSO2CH3 0 1.0016 H H CH2OCH2CH3 H Cl NSO2CH3 0 1.0017 H H CH2OCH2CH3 H H NSO2CH3 0 1.0018 H H CH2OCH2CH2OCH3 H F NSO2CH3 0 1.0019 H H CH2OCH2CH2OCH3 H Cl NSO2CH3 0 1.0020 H H CH2OCH2CH2OCH3 H H NSO2CH3 0 1.0021 H H CH2OCH2CH2OCH2CH3 H F NSO2CH3 0 1.0022 H H CH2OCH2CH2OCH2CH3 H Cl NSO2CH3 0 1.0023 H H CH2OCH2CH2OCH2CH3 H H NSO2CH3 0 1.0024 H H CH2CH2OCH3 H F NSO2CH3 0 1.0025 H H CH2CH2OCH3 H Cl NSO2CH3 0 1.0026 H H CH2CH2OCH3 H H NSO2CH3 0 1.0027 H H CH2OCH2C≡CH H F NSO2CH3 0 1.0028 H H CH2OCH2C≡CH H Cl NSO2CH3 0 1.0029 H H CH2OCH2C≡CH H H NSO2CH3 0 1.0030 H H CH2OCH2C≡CCH3 H F NSO2CH3 0 1.0031 H H CH2OCH2C≡CCH3 H Cl NSO2CH3 0 1.0032 H H CH2OCH2C≡CCH3 H H NSO2CH3 0 1.0033 H H CH2CH2CH2OCH3 H F NSO2CH3 0 1.0034 H H CH2CH2CH2OCH3 H Cl NSO2CH3 0 1.0035 H H CH2CH2CH2OCH3 H H NSO2CH3 0 1.0036 H H CH2OCH2OCH3 H F NSO2CH3 0 1.0037 H H CH2OCH2OCH3 H Cl NSO2CH3 0 1.0038 H H CH2OCH2OCH3 H H NSO2CH3 0 1.0039 H H CH2N(CH3)SO2CH3 H F NSO2CH3 0 1.0040 H H CH2N(CH3)SO2CH3 H Cl NSO2CH3 0 1.0041 H H CH2N(CH3)SO2CH3 H H NSO2CH3 0 1.0042 H H CF3 H F NSO2CH3 0 1.0043 H H CF3 H Cl NSO2CH3 0 1.0044 H H CF3 H H NSO2CH3 0 1.0045 H H CH2OCH2CF3 H F NSO2CH3 0 1.0046 H H CH2OCH2CF3 H Cl NSO2CH3 0 1.0047 H H CH2OCH2CF3 H H NSO2CH3 0 1.0048 H H CH2OCH2Ph H F NSO2CH3 0 1.0049 H H CH2OCH2Ph H Cl NSO2CH3 0 1.0050 H H CH2OCH2Ph H H NSO2CH3 0 1.0051 H H CH2OCH2CH═CH2 H F NSO2CH3 0 1.0052 H H CH2OCH2CH═CH2 H Cl NSO2CH3 0 1.0053 H H CH2OCH2CH═CH2 H H NSO2CH3 0 1.0054 H H H F NSO2CH3 0 1.0055 H H H Cl NSO2CH3 0 1.0056 H H H H NSO2CH3 0 1.0057 H H H F NSO2CH3 0 1.0058 H H H Cl NSO2CH3 0 1.0059 H H H H NSO2CH3 0 1.0060 H H H F NSO2CH3 0 1.0061 H H H Cl NSO2CH3 0 1.0062 H H H H NSO2CH3 0 1.0063 H H H F NSO2CH3 0 1.0064 H H H Cl NSO2CH3 0 1.0065 H H H H NSO2CH3 0 1.0066 H H H F NSO2CH3 0 1.0067 H H H Cl NSO2CH3 0 1.0068 H H H H NSO2CH3 0 1.0069 H H H F NSO2CH3 0 1.0070 H H H Cl NSO2CH3 0 1.0071 H H H H NSO2CH3 0 1.0072 H H CH3 H F NSO2CH3 1 1.0073 H H CH2OCH3 H F NSO2CH3 1 1.0074 H H CH2OCH2CH2OCH3 H F NSO2CH3 1 1.0075 H H CH2CH2CH2OCH3 H F NSO2CH3 1 1.0076 H H CH2CH3 H F NSO2CH3 1 1.0077 H H CH3 H H NSO2CH3 1 1.0078 H H CH2OCH3 H H NSO2CH3 1 1.0079 H H CH2OCH2CH2OCH3 H H NSO2CH3 1 1.0080 H H CH2CH2CH2OCH3 H H NSO2CH3 1 1.0081 H H CH2CH3 H H NSO2CH3 1 1.0082 CH3 CH3 CH3 H F NSO2CH3 0 1.0083 CH3 CH3 CH3 H Cl NSO2CH3 0 1.0084 CH3 CH3 CH3 H H NSO2CH3 0 1.0085 CH3 CH3 CH3 CH3 F NSO2CH3 0 1.0086 CH3 CH3 CH3 CH3 Cl NSO2CH3 0 1.0087 CH3 CH3 CH3 CH3 H NSO2CH3 0 1.0088 CH3 CH3 CH2CH3 H F NSO2CH3 0 1.0089 CH3 CH3 CH2CH3 H Cl NSO2CH3 0 1.0090 CH3 CH3 CH2CH3 H H NSO2CH3 0 1.0091 CH3 CH3 CH2CH2CH3 H F NSO2CH3 0 1.0092 CH3 CH3 CH2CH2CH3 H Cl NSO2CH3 0 1.0093 CH3 CH3 CH2CH2CH3 H H NSO2CH3 0 1.0094 CH3 CH3 CH2OCH3 H F NSO2CH3 0 1.0095 CH3 CH3 CH2OCH3 H Cl NSO2CH3 0 1.0096 CH3 CH3 CH2OCH3 H H NSO2CH3 0 1.0097 CH3 CH3 CH2OCH2CH3 H F NSO2CH3 0 1.0098 CH3 CH3 CH2OCH2CH3 H Cl NSO2CH3 0 1.0099 CH3 CH3 CH2OCH2CH3 H H NSO2CH3 0 1.0100 CH3 CH3 CH2OCH2CH2OCH3 H F NSO2CH3 0 1.0101 CH3 CH3 CH2OCH2CH2OCH3 H Cl NSO2CH3 0 1.0102 CH3 CH3 CH2OCH2CH2OCH3 H H NSO2CH3 0 1.0103 CH3 CH3 CH2OCH2CH2OCH2CH3 H F NSO2CH3 0 1.0104 CH3 CH3 CH2OCH2CH2OCH2CH3 H Cl NSO2CH3 0 1.0105 CH3 CH3 CH2OCH2CH2OCH2CH3 H H NSO2CH3 0 1.0106 CH3 CH3 CH2CH2OCH3 H F NSO2CH3 0 1.0107 CH3 CH3 CH2CH2OCH3 H Cl NSO2CH3 0 1.0108 CH3 CH3 CH2CH2OCH3 H H NSO2CH3 0 1.0109 CH3 CH3 CH2OCH2C≡CH H F NSO2CH3 0 1.0110 CH3 CH3 CH2OCH2C≡CH H Cl NSO2CH3 0 1.0111 CH3 CH3 CH2OCH2C≡CH H H NSO2CH3 0 1.0112 CH3 CH3 CH2OCH2C≡CCH3 H F NSO2CH3 0 1.0113 CH3 CH3 CH2OCH2C≡CCH3 H Cl NSO2CH3 0 1.0114 CH3 CH3 CH2OCH2C≡CCH3 H H NSO2CH3 0 1.0115 CH3 CH3 CH2CH2CH2OCH3 H F NSO2CH3 0 1.0116 CH3 CH3 CH2CH2CH2OCH3 H Cl NSO2CH3 0 1.0117 CH3 CH3 CH2CH2CH2OCH3 H H NSO2CH3 0 1.0118 CH3 CH3 CH2OCH2OCH3 H F NSO2CH3 0 1.0119 CH3 CH3 CH2OCH2OCH3 H Cl NSO2CH3 0 1.0120 CH3 CH3 CH2OCH2OCH3 H H NSO2CH3 0 1.0121 CH3 CH3 CH2N(CH3)SO2CH3 H F NSO2CH3 0 1.0122 CH3 CH3 CH2N(CH3)SO2CH3 H Cl NSO2CH3 0 1.0123 CH3 CH3 CH2N(CH3)SO2CH3 H H NSO2CH3 0 1.0124 CH3 CH3 CF3 H F NSO2CH3 0 1.0125 CH3 CH3 CF3 H Cl NSO2CH3 0 1.0126 CH3 CH3 CF3 H H NSO2CH3 0 1.0127 CH3 CH3 CH2OCH2CF3 H F NSO2CH3 0 1.0128 CH3 CH3 CH2OCH2CF3 H Cl NSO2CH3 0 1.0129 CH3 CH3 CH2OCH2CF3 H H NSO2CH3 0 1.0130 CH3 CH3 CH2OCH2Ph H F NSO2CH3 0 1.0131 CH3 CH3 CH2OCH2Ph H Cl NSO2CH3 0 1.0132 CH3 CH3 CH2OCH2Ph H H NSO2CH3 0 1.0133 CH3 CH3 CH2OCH2CH═CH2 H F NSO2CH3 0 1.0134 CH3 CH3 CH2OCH2CH═CH2 H Cl NSO2CH3 0 1.0135 CH3 CH3 CH2OCH2CH═CH2 H H NSO2CH3 0 1.0136 CH3 CH3 H F NSO2CH3 0 1.0137 CH3 CH3 H Cl NSO2CH3 0 1.0138 CH3 CH3 H H NSO2CH3 0 1.0139 CH3 CH3 H F NSO2CH3 0 1.0140 CH3 CH3 H Cl NSO2CH3 0 1.0141 CH3 CH3 H H NSO2CH3 0 1.0142 CH3 CH3 H F NSO2CH3 0 1.0143 CH3 CH3 H Cl NSO2CH3 0 1.0144 CH3 CH3 H H NSO2CH3 0 1.0145 CH3 CH3 H F NSO2CH3 0 1.0146 CH3 CH3 H Cl NSO2CH3 0 1.0147 CH3 CH3 H H NSO2CH3 0 1.0148 CH3 CH3 H F NSO2CH3 0 1.0149 CH3 CH3 H Cl NSO2CH3 0 1.0150 CH3 CH3 H H NSO2CH3 0 1.0151 CH3 CH3 H F NSO2CH3 0 1.0152 CH3 CH3 H Cl NSO2CH3 0 1.0153 CH3 CH3 H H NSO2CH3 0 1.0154 CH3 CH3 CH3 H F NSO2CH3 1 1.0155 CH3 CH3 CH2OCH3 H F NSO2CH3 1 1.0156 CH3 CH3 CH2OCH2CH2OCH3 H F NSO2CH3 1 1.0157 CH3 CH3 CH2CH2CH2OCH3 H F NSO2CH3 I 1.0158 CH3 CH3 CH2CH3 H F NSO2CH3 1 1.0159 CH3 CH3 CH3 H H NSO2CH3 1 1.0160 CH3 CH3 CH2OCH3 H H NSO2CH3 1 1.0161 CH3 CH3 CH2OCH2CH2OCH3 H H NSO2CH3 1 1.0162 CH3 CH3 CH2CH2CH2OCH3 H H NSO2CH3 1 1.0163 CH3 CH3 CH2CH3 H H NSO2CH3 1 1.0164 H CH3 CH3 H F NSO2CH3 0 1.0165 H CH3 CH3 H Cl NSO2CH3 0 1.0166 H CH3 CH3 H H NSO2CH3 0 1.0167 H CH3 CH3 CH3 F NSO2CH3 0 1.0168 H CH3 CH3 CH3 Cl NSO2CH3 0 1.0169 H CH3 CH3 CH3 H NSO2CH3 0 1.0170 H CH3 CH2CH3 H F NSO2CH3 0 1.0171 H CH3 CH2CH3 H Cl NSO2CH3 0 1.0172 H CH3 CH2CH3 H H NSO2CH3 0 1.0173 H CH3 CH2CH2CH3 H F NSO2CH3 0 1.0174 H CH3 CH2CH2CH3 H Cl NSO2CH3 0 1.0175 H CH3 CH2CH2CH3 H H NSO2CH3 0 1.0176 H CH3 CH2OCH3 H F NSO2CH3 0 1.0177 H CH3 CH2OCH3 H Cl NSO2CH3 0 1.0178 H CH3 CH2OCH3 H H NSO2CH3 0 1.0179 H CH3 CH2OCH2CH3 H F NSO2CH3 0 1.0180 H CH3 CH2OCH2CH3 H Cl NSO2CH3 0 1.0181 H CH3 CH2OCH2CH3 H H NSO2CH3 0 1.0182 H CH3 CH2OCH2CH2OCH3 H F NSO2CH3 0 1.0183 H CH3 CH2OCH2CH2OCH3 H Cl NSO2CH3 0 1.0184 H CH3 CH2OCH2CH2OCH3 H H NSO2CH3 0 1.0185 H CH3 CH2OCH2CH2OCH2CH3 H F NSO2CH3 0 1.0186 H CH3 CH2OCH2CH2OCH2CH3 H Cl NSO2CH3 0 1.0187 H CH3 CH2OCH2CH2OCH2CH3 H H NSO2CH3 0 1.0188 H CH3 CH2CH2OCH3 H F NSO2CH3 0 1.0189 H CH3 CH2CH2OCH3 H Cl NSO2CH3 0 1.0190 H CH3 CH2CH2OCH3 H H NSO2CH3 0 1.0191 H CH3 CH2OCH2C≡CH H F NSO2CH3 0 1.0192 H CH3 CH2OCH2C≡CH H Cl NSO2CH3 0 1.0193 H CH3 CH2OCH2C≡CH H H NSO2CH3 0 1.0194 H CH3 CH2OCH2C≡CCH3 H F NSO2CH3 0 1.0195 H CH3 CH2OCH2C≡CCH3 H Cl NSO2CH3 0 1.0196 H CH3 CH2OCH2C≡CCH3 H H NSO2CH3 0 1.0197 H CH3 CH2CH2CH2OCH3 H F NSO2CH3 0 1.0198 H CH3 CH2CH2CH2OCH3 H Cl NSO2CH3 0 1.0199 H CH3 CH2CH2CH2OCH3 H H NSO2CH3 0 1.0200 H CH3 CH2OCH2OCH3 H F NSO2CH3 0 1.0201 H CH3 CH2OCH2OCH3 H Cl NSO2CH3 0 1.0202 H CH3 CH2OCH2OCH3 H H NSO2CH3 0 1.0203 H CH3 CH2N(CH3)SO2CH3 H F NSO2CH3 0 1.0204 H CH3 CH2N(CH3)SO2CH3 H Cl NSO2CH3 0 1.0205 H CH3 CH2N(CH3)SO2CH3 H H NSO2CH3 0 1.0206 H CH3 CF3 H F NSO2CH3 0 1.0207 H CH3 CF3 H Cl NSO2CH3 0 1.0208 H CH3 CF3 H H NSO2CH3 0 1.0209 H CH3 CH2OCH2CF3 H F NSO2CH3 0 1.0210 H CH3 CH2OCH2CF3 H Cl NSO2CH3 0 1.0211 H CH3 CH2OCH2CF3 H H NSO2CH3 0 1.0212 H CH3 CH2OCH2Ph H F NSO2CH3 0 1.0213 H CH3 CH2OCH2Ph H Cl NSO2CH3 0 1.0214 H CH3 CH2OCH2Ph H H NSO2CH3 0 1.0215 H CH3 CH2OCH2CH═CH2 H F NSO2CH3 0 1.0216 H CH3 CH2OCH2CH═CH2 H Cl NSO2CH3 0 1.0217 H CH3 CH2OCH2CH═CH2 H H NSO2CH3 0 1.0218 H CH3 H F NSO2CH3 0 1.0219 H CH3 H Cl NSO2CH3 0 1.0220 H CH3 H H NSO2CH3 0 1.0221 H CH3 H F NSO2CH3 0 1.0222 H CH3 H Cl NSO2CH3 0 1.0223 H CH3 H H NSO2CH3 0 1.0224 H CH3 H F NSO2CH3 0 1.0225 H CH3 H Cl NSO2CH3 0 1.0226 H CH3 H H NSO2CH3 0 1.0227 H CH3 H F NSO2CH3 0 1.0228 H CH3 H Cl NSO2CH3 0 1.0229 H CH3 H H NSO2CH3 0 1.0230 H CH3 H F NSO2CH3 0 1.0231 H CH3 H Cl NSO2CH3 0 1.0232 H CH3 H H NSO2CH3 0 1.0233 H CH3 H F NSO2CH3 0 1.0234 H CH3 H Cl NSO2CH3 0 1.0235 H CH3 H H NSO2CH3 0 1.0236 H CH3 CH3 H F NSO2CH3 1 1.0237 H CH3 CH2OCH3 H F NSO2CH3 1 1.0238 H CH3 CH2OCH2CH2OCH3 H F NSO2CH3 1 1.0239 H CH3 CH2CH2CH2OCH3 H F NSO2CH3 1 1.0240 H CH3 CH2CH3 H F NSO2CH3 1 1.0241 H CH3 CH3 H H NSO2CH3 1 1.0242 H CH3 CH2OCH3 H H NSO2CH3 1 1.0243 H CH3 CH2OCH2CH2OCH3 H H NSO2CH3 1 1.0244 H CH3 CH2CH2CH2OCH3 H H NSO2CH3 1 1.0245 H CH3 CH2CH3 H H NSO2CH3 1 1.0246 H H CH2OCH2CH2OCH3 H F O 0 1.0247 H H CH2OCH2CH2OCH3 H Cl O 0 1.0248 H H CH2OCH2CH2OCH3 H H O 0 1.0249 H H CH2OCH2CH2OCH2CH3 H F O 0 1.0250 H H CH2OCH2CH2OCH2CH3 H Cl O 0 1.0251 H H CH2OCH2CH2OCH2CH3 H H O 0 1.0252 H H CH2N(CH3)SO2CH3 H F O 0 1.0253 H H CH2N(CH3)SO2CH3 H Cl O 0 1.0254 H H CH2N(CH3)SO2CH3 H H O 0 1.0255 H H CH2OCH2Ph H F O 0 1.0256 H H CH2OCH2Ph H Cl O 0 1.0257 H H CH2OCH2Ph H H O 0 1.0258 H H CH2OCH2CH2OH H F O 0 1.0259 H H CH2OCH2CH2OH H Cl O 0 1.0260 H H CH2OCH2CH2OH H H O 0 1.0261 H H CH2OCH2CH2Cl H F O 0 1.0262 H H CH2OCH2CH2Cl H Cl O 0 1.0263 H H CH2OCH2CH2Cl H H O 0 1.0264 H H CH2OCH2CF3 H F O 0 1.0265 H H CH2OCH2CF3 H Cl O 0 1.0266 H H CH2OCH2CF3 H H O 0 1.0267 H H CH2OCH2CH═CH2 H F O 0 1.0268 H H CH2OCH2CH═CH2 H Cl O 0 1.0269 H H CH2OCH2CH═CH2 H H O 0 1.0270 H H CH2O(CO)CH3 H F O 0 1.0271 H H CH2O(CO)CH3 H Cl O 0 1.0272 H H CH2O(CO)CH3 H H O 0 1.0273 H H CH2OCH2C≡CH H F O 0 1.0274 H H CH2OCH2C≡CH H Cl O 0 1.0275 H H CH2OCH2C≡CH H H O 0 1.0276 H H CH2OCH2C≡CCH3 H F O 0 1.0277 H H CH2OCH2C≡CCH3 H Cl O 0 1.0278 H H CH2OCH2C≡CCH3 H H O 0 1.0279 H H H F O 0 1.0280 H H H Cl O 0 1.0281 H H H H O 0 1.0282 H H H F O 0 1.0283 H H H Cl O 0 1.0284 H H H H O 0 1.0285 H H H F O 0 1.0286 H H H Cl O 0 1.0287 H H H H O 0 1.0288 H H H F O 0 1.0289 H H H Cl O 0 1.0290 H H H H O 0 1.0291 H H H F O 0 1.0292 H H H Cl O 0 1.0293 H H H H O 0 1.0294 H H H F O 0 1.0295 H H H Cl O 0 1.0296 H H H H O 0 1.0297 H H CH2OCH2CH2OCH3 H F O 1 1.0298 H H CH2OCH2CH2OCH3 H H O 1 1.0299 H H CH2OCH2CH2OCH2CH3 H F O 1 1.0300 H H CH2OCH2CH2OCH2CH3 H H O 1 1.0301 CH3 CH3 CH2OCH2CH2OCH3 H F O 0 see Example P10 1.0302 CH3 CH3 CH2OCH2CH2OCH3 H Cl O 0 1.0303 CH3 CH3 CH2OCH2CH2OCH3 H H O 0 1.0304 CH3 CH3 CH2OCH2CH2OCH2CH3 H F O 0 1.0305 CH3 CH3 CH2OCH2CH2OCH2CH3 H Cl O 0 1.0306 CH3 CH3 CH2OCH2CH2OCH2CH3 H H O 0 1.0307 CH3 CH3 CH2N(CH3)SO2CH3 H F O 0 1.0308 CH3 CH3 CH2N(CH3)SO2CH3 H Cl O 0 1.0309 CH3 CH3 CH2N(CH3)SO2CH3 H H O 0 1.0310 CH3 CH3 CH2OCH2Ph H F O 0 1.0311 CH3 CH3 CH2OCH2Ph H Cl O 0 1.0312 CH3 CH3 CH2OCH2Ph H H O 0 1.0313 CH3 CH3 CH2OCH2CH2OH H F O 0 1.0314 CH3 CH3 CH2OCH2CH2OH H Cl O 0 1.0315 CH3 CH3 CH2OCH2CH2OH H H O 0 1.0316 CH3 CH3 CH2OCH2CH2Cl H F O 0 1.0317 CH3 CH3 CH2OCH2CH2Cl H Cl O 0 1.0318 CH3 CH3 CH2OCH2CH2Cl H H O 0 1.0319 CH3 CH3 CH2OCH2CF3 H F O 0 1.0320 CH3 CH3 CH2OCH2CF3 H Cl O 0 1.0321 CH3 CH3 CH2OCH2CF3 H H O 0 1.0322 CH3 CH3 CH2OCH2CH═CH2 H F O 0 1.0323 CH3 CH3 CH2OCH2CH═CH2 H Cl O 0 1.0324 CH3 CH3 CH2OCH2CH═CH2 H H O 0 1.0325 CH3 CH3 CH2O(CO)CH3 H F O 0 1.0326 CH3 CH3 CH2O(CO)CH3 H Cl O 0 1.0327 CH3 CH3 CH2O(CO)CH3 H H O 0 1.0328 CH3 CH3 CH2OCH2C≡CH H F O 0 1.0329 CH3 CH3 CH2OCH2C≡CH H Cl O 0 1.0330 CH3 CH3 CH2OCH2C≡CH H H O 0 1.0331 CH3 CH3 CH2OCH2C≡CCH3 H F O 0 1.0332 CH3 CH3 CH2OCH2C≡CCH3 H Cl O 0 1.0333 CH3 CH3 CH2OCH2C≡CCH3 H H O 0 1.0334 CH3 CH3 H F O 0 1.0335 CH3 CH3 H Cl O 0 1.0336 CH3 CH3 H H O 0 1.0337 CH3 CH3 H F O 0 1.0338 CH3 CH3 H Cl O 0 1.0339 CH3 CH3 H H O 0 1.0340 CH3 CH3 H F O 0 1.0341 CH3 CH3 H Cl O 0 1.0342 CH3 CH3 H H O 0 1.0343 CH3 CH3 H F O 0 1.0344 CH3 CH3 H Cl O 0 1.0345 CH3 CH3 H H O 0 1.0346 CH3 CH3 H F O 0 1.0347 CH3 CH3 H Cl O 0 1.0348 CH3 CH3 H H O 0 1.0349 CH3 CH3 H F O 0 1.0350 CH3 CH3 H Cl O 0 1.0351 CH3 CH3 H H O 0 1.0352 CH3 CH3 CH2OCH2CH2OCH3 H F O 1 1.0353 CH3 CH3 CH2OCH2CH2OCH3 H H O 1 1.0354 CH3 CH3 CH2OCH2CH2OCH2CH3 H F O 1 1.0355 CH3 CH3 CH2OCH2CH2OCH2CH3 H H O 1 1.0356 H CH3 CH2OCH2CH2OCH3 H F O 0 1.0357 H CH3 CH2OCH2CH2OCH3 H Cl O 0 1.0358 H CH3 CH2OCH2CH2OCH3 H H O 0 1.0359 H CH3 CH2OCH2CH2OCH2CH3 H F O 0 1.0360 H CH3 CH2OCH2CH2OCH2CH3 H Cl O 0 1.0361 H CH3 CH2OCH2CH2OCH2CH3 H H O 0 1.0362 H CH3 CH2N(CH3)SO2CH3 H F O 0 1.0363 H CH3 CH2N(CH3)SO2CH3 H Cl O 0 1.0364 H CH3 CH2N(CH3)SO2CH3 H H O 0 1.0365 H CH3 CH2OCH2Ph H F O 0 1.0366 H CH3 CH2OCH2Ph H Cl O 0 1.0367 H CH3 CH2OCH2Ph H H O 0 1.0368 H CH3 CH2OCH2CH2OH H F O 0 1.0369 H CH3 CH2OCH2CH2OH H Cl O 0 1.0370 H CH3 CH2OCH2CH2OH H H O 0 1.0371 H CH3 CH2OCH2CH2Cl H F O 0 1.0372 H CH3 CH2OCH2CH2Cl H Cl O 0 1.0373 H CH3 CH2OCH2CH2Cl H H O 0 1.0374 H CH3 CH2OCH2CF3 H F O 0 1.0375 H CH3 CH2OCH2CF3 H Cl O 0 1.0376 H CH3 CH2OCH2CF3 H H O 0 1.0377 H CH3 CH2OCH2CH═CH2 H F O 0 1.0378 H CH3 CH2OCH2CH═CH2 H Cl O 0 1.0379 H CH3 CH2OCH2CH═CH2 H H O 0 1.0380 H CH3 CH2O(CO)CH3 H F O 0 1.0381 H CH3 CH2O(CO)CH3 H Cl O 0 1.0382 H CH3 CH2O(CO)CH3 H H O 0 1.0383 H CH3 CH2OCH2C≡CH H F O 0 1.0384 H CH3 CH2OCH2C≡CH H Cl O 0 1.0385 H CH3 CH2OCH2C≡CH H H O 0 1.0386 H CH3 CH2OCH2C≡CCH3 H F O 0 1.0387 H CH3 CH2OCH2C≡CCH3 H Cl O 0 1.0388 H CH3 CH2OCH2C≡CCH3 H H O 0 1.0389 H CH3 H F O 0 1.0390 H CH3 H Cl O 0 1.0391 H CH3 H H O 0 1.0392 H CH3 H F O 0 1.0393 H CH3 H Cl O 0 1.0394 H CH3 H H O 0 1.0395 H CH3 H F O 0 1.0396 H CH3 H Cl O 0 1.0397 H CH3 H H O 0 1.0398 H CH3 H F O 0 1.0399 H CH3 H Cl O 0 1.0400 H CH3 H H O 0 1.0401 H CH3 H F O 0 1.0402 H CH3 H Cl O 0 1.0403 H CH3 H H O 0 1.0404 H CH3 H F O 0 1.0405 H CH3 H Cl O 0 1.0406 H CH3 H H O 0 1.0407 H CH3 CH2OCH2CH2OCH3 H F O 1 1.0408 H CH3 CH2OCH2CH2OCH3 H H O 1 1.0409 H CH3 CH2OCH2CH2OCH2CH3 H F O 1 1.0410 H CH3 CH2OCH2CH2OCH2CH3 H H O 1 1.0411 H H CH2OCH2CH2OCH3 H F CH2 0 1H NMR (300 MHz; CDCl3) δ 17.0 (broad s, 1H); 7.62 (s, 2H); 6.47 (m, 1H); 6.35 (m, 1H); 4.73 (m, 2H); 3.50 (m, 3H); 3.39 (m, 2H); 3.31 (s, 3H); 3.30 (m, 1H); 2.72-2.50 (m, 2H). 1.0412 H H CH2OCH2CH2OCH3 H Cl CH2 0 1.0413 H H CH2OCH2CH2OCH3 H H CH2 0 1.0414 H H CH2OCH2CH2OCH2CH3 H F CH2 0 1.0415 H H CH2OCH2CH2OCH2CH3 H Cl CH2 0 1.0416 H H CH2OCH2CH2OCH2CH3 H H CH2 0 1.0417 H H CH2N(CH3)SO2CH3 H F CH2 0 1.0418 H H CH2N(CH3)SO2CH3 H Cl CH2 0 1.0419 H H CH2N(CH3)SO2CH3 H H CH2 0 1.0420 H H CH2OCH2Ph H F CH2 0 1.0421 H H CH2OCH2Ph H Cl CH2 0 1.0422 H H CH2OCH2Ph H H CH2 0 1.0423 H H CH2OCH2CH2OH H F CH2 0 1.0424 H H CH2OCH2CH2OH H Cl CH2 0 1.0425 H H CH2OCH2CH2OH H H CH2 0 1.0426 H H CH2OCH2CH2Cl H F CH2 0 1.0427 H H CH2OCH2CH2Cl H Cl CH2 0 1.0428 H H CH2OCH2CH2Cl H H CH2 0 1.0429 H H CH2OCH2CF3 H F CH2 0 1.0430 H H CH2OCH2CF3 H Cl CH2 0 1.0431 H H CH2OCH2CF3 H H CH2 0 1.0432 H H CH2OCH2CH═CH2 H F CH2 0 1.0433 H H CH2OCH2CH═CH2 H Cl CH2 0 1.0434 H H CH2OCH2CH═CH2 H H CH2 0 1.0435 H H CH2O(CO)CH3 H F CH2 0 1.0436 H H CH2O(CO)CH3 H Cl CH2 0 1.0437 H H CH2O(CO)CH3 H H CH2 0 1.0438 H H CH2OCH2C≡CH H F CH2 0 1.0439 H H CH2OCH2C≡CH H Cl CH2 0 1.0440 H H CH2OCH2C≡CH H H CH2 0 1.0441 H H CH2OCH2C≡CCH3 H F CH2 0 1.0442 H H CH2OCH2C≡CCH3 H Cl CH2 0 1.0443 H H CH2OCH2C≡CCH3 H H CH2 0 1.0444 H H H F CH2 0 1.0445 H H H Cl CH2 0 1.0446 H H H H CH2 0 1.0447 H H H F CH2 0 1.0448 H H H Cl CH2 0 1.0449 H H H H CH2 0 1.0450 H H H F CH2 0 1.0451 H H H Cl CH2 0 1.0452 H H H H CH2 0 1.0453 H H H F CH2 0 1.0454 H H H Cl CH2 0 1.0455 H H H H CH2 0 1.0456 H H H F CH2 0 1.0457 H H H Cl CH2 0 1.0458 H H H H CH2 0 1.0459 H H H F CH2 0 1.0460 H H H Cl CH2 0 1.0461 H H H H CH2 0 1.0462 H H CH2OCH2CH2OCH3 H F CH2 1 1.0463 H H CH2OCH2CH2OCH3 H H CH2 1 1.0464 H H CH2OCH2CH2OCH2CH3 H F CH2 1 1.0465 H H CH2OCH2CH2OCH2CH3 H H CH2 1 1.0466 CH3 CH3 CH2OCH2CH2OCH3 H F CH2 0 1.0467 CH3 CH3 CH2OCH2CH2OCH3 H Cl CH2 0 1.0468 CH3 CH3 CH2OCH2CH2OCH3 H H CH2 0 1.0469 CH3 CH3 CH2OCH2CH2OCH2CH3 H F CH2 0 1.0470 CH3 CH3 CH2OCH2CH2OCH2CH3 H Cl CH2 0 1.0471 CH3 CH3 CH2OCH2CH2OCH2CH3 H H CH2 0 1.0472 CH3 CH3 CH2N(CH3)SO2CH3 H F CH2 0 1.0473 CH3 CH3 CH2N(CH3)SO2CH3 H Cl CH2 0 1.0474 CH3 CH3 CH2N(CH3)SO2CH3 H H CH2 0 1.0475 CH3 CH3 CH2OCH2Ph H F CH2 0 1.0476 CH3 CH3 CH2OCH2Ph H Cl CH2 0 1.0477 CH3 CH3 CH2OCH2Ph H H CH2 0 1.0478 CH3 CH3 CH2OCH2CH2OH H F CH2 0 1.0479 CH3 CH3 CH2OCH2CH2OH H Cl CH2 0 1.0480 CH3 CH3 CH2OCH2CH2OH H H CH2 0 1.0481 CH3 CH3 CH2OCH2CH2Cl H F CH2 0 1.0482 CH3 CH3 CH2OCH2CH2Cl H Cl CH2 0 1.0483 CH3 CH3 CH2OCH2CH2Cl H H CH2 0 1.0484 CH3 CH3 CH2OCH2CF3 H F CH2 0 1.0485 CH3 CH3 CH2OCH2CF3 H Cl CH2 0 1.0486 CH3 CH3 CH2OCH2CF3 H H CH2 0 1.0487 CH3 CH3 CH2OCH2CH═CH2 H F CH2 0 1.0488 CH3 CH3 CH2OCH2CH═CH2 H Cl CH2 0 1.0489 CH3 CH3 CH2OCH2CH═CH2 H H CH2 0 1.0490 CH3 CH3 CH2O(CO)CH3 H F CH2 0 1.0491 CH3 CH3 CH2O(CO)CH3 H Cl CH2 0 1.0492 CH3 CH3 CH2O(CO)CH3 H H CH2 0 1.0493 CH3 CH3 CH2OCH2C≡CH H F CH2 0 1.0494 CH3 CH3 CH2OCH2C≡CH H Cl CH2 0 1.0495 CH3 CH3 CH2OCH2C≡CH H H CH2 0 1.0496 CH3 CH3 CH2OCH2C≡CCH3 H F CH2 0 1.0497 CH3 CH3 CH2OCH2C≡CCH3 H Cl CH2 0 1.0498 CH3 CH3 CH2OCH2C≡CCH3 H H CH2 0 1.0499 CH3 CH3 H F CH2 0 1.0500 CH3 CH3 H Cl CH2 0 1.0501 CH3 CH3 H H CH2 0 1.0502 CH3 CH3 H F CH2 0 1.0503 CH3 CH3 H Cl CH2 0 1.0504 CH3 CH3 H H CH2 0 1.0505 CH3 CH3 H F CH2 0 1.0506 CH3 CH3 H Cl CH2 0 1.0507 CH3 CH3 H H CH2 0 1.0508 CH3 CH3 H F CH2 0 1.0509 CH3 CH3 H Cl CH2 0 1.0510 CH3 CH3 H H CH2 0 1.0511 CH3 CH3 H F CH2 0 1.0512 CH3 CH3 H Cl CH2 0 1.0513 CH3 CH3 H H CH2 0 1.0514 CH3 CH3 H F CH2 0 1.0515 CH3 CH3 H Cl CH2 0 1.0516 CH3 CH3 H H CH2 0 1.0517 CH3 CH3 CH2OCH2CH2OCH3 H F CH2 1 1.0518 CH3 CH3 CH2OCH2CH2OCH3 H H CH2 1 1.0519 CH3 CH3 CH2OCH2CH2OCH2CH3 H F CH2 1 1.0520 CH3 CH3 CH2OCH2CH2OCH2CH3 H H CH2 1 1.0521 H CH3 CH2OCH2CH2OCH3 H F CH2 0 1.0522 H CH3 CH2OCH2CH2OCH3 H Cl CH2 0 1.0523 H CH3 CH2OCH2CH2OCH3 H H CH2 0 1.0524 H CH3 CH2OCH2CH2OCH2CH3 H F CH2 0 1.0525 H CH3 CH2OCH2CH2OCH2CH3 H Cl CH2 0 1.0526 H CH3 CH2OCH2CH2OCH2CH3 H H CH2 0 1.0527 H CH3 CH2N(CH3)SO2CH3 H F CH2 0 1.0528 H CH3 CH2N(CH3)SO2CH3 H Cl CH2 0 1.0529 H CH3 CH2N(CH3)SO2CH3 H H CH2 0 1.0530 H CH3 CH2OCH2Ph H F CH2 0 1.0531 H CH3 CH2OCH2Ph H Cl CH2 0 1.0532 H CH3 CH2OCH2Ph H H CH2 0 1.0533 H CH3 CH2OCH2CH2OH H F CH2 0 1.0534 H CH3 CH2OCH2CH2OH H Cl CH2 0 1.0535 H CH3 CH2OCH2CH2OH H H CH2 0 1.0536 H CH3 CH2OCH2CH2Cl H F CH2 0 1.0537 H CH3 CH2OCH2CH2Cl H Cl CH2 0 1.0538 H CH3 CH2OCH2CH2Cl H H CH2 0 1.0539 H CH3 CH2OCH2CF3 H F CH2 0 1.0540 H CH3 CH2OCH2CF3 H Cl CH2 0 1.0541 H CH3 CH2OCH2CF3 H H CH2 0 1.0542 H CH3 CH2OCH2CH═CH2 H F CH2 0 1.0543 H CH3 CH2OCH2CH═CH2 H Cl CH2 0 1.0544 H CH3 CH2OCH2CH═CH2 H H CH2 0 1.0545 H CH3 CH2O(CO)CH3 H F CH2 0 1.0546 H CH3 CH2O(CO)CH3 H Cl CH2 0 1.0547 H CH3 CH2O(CO)CH3 H H CH2 0 1.0548 H CH3 CH2OCH2C≡CH H F CH2 0 1.0549 H CH3 CH2OCH2C≡CH H Cl CH2 0 1.0550 H CH3 CH2OCH2C≡CH H H CH2 0 1.0551 H CH3 CH2OCH2C≡CCH3 H F CH2 0 1.0552 H CH3 CH2OCH2C≡CCH3 H Cl CH2 0 1.0553 H CH3 CH2OCH2C≡CCH3 H H CH2 0 1.0554 H CH3 H F CH2 0 1.0555 H CH3 H Cl CH2 0 1.0556 H CH3 H H CH2 0 1.0557 H CH3 H F CH2 0 1.0558 H CH3 H Cl CH2 0 1.0559 H CH3 H H CH2 0 1.0560 H CH3 H F CH2 0 1.0561 H CH3 H Cl CH2 0 1.0562 H CH3 H H CH2 0 1.0563 H CH3 H F CH2 0 1.0564 H CH3 H Cl CH2 0 1.0565 H CH3 H H CH2 0 1.0566 H CH3 H F CH2 0 1.0567 H CH3 H Cl CH2 0 1.0568 H CH3 H H CH2 0 1.0569 H CH3 H F CH2 0 1.0570 H CH3 H Cl CH2 0 1.0571 H CH3 H H CH2 0 1.0572 H CH3 CH2OCH2CH2OCH3 H F CH2 1 1.0573 H CH3 CH2OCH2CH2OCH3 H H CH2 1 1.0574 H CH3 CH2OCH2CH2OCH2CH3 H F CH2 1 1.0575 H CH3 CH2OCH2CH2OCH2CH3 H H CH2 1 1.0576 H H CH2OCH2CH2OCH3 H F CH2CH2 0 resin 1.0577 H H CH2OCH2CH2OCH3 H Cl CH2CH2 0 1.0578 H H CH2OCH2CH2OCH3 H H CH2CH2 0 1.0579 H H CH2OCH2CH2OCH2CH3 H F CH2CH2 0 1.0580 H H CH2OCH2CH2OCH2CH3 H Cl CH2CH2 0 1.0581 H H CH2OCH2CH2OCH2CH3 H H CH2CH2 0 1.0582 H H CH2N(CH3)SO2CH3 H F CH2CH2 0 1.0583 H H CH2N(CH3)SO2CH3 H Cl CH2CH2 0 1.0584 H H CH2N(CH3)SO2CH3 H H CH2CH2 0 1.0585 H H CH2OCH2Ph H F CH2CH2 0 1.0586 H H CH2OCH2Ph H Cl CH2CH2 0 1.0587 H H CH2OCH2Ph H H CH2CH2 0 1.0588 H H CH2OCH2CH2OH H F CH2CH2 0 1.0589 H H CH2OCH2CH2OH H Cl CH2CH2 0 1.0590 H H CH2OCH2CH2OH H H CH2CH2 0 1.0591 H H CH2OCH2CH2Cl H F CH2CH2 0 1.0592 H H CH2OCH2CH2Cl H Cl CH2CH2 0 1.0593 H H CH2OCH2CH2Cl H H CH2CH2 0 1.0594 H H CH2OCH2CF3 H F CH2CH2 0 1.0595 H H CH2OCH2CF3 H Cl CH2CH2 0 1.0596 H H CH2OCH2CF3 H H CH2CH2 0 1.0597 H H CH2OCH2CH═CH2 H F CH2CH2 0 1.0598 H H CH2OCH2CH═CH2 H Cl CH2CH2 0 1.0599 H H CH2OCH2CH═CH2 H H CH2CH2 0 1.0600 H H CH2O(CO)CH3 H F CH2CH2 0 1.0601 H H CH2O(CO)CH3 H Cl CH2CH2 0 1.0602 H H CH2O(CO)CH3 H H CH2CH2 0 1.0603 H H CH2OCH2C≡CH H F CH2CH2 0 1.0604 H H CH2OCH2C≡CH H Cl CH2CH2 0 1.0605 H H CH2OCH2C≡CH H H CH2CH2 0 1.0606 H H CH2OCH2C≡CCH3 H F CH2CH2 0 1.0607 H H CH2OCH2C≡CCH3 H Cl CH2CH2 0 1.0608 H H CH2OCH2C≡CCH3 H H CH2CH2 0 1.0609 H H H F CH2CH2 0 1.0610 H H H Cl CH2CH2 0 1.0611 H H H H CH2CH2 0 1.0612 H H H F CH2CH2 0 1.0613 H H H Cl CH2CH2 0 1.0614 H H H H CH2CH2 0 1.0615 H H H F CH2CH2 0 1.0616 H H H Cl CH2CH2 0 1.0617 H H H H CH2CH2 0 1.0618 H H H F CH2CH2 0 1.0619 H H H Cl CH2CH2 0 1.0620 H H H H CH2CH2 0 1.0621 H H H F CH2CH2 0 1.0622 H H H Cl CH2CH2 0 1.0623 H H H H CH2CH2 0 1.0624 H H H F CH2CH2 0 1.0625 H H H Cl CH2CH2 0 1.0626 H H H H CH2CH2 0 1.0627 H H CH2OCH2CH2OCH3 H F CH2CH2 1 1.0628 H H CH2OCH2CH2OCH3 H H CH2CH2 1 1.0629 H H CH2OCH2CH2OCH2CH3 H F CH2CH2 1 1.0630 H H CH2OCH2CH2OCH2CH3 H H CH2CH2 1 1.0631 CH3 CH3 CH2OCH2CH2OCH3 H F CH2CH2 0 1.0632 CH3 CH3 CH2OCH2CH2OCH3 H Cl CH2CH2 0 1.0633 CH3 CH3 CH2OCH2CH2OCH3 H H CH2CH2 0 1.0634 CH3 CH3 CH2OCH2CH2OCH2CH3 H F CH2CH2 0 1.0635 CH3 CH3 CH2OCH2CH2OCH2CH3 H Cl CH2CH2 0 1.0636 CH3 CH3 CH2OCH2CH2OCH2CH3 H H CH2CH2 0 1.0637 CH3 CH3 CH2N(CH3)SO2CH3 H F CH2CH2 0 1.0638 CH3 CH3 CH2N(CH3)SO2CH3 H Cl CH2CH2 0 1.0639 CH3 CH3 CH2N(CH3)SO2CH3 H H CH2CH2 0 1.0640 CH3 CH3 CH2OCH2Ph H F CH2CH2 0 1.0641 CH3 CH3 CH2OCH2Ph H Cl CH2CH2 0 1.0642 CH3 CH3 CH2OCH2Ph H H CH2CH2 0 1.0643 CH3 CH3 CH2OCH2CH2OH H F CH2CH2 0 1.0644 CH3 CH3 CH2OCH2CH2OH H Cl CH2CH2 0 1.0645 CH3 CH3 CH2OCH2CH2OH H H CH2CH2 0 1.0646 CH3 CH3 CH2OCH2CH2Cl H F CH2CH2 0 1.0647 CH3 CH3 CH2OCH2CH2Cl H Cl CH2CH2 0 1.0648 CH3 CH3 CH2OCH2CH2Cl H H CH2CH2 0 1.0649 CH3 CH3 CH2OCH2CF3 H F CH2CH2 0 1.0650 CH3 CH3 CH2OCH2CF3 H Cl CH2CH2 0 1.0651 CH3 CH3 CH2OCH2CF3 H H CH2CH2 0 1.0652 CH3 CH3 CH2OCH2CH═CH2 H F CH2CH2 0 1.0653 CH3 CH3 CH2OCH2CH═CH2 H Cl CH2CH2 0 1.0654 CH3 CH3 CH2OCH2CH═CH2 H H CH2CH2 0 1.0655 CH3 CH3 CH2O(CO)CH3 H F CH2CH2 0 1.0656 CH3 CH3 CH2O(CO)CH3 H Cl CH2CH2 0 1.0657 CH3 CH3 CH2O(CO)CH3 H H CH2CH2 0 1.0658 CH3 CH3 CH2OCH2C≡CH H F CH2CH2 0 1.0659 CH3 CH3 CH2OCH2C≡CH H Cl CH2CH2 0 1.0660 CH3 CH3 CH2OCH2C≡CH H H CH2CH2 0 1.0661 CH3 CH3 CH2OCH2C≡CCH3 H F CH2CH2 0 1.0662 CH3 CH3 CH2OCH2C≡CCH3 H 01 CH2CH2 0 1.0663 CH3 CH3 CH2OCH2C≡CCH3 H H CH2CH2 0 1.0664 CH3 CH3 H F CH2CH2 0 1.0665 CH3 CH3 H Cl CH2CH2 0 1.0666 CH3 CH3 H H CH2CH2 0 1.0667 CH3 CH3 H F CH2CH2 0 1.0668 CH3 CH3 H Cl CH2CH2 0 1.0669 CH3 CH3 H H CH2CH2 0 1.0670 CH3 CH3 H F CH2CH2 0 1.0671 CH3 CH3 H Cl CH2CH2 0 1.0672 CH3 CH3 H H CH2CH2 0 1.0673 CH3 CH3 H F CH2CH2 0 1.0674 CH3 CH3 H Cl CH2CH2 0 1.0675 CH3 CH3 H H CH2CH2 0 1.0676 CH3 CH3 H F CH2CH2 0 1.0677 CH3 CH3 H Cl CH2CH2 0 1.0678 CH3 CH3 H H CH2CH2 0 1.0679 CH3 CH3 H F CH2CH2 0 1.0680 CH3 CH3 H Cl CH2CH2 0 1.0681 CH3 CH3 H H CH2CH2 0 1.0682 CH3 CH3 CH2OCH2CH2OCH3 H F CH2CH2 1 1.0683 CH3 CH3 CH2OCH2CH2OCH3 H H CH2CH2 1 1.0684 CH3 CH3 CH2OCH2CH2OCH2CH3 H F CH2CH2 1 1.0685 CH3 CH3 CH2OCH2CH2OCH2CH3 H H CH2CH2 1 1.0686 H CH3 CH2OCH2CH2OCH3 H F CH2CH2 0 1.0687 H CH3 CH2OCH2CH2OCH3 H Cl CH2CH2 0 1.0688 H CH3 CH2OCH2CH2OCH3 H H CH2CH2 0 1.0689 H CH3 CH2OCH2CH2OCH2CH3 H F CH2CH2 0 1.0690 H CH3 CH2OCH2CH2OCH2CH3 H Cl CH2CH2 0 1.0691 H CH3 CH2OCH2CH2OCH2CH3 H H CH2CH2 0 1.0692 H CH3 CH2N(CH3)SO2CH3 H F CH2CH2 0 1.0693 H CH3 CH2N(CH3)SO2CH3 H Cl CH2CH2 0 1.0694 H CH3 CH2N(CH3)SO2CH3 H H CH2CH2 0 1.0695 H CH3 CH2OCH2Ph H F CH2CH2 0 1.0696 H CH3 CH2OCH2Ph H Cl CH2CH2 0 1.0697 H CH3 CH2OCH2Ph H H CH2CH2 0 1.0698 H CH3 CH2OCH2CH2OH H F CH2CH2 0 1.0699 H CH3 CH2OCH2CH2OH H Cl CH2CH2 0 1.0700 H CH3 CH2OCH2CH2OH H H CH2CH2 0 1.0701 H CH3 CH2OCH2CH2Cl H F CH2CH2 0 1.0702 H CH3 CH2OCH2CH2Cl H Cl CH2CH2 0 1.0703 H CH3 CH2OCH2CH2Cl H H CH2CH2 0 1.0704 H CH3 CH2OCH2CF3 H F CH2CH2 0 1.0705 H CH3 CH2OCH2CF3 H Cl CH2CH2 0 1.0706 H CH3 CH2OCH2CF3 H H CH2CH2 0 1.0707 H CH3 CH2OCH2CH═CH2 H F CH2CH2 0 1.0708 H CH3 CH2OCH2CH═CH2 H Cl CH2CH2 0 1.0709 H CH3 CH2OCH2CH═CH2 H H CH2CH2 0 1.0710 H CH3 CH2O(CO)CH3 H F CH2CH2 0 1.0711 H CH3 CH2O(CO)CH3 H Cl CH2CH2 0 1.0712 H CH3 CH2O(CO)CH3 H H CH2CH2 0 1.0713 H CH3 CH2OCH2C≡CH H F CH2CH2 0 1.0714 H CH3 CH2OCH2C≡CH H Cl CH2CH2 0 1.0715 H CH3 CH2OCH2C≡CH H H CH2CH2 0 1.0716 H CH3 CH2OCH2C≡CCH3 H F CH2CH2 0 1.0717 H CH3 CH2OCH2C≡CCH3 H Cl CH2CH2 0 1.0718 H CH3 CH2OCH2C≡CCH3 H H CH2CH2 0 1.0719 H CH3 H F CH2CH2 0 1.0720 H CH3 H Cl CH2CH2 0 1.0721 H CH3 H H CH2CH2 0 1.0722 H CH3 H F CH2CH2 0 1.0723 H CH3 H Cl CH2CH2 0 1.0724 H CH3 H H CH2CH2 0 1.0725 H CH3 H F CH2CH2 0 1.0726 H CH3 H Cl CH2CH2 0 1.0727 H CH3 H H CH2CH2 0 1.0728 H CH3 H F CH2CH2 0 1.0729 H CH3 H Cl CH2CH2 0 1.0730 H CH3 H H CH2CH2 Q 1.0731 H CH3 H F CH2CH2 0 1.0732 H CH3 H Cl CH2CH2 0 1.0733 H CH3 H H CH2CH2 0 1.0734 H CH3 H F CH2CH2 0 1.0735 H CH3 H Cl CH2CH2 0 1.0736 H CH3 H H CH2CH2 0 1.0737 H CH3 CH2OCH2CH2OCH3 H F CH2CH2 1 1.0738 H CH3 CH2OCH2CH2OCH3 H H CH2CH2 1 1.0739 H CH3 CH2OCH2CH2OCH2CH3 H F CH2CH2 1 1.0740 H CH3 CH2OCH2CH2OCH2CH3 H H CH2CH2 1 1.0741 H CH3 CH2OCH2CH2OCH3 H Cl CH2CH2 1 1.0742 H H CH2OCH2CH2OCH3 H F NC(O)C(CH3)3 0 1.0743 H H CH2OCH2CH2OCH3 H Cl NC(O)C(CH3)3 0 1.0744 H H CH2OCH2CH2OCH3 H H NC(O)C(CH3)3 0 1.0745 H H CH2OCH2CH2OCH2CH3 H F NC(O)C(CH3)3 0 1.0746 H H CH2OCH2CH2OCH2CH3 H Cl NC(O)C(CH3)3 0 1.0747 H H CH2OCH2CH2OCH2CH3 H H NC(O)C(CH3)3 0 1.0748 H H CH2N(CH3)SO2CH3 H F NC(O)C(CH3)3 0 1.0749 H H CH2N(CH3)SO2CH3 H Cl NC(O)C(CH3)3 0 1.0750 H H CH2N(CH3)SO2CH3 H H NC(O)C(CH3)3 0 1.0751 H H CH2OCH2Ph H F NC(O)C(CH3)3 0 1.0752 H H CH2OCH2Ph H Cl NC(O)C(CH3)3 0 1.0753 H H CH2OCH2Ph H H NC(O)C(CH3)3 0 1.0754 H H CH2OCH2CH2OH H F NC(O)C(CH3)3 0 1.0755 H H CH2OCH2CH2OH H Cl NC(O)C(CH3)3 0 1.0756 H H CH2OCH2CH2OH H H NC(O)C(CH3)3 0 1.0757 H H CH2OCH2CH2Cl H F NO(O)O(CH3)3 0 1.0758 H H CH2OCH2CH2Cl H Cl NC(O)C(CH3)3 0 1.0759 H H CH2OCH2CH2Cl H H NO(O)C(CH3)3 0 1.0760 H H CH2OCH2CF3 H F NC(O)C(CH3)3 0 1.0761 H H CH2OCH2CF3 H Cl NC(O)C(CH3)3 0 1.0762 H H CH2OCH2CF3 H H NC(O)C(CH3)3 0 1.0763 H H CH2OCH2CH═CH2 H F NC(O)C(CH3)3 0 1.0764 H H CH2OCH2CH═CH2 H Cl NC(O)C(CH3)3 0 1.0765 H H CH2OCH2CH═CH2 H H NC(O)C(CH3)3 0 1.0766 H H CH2O(CO)CH3 H F NC(O)C(CH3)3 0 1.0767 H H CH2O(CO)CH3 H Cl NC(O)C(CH3)3 0 1.0768 H H CH2O(CO)CH3 H H NC(O)C(CH3)3 0 1.0769 H H CH2OCH2C≡CH H F NC(O)C(CH3)3 0 1.0770 H H CH2OCH2C≡CH H Cl NC(O)C(CH3)3 0 1.0771 H H CH2OCH2C≡CH H H NC(O)C(CH3)3 0 1.0772 H H CH2OCH2C≡CCH3 H F NC(O)C(CH3)3 0 1.0773 H H CH2OCH2C≡CCH3 H Cl NC(O)C(CH3)3 0 1.0774 H H CH2OCH2C≡CCH3 H H NC(O)C(CH3)3 0 1.0775 H H H F NC(O)C(CH3)3 0 1.0776 H H H Cl NC(O)C(CH3)3 0 1.0777 H H H H NC(O)C(CH3)3 0 1.0778 H H H F NC(O)C(CH3)3 0 1.0779 H H H Cl NC(O)C(CH3)3 0 1.0780 H H H H NC(O)C(CH3)3 0 1.0781 H H H F NC(O)C(CH3)3 0 1.0782 H H H Cl NC(O)C(CH3)3 0 1.0783 H H H H NC(O)C(CH3)3 0 1.0784 H H H F NC(O)C(CH3)3 0 1.0785 H H H Cl NC(O)C(CH3)3 0 1.0786 H H H H NC(O)C(CH3)3 0 1.0787 H H H F NC(O)C(CH3)3 0 1.0788 H H H Cl NC(O)C(CH3)3 0 1.0789 H H H H NC(O)C(CH3)3 0 1.0790 H H H F NC(O)C(CH3)3 0 1.0791 H H H Cl NC(O)C(CH3)3 0 1.0792 H H H H NC(O)C(CH3)3 0 1.0793 H H CH2OCH2CH2OCH3 H F NC(O)C(CH3)3 1 1.0794 H H CH2OCH2CH2OCH3 H H NC(O)C(CH3)3 1 1.0795 H H CH2OCH2CH2OCH2CH3 H F NC(O)C(CH3)3 1 1.0796 H H CH2OCH2CH2OCH2CH3 H H NC(O)C(CH3)3 1 1.0797 CH3 CH3 CH2OCH2CH2OCH3 H F NC(O)C(CH3)3 0 1.0798 CH3 CH3 CH2OCH2CH2OCH3 H Cl NC(O)C(CH3)3 0 1.0799 CH3 CH3 CH2OCH2CH2OCH3 H H NC(O)C(CH3)3 0 1.0800 CH3 CH3 CH2OCH2CH2OCH2CH3 H F NC(O)C(CH3)3 0 1.0801 CH3 CH3 CH2OCH2CH2OCH2CH3 H Cl NC(O)C(CH3)3 0 1.0802 CH3 CH3 CH2OCH2CH2OCH2CH3 H H NC(O)C(CH3)3 0 1.0803 CH3 CH3 CH2N(CH3)SO2CH3 H F NC(O)C(CH3)3 0 1.0804 CH3 CH3 CH2N(CH3)SO2CH3 H Cl NC(O)C(CH3)3 0 1.0805 CH3 CH3 CH2N(CH3)SO2CH3 H H NC(O)C(CH3)3 0 1.0806 CH3 CH3 CH2OCH2Ph H F NC(O)C(CH3)3 0 1.0807 CH3 CH3 CH2OCH2Ph H Cl NC(O)C(CH3)3 0 1.0808 CH3 CH3 CH2OCH2Ph H H NC(O)C(CH3)3 0 1.0809 CH3 CH3 CH2OCH2CH2OH H F NC(O)C(CH3)3 0 1.0810 CH3 CH3 CH2OCH2CH2OH H Cl NC(O)C(CH3)3 0 1.0811 CH3 CH3 CH2OCH2CH2OH H H NC(O)C(CH3)3 0 1.0812 CH3 CH3 CH2OCH2CH2Cl H F NC(O)C(CH3)3 0 1.0813 CH3 CH3 CH2OCH2CH2Cl H Cl NC(O)C(CH3)3 0 1.0814 CH3 CH3 CH2OCH2CH2Cl H H NC(O)C(CH3)3 0 1.0815 CH3 CH3 CH2OCH2CF3 H F NC(O)C(CH3)3 0 1.0816 CH3 CH3 CH2OCH2CF3 H Cl NC(O)C(CH3)3 0 1.0817 CH3 CH3 CH2OCH2CF3 H H NC(O)C(CH3)3 0 1.0818 CH3 CH3 CH2OCH2CH═CH2 H F NC(O)C(CH3)3 0 1.0819 CH3 CH3 CH2OCH2CH═CH2 H Cl NC(O)C(CH3)3 0 1.0820 CH3 CH3 CH2OCH2CH═CH2 H H NC(O)C(CH3)3 0 1.0821 CH3 CH3 CH2O(CO)CH3 H F NC(O)C(CH3)3 0 1.0822 CH3 CH3 CH2O(CO)CH3 H Cl NC(O)C(CH3)3 0 1.0823 CH3 CH3 CH2O(CO)CH3 H H NC(O)C(CH3)3 0 1.0824 CH3 CH3 CH2OCH2C≡CH H F NC(O)C(CH3)3 0 1.0825 CH3 CH3 CH2OCH2C≡CH H Cl NC(O)C(CH3)3 0 1.0826 CH3 CH3 CH2OCH2C≡CH H H NC(O)C(CH3)3 0 1.0827 CH3 CH3 CH2OCH2C≡CCH3 H F NC(O)C(CH3)3 0 1.0828 CH3 CH3 CH2OCH2C≡CCH3 H Cl NC(O)C(CH3)3 0 1.0829 CH3 CH3 CH2OCH2C≡CCH3 H H NC(O)C(CH3)3 0 1.0830 CH3 CH3 H F NC(O)C(CH3)3 0 1.0831 CH3 CH3 H Cl NC(O)C(CH3)3 0 1.0832 CH3 CH3 H H NC(O)C(CH3)3 0 1.0833 CH3 CH3 H F NC(O)C(CH3)3 0 1.0834 CH3 CH3 H Cl NC(O)C(CH3)3 0 1.0835 CH3 CH3 H H NC(O)C(CH3)3 0 1.0836 CH3 CH3 H F NC(O)C(CH3)3 0 1.0837 CH3 CH3 H Cl NC(O)C(CH3)3 0 1.0838 CH3 CH3 H H NC(O)C(CH3)3 0 1.0839 CH3 CH3 H F NC(O)C(CH3)3 0 1.0840 CH3 CH3 H Cl NC(O)C(CH3)3 0 1.0841 CH3 CH3 H H NC(O)C(CH3)3 0 1.0842 CH3 CH3 H F NC(O)C(CH3)3 0 1.0843 CH3 CH3 H Cl NC(O)C(CH3)3 0 1.0844 CH3 CH3 H H NC(O)C(CH3)3 0 1.0845 CH3 CH3 H F NC(O)C(CH3)3 0 1.0846 CH3 CH3 H Cl NC(O)C(CH3)3 0 1.0847 CH3 CH3 H H NC(O)C(CH3)3 0 1.0848 CH3 CH3 CH2OCH2CH2OCH3 H F NC(O)C(CH3)3 1 1.0849 CH3 CH3 CH2OCH2CH2OCH3 H H NC(O)C(CH3)3 1 1.0850 CH3 CH3 CH2OCH2CH2OCH2CH3 H F NC(O)C(CH3)3 1 1.0851 CH3 CH3 CH2OCH2CH2OCH2CH3 H H NC(O)C(CH3)3 1 1.0852 H CH3 CH2OCH2CH2OCH3 H F NC(O)C(CH3)3 0 1.0853 H CH3 CH2OCH2CH2OCH3 H Cl NC(O)C(CH3)3 0 1.0854 H CH3 CH2OCH2CH2OCH3 H H NC(O)C(CH3)3 0 1.0855 H CH3 CH2OCH2CH2OCH2CH3 H F NC(O)C(CH3)3 0 1.0856 H CH3 CH2OCH2CH2OCH2CH3 H Cl NC(O)C(CH3)3 0 1.0857 H CH3 CH2OCH2CH2OCH2CH3 H H NC(O)C(CH3)3 0 1.0858 H CH3 CH2N(CH3)SO2CH3 H F NC(O)C(CH3)3 0 1.0859 H CH3 CH2N(CH3)SO2CH3 H Cl NC(O)C(CH3)3 0 1.0860 H CH3 CH2N(CH3)SO2CH3 H H NC(O)C(CH3)3 0 1.0861 H CH3 CH2OCH2Ph H F NC(O)C(CH3)3 0 1.0862 H CH3 CH2OCH2Ph H Cl NC(O)C(CH3)3 0 1.0863 H CH3 CH2OCH2Ph H H NC(O)C(CH3)3 0 1.0864 H CH3 CH2OCH2CH2OH H F NC(O)C(CH3)3 0 1.0865 H CH3 CH2OCH2CH2OH H Cl NC(O)C(CH3)3 0 1.0866 H CH3 CH2OCH2CH2OH H H NC(O)C(CH3)3 0 1.0867 H CH3 CH2OCH2CH2Cl H F NC(O)C(CH3)3 0 1.0868 H CH3 CH2OCH2CH2Cl H Cl NC(O)C(CH3)3 0 1.0869 H CH3 CH2OCH2CH2Cl H H NC(O)C(CH3)3 0 1.0870 H CH3 CH2OCH2CF3 H F NC(O)C(CH3)3 0 1.0871 H CH3 CH2OCH2CF3 H Cl NC(O)C(CH3)3 0 1.0872 H CH3 CH2OCH2CF3 H H NC(O)C(CH3)3 0 1.0873 H CH3 CH2OCH2CH═CH2 H F NC(O)C(CH3)3 0 1.0874 H CH3 CH2OCH2CH═CH2 H Cl NC(O)C(CH3)3 0 1.0875 H CH3 CH2OCH2CH═CH2 H H NC(O)C(CH3)3 0 1.0876 H CH3 CH2O(CO)CH3 H F NC(O)C(CH3)3 0 1.0877 H CH3 CH2O(CO)CH3 H Cl NC(O)C(CH3)3 0 1.0878 H CH3 CH2O(CO)CH3 H H NC(O)C(CH3)3 0 1.0879 H CH3 CH2OCH2C≡CH H F NC(O)C(CH3)3 0 1.0880 H CH3 CH2OCH2C≡CH H Cl NC(O)C(CH3)3 0 1.0881 H CH3 CH2OCH2C≡CH H H NC(O)C(CH3)3 0 1.0882 H CH3 CH2OCH2C≡CCH3 H F NC(O)C(CH3)3 0 1.0883 H CH3 CH2OCH2C≡CCH3 H Cl NC(O)C(CH3)3 0 1.0884 H CH3 CH2OCH2C≡CCH3 H H NC(O)C(CH3)3 0 1.0885 H CH3 H F NC(O)C(CH3)3 0 1.0886 H CH3 H Cl NC(O)C(CH3)3 0 1.0887 H CH3 H H NC(O)C(CH3)3 0 1.0888 H CH3 H F NC(O)C(CH3)3 0 1.0889 H CH3 H Cl NC(O)C(CH3)3 0 1.0890 H CH3 H H NC(O)C(CH3)3 0 1.0891 H CH3 H F NC(O)C(CH3)3 0 1.0892 H CH3 H Cl NC(O)C(CH3)3 0 1.0893 H CH3 H H NC(O)C(CH3)3 0 1.0894 H CH3 H F NC(O)C(CH3)3 0 1.0895 H CH3 H Cl NC(O)C(CH3)3 0 1.0896 H CH3 H H NC(O)C(CH3)3 0 1.0897 H CH3 H F NC(O)C(CH3)3 0 1.0898 H CH3 H Cl NC(O)C(CH3)3 0 1.0899 H CH3 H H NC(O)C(CH3)3 0 1.0900 H CH3 H F NC(O)C(CH3)3 0 1.0901 H CH3 H Cl NC(O)C(CH3)3 0 1.0902 H CH3 H H NC(O)C(CH3)3 0 1.0903 H CH3 CH2OCH2CH2OCH3 H F NC(O)C(CH3)3 1 1.0904 H CH3 CH2OCH2CH2OCH3 H H NC(O)C(CH3)3 1 1.0905 H CH3 CH2OCH2CH2OCH2CH3 H F NC(O)C(CH3)3 1 1.0906 H CH3 CH2OCH2CH2OCH2CH3 H H NC(O)C(CH3)3 1 1.0907 H H CH3 H F NSO2N(CH3)2 0 1.0908 H H CH3 H Cl NSO2N(CH3)2 0 1.0909 H H CH3 H H NSO2N(CH3)2 0 1.0910 H H CH3 CH3 F NSO2N(CH3)2 0 1.0911 H H CH3 CH3 Cl NSO2N(CH3)2 0 1.0912 H H CH3 CH3 H NSO2N(CH3)2 0 1.0913 H H CH2CH3 H F NSO2N(CH3)2 0 1.0914 H H CH2CH3 H Cl NSO2N(CH3)2 0 1.0915 H H CH2CH3 H H NSO2N(CH3)2 0 1.0916 H H CH2CH2CH3 H F NSO2N(CH3)2 0 1.0917 H H CH2CH2CH3 H Cl NSO2N(CH3)2 0 1.0918 H H CH2CH2CH3 H H NSO2N(CH3)2 0 1.0919 H H CH2OCH3 H F NSO2N(CH3)2 0 1.0920 H H CH2OCH3 H Cl NSO2N(CH3)2 0 1.0921 H H CH2OCH3 H H NSO2N(CH3)2 0 1.0922 H H CH2OCH2CH3 H F NSO2N(CH3)2 0 1.0923 H H CH2OCH2CH3 H Cl NSO2N(CH3)2 0 1.0924 H H CH2OCH2CH3 H H NSO2N(CH3)2 0 1.0925 H H CH2OCH2CH2OCH3 H F NSO2N(CH3)2 0 1.0926 H H CH2OCH2CH2OCH3 H Cl NSO2N(CH3)2 0 1.0927 H H CH2OCH2CH2OCH3 H H NSO2N(CH3)2 0 1.0928 H H CH2OCH2CH2OCH2CH3 H F NSO2N(CH3)2 0 1.0929 H H CH2OCH2CH2OCH2CH3 H Cl NSO2N(CH3)2 0 1.0930 H H CH2OCH2CH2OCH2CH3 H H NSO2N(CH3)2 0 1.0931 H H CH2CH2OCH3 H F NSO2N(CH3)2 0 1.0932 H H CH2CH2OCH3 H Cl NSO2N(CH3)2 0 1.0933 H H CH2CH2OCH3 H H NSO2N(CH3)2 0 1.0934 H H CH2OCH2C≡CH H F NSO2N(CH3)2 0 1.0935 H H CH2OCH2C≡CH H Cl NSO2N(CH3)2 0 1.0936 H H CH2OCH2C≡CH H H NSO2N(CH3)2 0 1.0937 H H CH2OCH2C≡CCH3 H F NSO2N(CH3)2 0 1.0938 H H CH2OCH2C≡CCH3 H Cl NSO2N(CH3)2 0 1.0939 H H CH2OCH2C≡CCH3 H H NSO2N(CH3)2 0 1.0940 H H CH2CH2CH2OCH3 H F NSO2N(CH3)2 0 1.0941 H H CH2CH2CH2OCH3 H Cl NSO2N(CH3)2 0 1.0942 H H CH2CH2CH2OCH3 H H NSO2N(CH3)2 0 1.0943 H H CH2OCH2OCH3 H F NSO2N(CH3)2 0 1.0944 H H CH2OCH2OCH3 H Cl NSO2N(CH3)2 0 1.0945 H H CH2OCH2OCH3 H H NSO2N(CH3)2 0 1.0946 H H CH2N(CH3)SO2CH3 H F NSO2N(CH3)2 0 1.0947 H H CH2N(CH3)SO2CH3 H Cl NSO2N(CH3)2 0 1.0948 H H CH2N(CH3)SO2CH3 H H NSO2N(CH3)2 0 1.0949 H H CF3 H F NSO2N(CH3)2 0 1.0950 H H CF3 H Cl NSO2N(CH3)2 0 1.0951 H H CF3 H H NSO2N(CH3)2 0 1.0952 H H CH2OCH2CF3 H F NSO2N(CH3)2 0 1.0953 H H CH2OCH2CF3 H Cl NSO2N(CH3)2 0 1.0954 H H CH2OCH2CF3 H H NSO2N(CH3)2 0 1.0955 H H CH2OCH2Ph H F NSO2N(CH3)2 0 1.0956 H H CH2OCH2Ph H Cl NSO2N(CH3)2 0 1.0957 H H CH2OCH2Ph H H NSO2N(CH3)2 0 1.0958 H H CH2OCH2CH═CH2 H F NSO2N(CH3)2 0 1.0959 H H CH2OCH2CH═CH2 H Cl NSO2N(CH3)2 0 1.0960 H H CH2OCH2CH═CH2 H H NSO2N(CH3)2 0 1.0961 H H H F NSO2N(CH3)2 0 1.0962 H H H Cl NSO2N(CH3)2 0 1.0963 H H H H NSO2N(CH3)2 0 1.0964 H H H F NSO2N(CH3)2 0 1.0965 H H H Cl NSO2N(CH3)2 0 1.0966 H H H H NSO2N(CH3)2 0 1.0967 H H H F NSO2N(CH3)2 0 1.0968 H H H Cl NSO2N(CH3)2 0 1.0969 H H H H NSO2N(CH3)2 0 1.0970 H H H F NSO2N(CH3)2 0 1.0971 H H H Cl NSO2N(CH3)2 0 1.0972 H H H H NSO2N(CH3)2 0 1.0973 H H H F NSO2N(CH3)2 0 1.0974 H H H Cl NSO2N(CH3)2 0 1.0975 H H H H NSO2N(CH3)2 0 1.0976 H H H F NSO2N(CH3)2 0 1.0977 H H H Cl NSO2N(CH3)2 0 1.0978 H H H H NSO2N(CH3)2 0 1.0979 H H CH3 H F NSO2N(CH3)2 1 1.0980 H H CH2OCH3 H F NSO2N(CH3)2 1 1.0981 H H CH2OCH2CH2OCH3 H F NSO2N(CH3)2 1 1.0982 H H CH2CH2CH2OCH3 H F NSO2N(CH3)2 1 1.0983 H H CH2CH3 H F NSO2N(CH3)2 1 1.0984 H H CH3 H H NSO2N(CH3)2 1 1.0985 H H CH2OCH3 H H NSO2N(CH3)2 1 1.0986 H H CH2OCH2CH2OCH3 H H NSO2N(CH3)2 1 1.0987 H H CH2CH2CH2OCH3 H H NSO2N(CH3)2 1 1.0988 H H CH2CH3 H H NSO2N(CH3)2 1 1.0989 CH3 CH3 CH3 H F NSO2N(CH3)2 0 1.0990 CH3 CH3 CH3 H Cl NSO2N(CH3)2 0 1.0991 CH3 CH3 CH3 H H NSO2N(CH3)2 0 1.0992 CH3 CH3 CH3 CH3 F NSO2N(CH3)2 0 1.0993 CH3 CH3 CH3 CH3 Cl NSO2N(CH3)2 0 1.0994 CH3 CH3 CH3 CH3 H NSO2N(CH3)2 0 1.0995 CH3 CH3 CH2CH3 H F NSO2N(CH3)2 0 1.0996 CH3 CH3 CH2CH3 H Cl NSO2N(CH3)2 0 1.0997 CH3 CH3 CH2CH3 H H NSO2N(CH3)2 0 1.0998 CH3 CH3 CH2CH2CH3 H F NSO2N(CH3)2 0 1.0999 CH3 CH3 CH2CH2CH3 H Cl NSO2N(CH3)2 0 1.1000 CH3 CH3 CH2CH2CH3 H H NSO2N(CH3)2 0 1.1001 CH3 CH3 CH2OCH3 H F NSO2N(CH3)2 0 1.1002 CH3 CH3 CH2OCH3 H Cl NSO2N(CH3)2 0 1.1003 CH3 CH3 CH2OCH3 H H NSO2N(CH3)2 0 1.1004 CH3 CH3 CH2OCH2CH3 H F NSO2N(CH3)2 0 1.1005 CH3 CH3 CH2OCH2CH3 H Cl NSO2N(CH3)2 0 1.1006 CH3 CH3 CH2OCH2CH3 H H NSO2N(CH3)2 0 1.1007 CH3 CH3 CH2OCH2CH2OCH3 H F NSO2N(CH3)2 0 1.1008 CH3 CH3 CH2OCH2CH2OCH3 H Cl NSO2N(CH3)2 0 1.1009 CH3 CH3 CH2OCH2CH2OCH3 H H NSO2N(CH3)2 0 1.1010 CH3 CH3 CH2OCH2CH2OCH2CH3 H F NSO2N(CH3)2 0 1.1011 CH3 CH3 CH2OCH2CH2OCH2CH3 H Cl NSO2N(CH3)2 0 1.1012 CH3 CH3 CH2OCH2CH2OCH2CH3 H H NSO2N(CH3)2 0 1.1013 CH3 CH3 CH2CH2OCH3 H F NSO2N(CH3)2 0 1.1014 CH3 CH3 CH2CH2OCH3 H Cl NSO2N(CH3)2 0 1.1015 CH3 CH3 CH2CH2OCH3 H H NSO2N(CH3)2 0 1.1016 CH3 CH3 CH2OCH2C≡CH H F NSO2N(CH3)2 0 1.1017 CH3 CH3 CH2OCH2C≡CH H Cl NSO2N(CH3)2 0 1.1018 CH3 CH3 CH2OCH2C≡CH H H NSO2N(CH3)2 0 1.1019 CH3 CH3 CH2OCH2C≡CCH3 H F NSO2N(CH3)2 0 1.1020 CH3 CH3 CH2OCH2C≡CCH3 H Cl NSO2N(CH3)2 0 1.1021 CH3 CH3 CH2OCH2C≡CCH3 H H NSO2N(CH3)2 0 1.1022 CH3 CH3 CH2CH2CH2OCH3 H F NSO2N(CH3)2 0 1.1023 CH3 CH3 CH2CH2CH2OCH3 H Cl NSO2N(CH3)2 0 1.1024 CH3 CH3 CH2CH2CH2OCH3 H H NSO2N(CH3)2 0 1.1025 CH3 CH3 CH2OCH2OCH3 H F NSO2N(CH3)2 0 1.1026 CH3 CH3 CH2OCH2OCH3 H Cl NSO2N(CH3)2 0 1.1027 CH3 CH3 CH2OCH2OCH3 H H NSO2N(CH3)2 0 1.1028 CH3 CH3 CH2N(CH3)SO2CH3 H F NSO2N(CH3)2 0 1.1029 CH3 CH3 CH2N(CH3)SO2CH3 H Cl NSO2N(CH3)2 0 1.1030 CH3 CH3 CH2N(CH3)SO2CH3 H H NSO2N(CH3)2 0 1.1031 CH3 CH3 CF3 H F NSO2N(CH3)2 0 1.1032 CH3 CH3 CF3 H Cl NSO2N(CH3)2 0 1.1033 CH3 CH3 CF3 H H NSO2N(CH3)2 0 1.1034 CH3 CH3 CH2OCH2CF3 H F NSO2N(CH3)2 0 1.1035 CH3 CH3 CH2OCH2CF3 H Cl NSO2N(CH3)2 0 1.1036 CH3 CH3 CH2OCH2CF3 H H NSO2N(CH3)2 0 1.1037 CH3 CH3 CH2OCH2Ph H F NSO2N(CH3)2 0 1.1038 CH3 CH3 CH2OCH2Ph H Cl NSO2N(CH3)2 0 1.1039 CH3 CH3 CH2OCH2Ph H H NSO2N(CH3)2 0 1.1040 CH3 CH3 CH2OCH2CH═CH2 H F NSO2N(CH3)2 0 1.1041 CH3 CH3 CH2OCH2CH═CH2 H Cl NSO2N(CH3)2 0 1.1042 CH3 CH3 CH2OCH2CH═CH2 H H NSO2N(CH3)2 0 1.1043 CH3 CH3 H F NSO2N(CH3)2 0 1.1044 CH3 CH3 H Cl NSO2N(CH3)2 0 1.1045 CH3 CH3 H H NSO2N(CH3)2 0 1.1046 CH3 CH3 H F NSO2N(CH3)2 0 1.1047 CH3 CH3 H Cl NSO2N(CH3)2 0 1.1048 CH3 CH3 H H NSO2N(CH3)2 0 1.1049 CH3 CH3 H F NSO2N(CH3)2 0 1.1050 CH3 CH3 H Cl NSO2N(CH3)2 0 1.1051 CH3 CH3 H H NSO2N(CH3)2 0 1.1052 CH3 CH3 H F NSO2N(CH3)2 0 1.1053 CH3 CH3 H Cl NSO2N(CH3)2 0 1.1054 CH3 CH3 H H NSO2N(CH3)2 0 1.1055 CH3 CH3 H F NSO2N(CH3)2 0 1.1056 CH3 CH3 H Cl NSO2N(CH3)2 0 1.1057 CH3 CH3 H H NSO2N(CH3)2 0 1.1058 CH3 CH3 H F NSO2N(CH3)2 0 1.1059 CH3 CH3 H Cl NSO2N(CH3)2 0 1.1060 CH3 CH3 H H NSO2N(CH3)2 0 1.1061 CH3 CH3 CH3 H F NSO2N(CH3)2 1 1.1062 CH3 CH3 CH2OCH3 H F NSO2N(CH3)2 1 1.1063 CH3 CH3 CH2OCH2CH2OCH3 H F NSO2N(CH3)2 1 1.1064 CH3 CH3 CH2CH2CH2OCH3 H F NSO2N(CH3)2 1 1.1065 CH3 CH3 CH2CH3 H F NSO2N(CH3)2 1 1.1066 CH3 CH3 CH3 H H NSO2N(CH3)2 1 1.1067 CH3 CH3 CH2OCH3 H H NSO2N(CH3)2 1 1.1068 CH3 CH3 CH2OCH2CH2OCH3 H H NSO2N(CH3)2 1 1.1069 CH3 CH3 CH2CH2CH2OCH3 H H NSO2N(CH3)2 1 1.1070 CH3 CH3 CH2CH3 H H NSO2N(CH3)2 1 1.1071 H CH3 CH3 H F NSO2N(CH3)2 0 1.1072 H CH3 CH3 H Cl NSO2N(CH3)2 0 1.1073 H CH3 CH3 H H NSO2N(CH3)2 0 1.1074 H CH3 CH3 CH3 F NSO2N(CH3)2 0 1.1075 H CH3 CH3 CH3 Cl NSO2N(CH3)2 0 1.1076 H CH3 CH3 CH3 H NSO2N(CH3)2 0 1.1077 H CH3 CH2CH3 H F NSO2N(CH3)2 0 1.1078 H CH3 CH2CH3 H Cl NSO2N(CH3)2 0 1.1079 H CH3 CH2CH3 H H NSO2N(CH3)2 0 1.1080 H CH3 CH2CH2CH3 H F NSO2N(CH3)2 0 1.1081 H CH3 CH2CH2CH3 H Cl NSO2N(CH3)2 0 1.1082 H CH3 CH2CH2CH3 H H NSO2N(CH3)2 0 1.1083 H CH3 CH2OCH3 H F NSO2N(CH3)2 0 1.1084 H CH3 CH2OCH3 H Cl NSO2N(CH3)2 0 1.1085 H CH3 CH2OCH3 H H NSO2N(CH3)2 0 1.1086 H CH3 CH2OCH2CH3 H F NSO2N(CH3)2 0 1.1087 H CH3 CH2OCH2CH3 H Cl NSO2N(CH3)2 0 1.1088 H CH3 CH2OCH2CH3 H H NSO2N(CH3)2 0 1.1089 H CH3 CH2OCH2CH2OCH3 H F NSO2N(CH3)2 0 1.1090 H CH3 CH2OCH2CH2OCH3 H Cl NSO2N(CH3)2 0 1.1091 H CH3 CH2OCH2CH2OCH3 H H NSO2N(CH3)2 0 1.1092 H CH3 CH2OCH2CH2OCH2CH3 H F NSO2N(CH3)2 0 1.1093 H CH3 CH2OCH2CH2OCH2CH3 H Cl NSO2N(CH3)2 0 1.1094 H CH3 CH2OCH2CH2OCH2CH3 H H NSO2N(CH3)2 0 1.1095 H CH3 CH2CH2OCH3 H F NSO2N(CH3)2 0 1.1096 H CH3 CH2CH2OCH3 H Cl NSO2N(CH3)2 0 1.1097 H CH3 CH2CH2OCH3 H H NSO2N(CH3)2 0 1.1098 H CH3 CH2OCH2C≡CH H F NSO2N(CH3)2 0 1.1099 H CH3 CH2OCH2C≡CH H Cl NSO2N(CH3)2 0 1.1100 H CH3 CH2OCH2C≡CH H H NSO2N(CH3)2 0 1.1101 H CH3 CH2OCH2C≡CCH3 H F NSO2N(CH3)2 0 1.1102 H CH3 CH2OCH2C≡CCH3 H Cl NSO2N(CH3)2 0 1.1103 H CH3 CH2OCH2C≡CCH3 H H NSO2N(CH3)2 0 1.1104 H CH3 CH2CH2CH2OCH3 H F NSO2N(CH3)2 0 1.1105 H CH3 CH2CH2CH2OCH3 H Cl NSO2N(CH3)2 0 1.1106 H CH3 CH2CH2CH2OCH3 H H NSO2N(CH3)2 0 1.1107 H CH3 CH2OCH2OCH3 H F NSO2N(CH3)2 0 1.1108 H CH3 CH2OCH2OCH3 H Cl NSO2N(CH3)2 0 1.1109 H CH3 CH2OCH2OCH3 H H NSO2N(CH3)2 0 1.1110 H CH3 CH2N(CH3)SO2CH3 H F NSO2N(CH3)2 0 1.1111 H CH3 CH2N(CH3)SO2CH3 H Cl NSO2N(CH3)2 0 1.1112 H CH3 CH2N(CH3)SO2CH3 H H NSO2N(CH3)2 0 1.1113 H CH3 CF3 H F NSO2N(CH3)2 0 1.1114 H CH3 CF3 H Cl NSO2N(CH3)2 0 1.1115 H CH3 CF3 H H NSO2N(CH3)2 0 1.1116 H CH3 CH2OCH2CF3 H F NSO2N(CH3)2 0 1.1117 H CH3 CH2OCH2CF3 H Cl NSO2N(CH3)2 0 1.1118 H CH3 CH2OCH2CF3 H H NSO2N(CH3)2 0 1.1119 H CH3 CH2OCH2Ph H F NSO2N(CH3)2 0 1.1120 H CH3 CH2OCH2Ph H Cl NSO2N(CH3)2 0 1.1121 H CH3 CH2OCH2Ph H H NSO2N(CH3)2 0 1.1122 H CH3 CH2OCH2CH═CH2 H F NSO2N(CH3)2 0 1.1123 H CH3 CH2OCH2CH═CH2 H Cl NSO2N(CH3)2 0 1.1124 H CH3 CH2OCH2CH═CH2 H H NSO2N(CH3)2 0 1.1125 H CH3 H F NSO2N(CH3)2 0 1.1126 H CH3 H Cl NSO2N(CH3)2 0 1.1127 H CH3 H H NSO2N(CH3)2 0 1.1128 H CH3 H F NSO2N(CH3)2 0 1.1129 H CH3 H Cl NSO2N(CH3)2 0 1.1130 H CH3 H H NSO2N(CH3)2 0 1.1131 H CH3 H F NSO2N(CH3)2 0 1.1132 H CH3 H Cl NSO2N(CH3)2 0 1.1133 H CH3 H H NSO2N(CH3)2 0 1.1134 H CH3 H F NSO2N(CH3)2 0 1.1135 H CH3 H Cl NSO2N(CH3)2 0 1.1136 H CH3 H H NSO2N(CH3)2 0 1.1137 H CH3 H F NSO2N(CH3)2 0 1.1138 H CH3 H Cl NSO2N(CH3)2 0 1.1139 H CH3 H H NSO2N(CH3)2 0 1.1140 H CH3 H F NSO2N(CH3)2 0 1.1141 H CH3 H Cl NSO2N(CH3)2 0 1.1142 H CH3 H H NSO2N(CH3)2 0 1.1143 H CH3 CH3 H F NSO2N(CH3)2 1 1.1144 H CH3 CH2OCH3 H F NSO2N(CH3)2 1 1.1145 H CH3 CH2OCH2CH2OCH3 H F NSO2N(CH3)2 1 1.1146 H CH3 CH2CH2CH2OCH3 H F NSO2N(CH3)2 1 1.1147 H CH3 CH2CH3 H F NSO2N(CH3)2 1 1.1148 H CH3 CH3 H H NSO2N(CH3)2 1 1.1149 H CH3 CH2OCH3 H H NSO2N(CH3)2 1 1.1150 H CH3 CH2OCH2CH2OCH3 H H NSO2N(CH3)2 1 1.1151 H CH3 CH2CH2CH2OCH3 H H NSO2N(CH3)2 1 1.1152 H CH3 CH2CH3 H H NSO2N(CH3)2 1 1.1153 H H CH3 H F 0 1H NMR (300 MHz; CDCl3) δ 16.58 (s, 1H); 7.55 (m, 2H); 6.48 (m, 1H); 6.40 (m, 1H); 2.94 (m, 1H): 2.72 (m, 1H); 2.50 (s, 3H); 0.90-0.65 (m, 4H). 1.1154 H H CH3 H F C(═C(CH3)2) 0 1H NMR (300 MHz; CDCl3) δ 16.25 (s, 1H); 7.56 (m, 2H); 6.52 (m, 1H); 6.45 (m, 1H); 4.20 (m, 1H); 3.98 (m, 1H); 2.45 (s, 3H); 1.80 (s, 3H); 1.71 (s, 3H). 1.1155 H H CH3 H H CH2CH(COOCH3) 0 R7 = Br; 1H NMR (300 MHz; CDCl3) i.a. δ 7.44 (d, 2H); 6.54 (t, 1H), 6.53 + 6.42 (2d, 1H); 3.71 + 3.58 (2s, 3H); 2.41 + 2.40 (2s, 3H); tautomeric mixture. 1.1156 H H CH3 H H CH2CH(COOCH3) 0 R7 = H; NEt3 salt (Example P14) TABLE 2 Compounds of formula Ic: (Ic) No. R1 R2 Z1 R30 X Y Physical data 2.0000 H H CH2OCH2CH2OCH3 H F CH2 2.0001 H H CH2OCH2CH2OCH3 H Cl CH2 2.0002 H H CH2OCH2CH2OCH3 H H CH2 2.0003 H H CH2OCH2CH2OCH2CH3 H F CH2 2.0004 H H CH2OCH2CH2OCH2CH3 H Cl CH2 2.0005 H H CH2OCH2CH2OCH2CH3 H H CH2 2.0006 H H CH2N(CH3)SO2CH3 H F CH2 2.0007 H H CH2N(CH3)SO2CH3 H Cl CH2 2.0008 H H CH2N(CH3)SO2CH3 H H CH2 2.0009 H H CH2OCH2Ph H F CH2 2.0010 H H CH2OCH2Ph H Cl CH2 2.0011 H H CH2OCH2Ph H H CH2 2.0012 H H CH2OCH2CH2OH H F CH2 2.0013 H H CH2OCH2CH2OH H Cl CH2 2.0014 H H CH2OCH2CH2OH H H CH2 2.0015 H H CH2OCH2CH2Cl H F CH2 2.0016 H H CH2OCH2CH2Cl H Cl CH2 2.0017 H H CH2OCH2CH2Cl H H CH2 2.0018 H H CH2OCH2CF3 H F CH2 2.0019 H H CH2OCH2CF3 H Cl CH2 2.0020 H H CH2OCH2CF3 H H CH2 2.0021 H H CH2OCH2CH═CH2 H F CH2 2.0022 H H CH2OCH2CH═CH2 H Cl CH2 2.0023 H H CH2OCH2CH═CH2 H H CH2 2.0024 H H CH2O(CO)CH3 H F CH2 2.0025 H H CH2O(CO)CH3 H Cl CH2 2.0026 H H CH2O(CO)CH3 H H CH2 2.0027 H H CH2OCH2C≡CH H F CH2 2.0028 H H CH2OCH2C≡CH H Cl CH2 2.0029 H H CH2OCH2C≡CH H H CH2 2.0030 H H CH2OCH2C≡CCH3 H F CH2 2.0031 H H CH2OCH2C≡CCH3 H Cl CH2 2.0032 H H CH2OCH2C≡CCH3 H H CH2 2.0033 H H H F CH2 2.0034 H H H Cl CH2 2.0035 H H H H CH2 2.0036 H H H F CH2 2.0037 H H H Cl CH2 2.0038 H H H H CH2 2.0039 H H H F CH2 2.0040 H H H Cl CH2 2.0041 H H H H CH2 2.0042 H H H F CH2 2.0043 H H H Cl CH2 2.0044 H H H H CH2 2.0045 H H H F CH2 2.0046 H H H Cl CH2 2.0047 H H H H CH2 2.0048 H H H F CH2 2.0049 H H H Cl CH2 2.0050 H H H H CH2 2.0051 CH3 CH3 CH2OCH2CH2OCH3 H F CH2 2.0052 CH3 CH3 CH2OCH2CH2OCH3 H Cl CH2 2.0053 CH3 CH3 CH2OCH2CH2OCH3 H H CH2 2.0054 CH3 CH3 CH2OCH2CH2OCH2CH3 H F CH2 2.0055 CH3 CH3 CH2OCH2CH2OCH2CH3 H Cl CH2 2.0056 CH3 CH3 CH2OCH2CH2OCH2CH3 H H CH2 2.0057 CH3 CH3 CH2N(CH3)SO2CH3 H F CH2 2.0058 CH3 CH3 CH2N(CH3)SO2CH3 H Cl CH2 2.0059 CH3 CH3 CH2N(CH3)SO2CH3 H H CH2 2.0060 CH3 CH3 CH2OCH2Ph H F CH2 2.0061 CH3 CH3 CH2OCH2Ph H Cl CH2 2.0062 CH3 CH3 CH2OCH2Ph H H CH2 2.0063 CH3 CH3 CH2OCH2CH2OH H F CH2 2.0064 CH3 CH3 CH2OCH2CH2OH H Cl CH2 2.0065 CH3 CH3 CH2OCH2CH2OH H H CH2 2.0066 CH3 CH3 CH2OCH2CH2Cl H F CH2 2.0067 CH3 CH3 CH2OCH2CH2Cl H Cl CH2 2.0068 CH3 CH3 CH2OCH2CH2Cl H H CH2 2.0069 CH3 CH3 CH2OCH2CF3 H F CH2 2.0070 CH3 CH3 CH2OCH2CF3 H Cl CH2 2.0071 CH3 CH3 CH2OCH2CF3 H H CH2 2.0072 CH3 CH3 CH2OCH2CH═CH2 H F CH2 2.0073 CH3 CH3 CH2OCH2CH═CH2 H Cl CH2 2.0074 CH3 CH3 CH2OCH2CH═CH2 H H CH2 2.0075 CH3 CH3 CH2O(CO)CH3 H F CH2 2.0076 CH3 CH3 CH2O(CO)CH3 H Cl CH2 2.0077 CH3 CH3 CH2O(CO)CH3 H H CH2 2.0078 CH3 CH3 CH2OCH2C≡CH H F CH2 2.0079 CH3 CH3 CH2OCH2C≡CH H Cl CH2 2.0080 CH3 CH3 CH2OCH2C≡CH H H CH2 2.0081 CH3 CH3 CH2OCH2C≡CCH3 H F CH2 2.0082 CH3 CH3 CH2OCH2C≡CCH3 H Cl CH2 2.0083 CH3 CH3 CH2OCH2C≡CCH3 H H CH2 2.0084 CH3 CH3 H F CH2 2.0085 CH3 CH3 H Cl CH2 2.0086 CH3 CH3 H H CH2 2.0087 CH3 CH3 H F CH2 2.0088 CH3 CH3 H Cl CH2 2.0089 CH3 CH3 H H CH2 2.0090 CH3 CH3 H F CH2 2.0091 CH3 CH3 H Cl CH2 2.0092 CH3 CH3 H H CH2 2.0093 CH3 CH3 H F CH2 2.0094 CH3 CH3 H Cl CH2 2.0095 CH3 CH3 H H CH2 2.0096 CH3 CH3 H F CH2 2.0097 CH3 CH3 H Cl CH2 2.0098 CH3 CH3 H H CH2 2.0099 CH3 CH3 H F CH2 2.0100 CH3 CH3 H Cl CH2 2.0101 CH3 CH3 H H CH2 2.0102 H CH3 CH2OCH2CH2OCH3 H F CH2 2.0103 H CH3 CH2OCH2CH2OCH3 H Cl CH2 2.0104 H CH3 CH2OCH2CH2OCH3 H H CH2 2.0105 H CH3 CH2OCH2CH2OCH2CH3 H F CH2 2.0106 H CH3 CH2OCH2CH2OCH2CH3 H Cl CH2 2.0107 H CH3 CH2OCH2CH2OCH2CH3 H H CH2 2.0108 H CH3 CH2N(CH3)SO2CH3 H F CH2 2.0109 H CH3 CH2N(CH3)SO2CH3 H Cl CH2 2.0110 H CH3 CH2N(CH3)SO2CH3 H H CH2 2.0111 H CH3 CH2OCH2Ph H F CH2 2.0112 H CH3 CH2OCH2Ph H Cl CH2 2.0113 H CH3 CH2OCH2Ph H H CH2 2.0114 H CH3 CH2OCH2CH2OH H F CH2 2.0115 H CH3 CH2OCH2CH2OH H Cl CH2 2.0116 H CH3 CH2OCH2CH2OH H H CH2 2.0117 H CH3 CH2OCH2CH2Cl H F CH2 2.0118 H CH3 CH2OCH2CH2Cl H Cl CH2 2.0119 H CH3 CH2OCH2CH2Cl H H CH2 2.0120 H CH3 CH2OCH2CF3 H F CH2 2.0121 H CH3 CH2OCH2CF3 H Cl CH2 2.0122 H CH3 CH2OCH2CF3 H H CH2 2.0123 H CH3 CH2OCH2CH═CH2 H F CH2 2.0124 H CH3 CH2OCH2CH═CH2 H Cl CH2 2.0125 H CH3 CH2OCH2CH═CH2 H H CH2 2.0126 H CH3 CH2O(CO)CH3 H F CH2 2.0127 H CH3 CH2O(CO)CH3 H Cl CH2 2.0128 H CH3 CH2O(CO)CH3 H H CH2 2.0129 H CH3 CH2OCH2C≡CH H F CH2 2.0130 H CH3 CH2OCH2C≡CH H Cl CH2 2.0131 H CH3 CH2OCH2C≡CH H H CH2 2.0132 H CH3 CH2OCH2C≡CCH3 H F CH2 2.0133 H CH3 CH2OCH2C≡CCH3 H Cl CH2 2.0134 H CH3 CH2OCH2C≡CCH3 H H CH2 2.0135 H CH3 H F CH2 2.0136 H CH3 H Cl CH2 2.0137 H CH3 H H CH2 2.0138 H CH3 H F CH2 2.0139 H CH3 H Cl CH2 2.0140 H CH3 H H CH2 2.0141 H CH3 H F CH2 2.0142 H CH3 H Cl CH2 2.0143 H CH3 H H CH2 2.0144 H CH3 H F CH2 2.0145 H CH3 H Cl CH2 2.0146 H CH3 H H CH2 2.0147 H CH3 H F CH2 2.0148 H CH3 H Cl CH2 2.0149 H CH3 H H CH2 2.0150 H CH3 H F CH2 2.0151 H CH3 H Cl CH2 2.0152 H CH3 H H CH2 2.0153 H H CH2OCH2CH2OCH3 CH3 F CH2 2.0154 H H CH2OCH2CH2OCH3 CH3 Cl CH2 2.0155 H H CH2OCH2CH2OCH3 CH3 H CH2 2.0156 H H CH2OCH2CH2OCH2CH3 CH3 F CH2 2.0157 H H CH2OCH2CH2OCH2CH3 CH3 Cl CH2 2.0158 H H CH2OCH2CH2OCH2CH3 CH3 H CH2 2.0159 H H CH2N(CH3)SO2CH3 CH3 F CH2 2.0160 H H CH2N(CH3)SO2CH3 CH3 Cl CH2 2.0161 H H CH2N(CH3)SO2CH3 CH3 H CH2 2.0162 H H CH2OCH2Ph CH3 F CH2 2.0163 H H CH2OCH2Ph CH3 Cl CH2 2.0164 H H CH2OCH2Ph CH3 H CH2 2.0165 H H CH2OCH2CH2OH CH3 F CH2 2.0166 H H CH2OCH2CH2OH CH3 Cl CH2 2.0167 H H CH2OCH2CH2OH CH3 H CH2 2.0168 H H CH2OCH2CH2Cl CH3 F CH2 2.0169 H H CH2OCH2CH2Cl CH3 Cl CH2 2.0170 H H CH2OCH2CH2Cl CH3 H CH2 2.0171 H H CH2OCH2CF3 CH3 F CH2 2.0172 H H CH2OCH2CF3 CH3 Cl CH2 2.0173 H H CH2OCH2CF3 CH3 H CH2 2.0174 H H CH2OCH2CH═CH2 CH3 F CH2 2.0175 H H CH2OCH2CH═CH2 CH3 Cl CH2 2.0176 H H CH2OCH2CH═CH2 CH3 H CH2 2.0177 H H CH2O(CO)CH3 CH3 F CH2 2.0178 H H CH2O(CO)CH3 CH3 Cl CH2 2.0179 H H CH2O(CO)CH3 CH3 H CH2 2.0180 H H CH2OCH2C≡CH CH3 F CH2 2.0181 H H CH2OCH2C≡CH CH3 Cl CH2 2.0182 H H CH2OCH2C≡CH CH3 H CH2 2.0183 H H CH2OCH2C≡CCH3 CH3 F CH2 2.0184 H H CH2OCH2C≡CCH3 CH3 Cl CH2 2.0185 H H CH2OCH2C≡CCH3 CH3 H CH2 2.0186 H H CH3 F CH2 2.0187 H H CH3 Cl CH2 2.0188 H H CH3 H CH2 2.0189 H H CH3 F CH2 2.0190 H H CH3 Cl CH2 2.0191 H H CH3 H CH2 2.0192 H H CH3 F CH2 2.0193 H H CH3 Cl CH2 2.0194 H H CH3 H CH2 2.0195 H H CH3 F CH2 2.0196 H H CH3 Cl CH2 2.0197 H H CH3 H CH2 2.0198 H H CH3 F CH2 2.0199 H H CH3 Cl CH2 2.0200 H H CH3 H CH2 2.0201 H H CH3 F CH2 2.0202 H H CH3 Cl CH2 2.0203 H H CH3 H CH2 2.0204 CH3 CH3 CH2OCH2CH2OCH3 CH3 F CH2 2.0205 CH3 CH3 CH2OCH2CH2OCH3 CH3 Cl CH2 2.0206 CH3 CH3 CH2OCH2CH2OCH3 CH3 H CH2 2.0207 CH3 CH3 CH2OCH2CH2OCH2CH3 CH3 F CH2 2.0208 CH3 CH3 CH2OCH2CH2OCH2CH3 CH3 Cl CH2 2.0209 CH3 CH3 CH2OCH2CH2OCH2CH3 CH3 H CH2 2.0210 CH3 CH3 CH2N(CH3)SO2CH3 CH3 F CH2 2.0211 CH3 CH3 CH2N(CH3)SO2CH3 CH3 Cl CH2 2.0212 CH3 CH3 CH2N(CH3)SO2CH3 CH3 H CH2 2.0213 CH3 CH3 CH2OCH2Ph CH3 F CH2 2.0214 CH3 CH3 CH2OCH2Ph CH3 Cl CH2 2.0215 CH3 CH3 CH2OCH2Ph CH3 H CH2 2.0216 CH3 CH3 CH2OCH2CH2OH CH3 F CH2 2.0217 CH3 CH3 CH2OCH2CH2OH CH3 Cl CH2 2.0218 CH3 CH3 CH2OCH2CH2OH CH3 H CH2 2.0219 CH3 CH3 CH2OCH2CH2Cl CH3 F CH2 2.0220 CH3 CH3 CH2OCH2CH2Cl CH3 Cl CH2 2.0221 CH3 CH3 CH2OCH2CH2Cl CH3 H CH2 2.0222 CH3 CH3 CH2OCH2CF3 CH3 F CH2 2.0223 CH3 CH3 CH2OCH2CF3 CH3 Cl CH2 2.0224 CH3 CH3 CH2OCH2CF3 CH3 H CH2 2.0225 CH3 CH3 CH2OCH2CH═CH2 CH3 F CH2 2.0226 CH3 CH3 CH2OCH2CH═CH2 CH3 Cl CH2 2.0227 CH3 CH3 CH2OCH2CH═CH2 CH3 H CH2 2.0228 CH3 CH3 CH2O(CO)CH3 CH3 F CH2 2.0229 CH3 CH3 CH2O(CO)CH3 CH3 Cl CH2 2.0230 CH3 CH3 CH2O(CO)CH3 CH3 H CH2 2.0231 CH3 CH3 CH2OCH2C≡CH CH3 F CH2 2.0232 CH3 CH3 CH2OCH2C≡CH CH3 Cl CH2 2.0233 CH3 CH3 CH2OCH2C≡CH CH3 H CH2 2.0234 CH3 CH3 CH2OCH2C≡CCH3 CH3 F CH2 2.0235 CH3 CH3 CH2OCH2C≡CCH3 CH3 Cl CH2 2.0236 CH3 CH3 CH2OCH2C≡CCH3 CH3 H CH2 2.0237 CH3 CH3 CH3 F CH2 2.0238 CH3 CH3 CH3 Cl CH2 2.0239 CH3 CH3 CH3 H CH2 2.0240 CH3 CH3 CH3 F CH2 2.0241 CH3 CH3 CH3 Cl CH2 2.0242 CH3 CH3 CH3 H CH2 2.0243 CH3 CH3 CH3 F CH2 2.0244 CH3 CH3 CH3 Cl CH2 2.0245 CH3 CH3 CH3 H CH2 2.0246 CH3 CH3 CH3 F CH2 2.0247 CH3 CH3 CH3 Cl CH2 2.0248 CH3 CH3 CH3 H CH2 2.0249 CH3 CH3 CH3 F CH2 2.0250 CH3 CH3 CH3 Cl CH2 2.0251 CH3 CH3 CH3 H CH2 2.0252 CH3 CH3 CH3 F CH2 2.0253 CH3 CH3 CH3 Cl CH2 2.0254 CH3 CH3 CH3 H CH2 2.0255 H CH3 CH2OCH2CH2OCH3 CH3 F CH2 2.0256 H CH3 CH2OCH2CH2OCH3 CH3 Cl CH2 2.0257 H CH3 CH2OCH2CH2OCH3 CH3 H CH2 2.0258 H CH3 CH2OCH2CH2OCH2CH3 CH3 F CH2 2.0259 H CH3 CH2OCH2CH2OCH2CH3 CH3 Cl CH2 2.0260 H CH3 CH2OCH2CH2OCH2CH3 CH3 H CH2 2.0261 H CH3 CH2N(CH3)SO2CH3 CH3 F CH2 2.0262 H CH3 CH2N(CH3)SO2CH3 CH3 Cl CH2 2.0263 H CH3 CH2N(CH3)SO2CH3 CH3 H CH2 2.0264 H CH3 CH2OCH2Ph CH3 F CH2 2.0265 H CH3 CH2OCH2Ph CH3 Cl CH2 2.0266 H CH3 CH2OCH2Ph CH3 H CH2 2.0267 H CH3 CH2OCH2CH2OH CH3 F CH2 2.0268 H CH3 CH2OCH2CH2OH CH3 Cl CH2 2.0269 H CH3 CH2OCH2CH2OH CH3 H CH2 2.0270 H CH3 CH2OCH2CH2Cl CH3 F CH2 2.0271 H CH3 CH2OCH2CH2Cl CH3 Cl CH2 2.0272 H CH3 CH2OCH2CH2Cl CH3 H CH2 2.0273 H CH3 CH2OCH2CF3 CH3 F CH2 2.0274 H CH3 CH2OCH2CF3 CH3 Cl CH2 2.0275 H CH3 CH2OCH2CF3 CH3 H CH2 2.0276 H CH3 CH2OCH2CH═CH2 CH3 F CH2 2.0277 H CH3 CH2OCH2CH═CH2 CH3 Cl CH2 2.0278 H CH3 CH2OCH2CH═CH2 CH3 H CH2 2.0279 H CH3 CH2O(CO)CH3 CH3 F CH2 2.0280 H CH3 CH2O(CO)CH3 CH3 Cl CH2 2.0281 H CH3 CH2O(CO)CH3 CH3 H CH2 2.0282 H CH3 CH2OCH2C≡CH CH3 F CH2 2.0283 H CH3 CH2OCH2C≡CH CH3 Cl CH2 2.0284 H CH3 CH2OCH2C≡CH CH3 H CH2 2.0285 H CH3 CH2OCH2C≡CCH3 CH3 F CH2 2.0286 H CH3 CH2OCH2C≡CCH3 CH3 Cl CH2 2.0287 H CH3 CH2OCH2C≡CCH3 CH3 H CH2 2.0288 H CH3 CH3 F CH2 2.0289 H CH3 CH3 Cl CH2 2.0290 H CH3 CH3 H CH2 2.0291 H CH3 CH3 F CH2 2.0292 H CH3 CH3 Cl CH2 2.0293 H CH3 CH3 H CH2 2.0294 H CH3 CH3 F CH2 2.0295 H CH3 CH3 Cl CH2 2.0296 H CH3 CH3 H CH2 2.0297 H CH3 CH3 F CH2 2.0298 H CH3 CH3 Cl CH2 2.0299 H CH3 CH3 H CH2 2.0300 H CH3 CH3 F CH2 2.0301 H CH3 CH3 Cl CH2 2.0302 H CH3 CH3 H CH2 2.0303 H CH3 CH3 F CH2 2.0304 H CH3 CH3 Cl CH2 2.0305 H CH3 CH3 H CH2 TABLE 3 Compounds of formula Id: (Id) No. R1 R2 Z1 R30 X Y p Phys. data, remarks 3.0000 H H CH2OCH2CH2OCH3 H F CH2 0 3.0001 H H CH2OCH2CH2OCH3 H Cl CH2 0 3.0002 H H CH2OCH2CH2OCH3 H H CH2 0 3.0003 H H CH2OCH2CH2OCH2CH3 H F CH2 0 3.0004 H H CH2OCH2CH2OCH2CH3 H Cl CH2 0 3.0005 H H CH2OCH2CH2OCH2CH3 H H CH2 0 3.0006 H H CH2N(CH3)SO2CH3 H F CH2 0 3.0007 H H CH2N(CH3)SO2CH3 H Cl CH2 0 3.0008 H H CH2N(CH3)SO2CH3 H H CH2 0 3.0009 H H CH2OCH2Ph H F CH2 0 3.0010 H H CH2OCH2Ph H Cl CH2 0 3.0011 H H CH2OCH2Ph H H CH2 0 3.0012 H H CH2OCH2CH2OH H F CH2 0 3.0013 H H CH2OCH2CH2OH H Cl CH2 0 3.0014 H H CH2OCH2CH2OH H H CH2 0 3.0015 H H CH2OCH2CH2Cl H F CH2 0 3.0016 H H CH2OCH2CH2Cl H Cl CH2 0 3.0017 H H CH2OCH2CH2Cl H H CH2 0 3.0018 H H CH2OCH2CF3 H F CH2 0 3.0019 H H CH2OCH2CF3 H Cl CH2 0 3.0020 H H CH2OCH2CF3 H H CH2 0 3.0021 H H CH2OCH2CH═CH2 H F CH2 0 3.0022 H H CH2OCH2CH═CH2 H Cl CH2 0 3.0023 H H CH2OCH2CH═CH2 H H CH2 0 3.0024 H H CH2O(CO)CH3 H F CH2 0 3.0025 H H CH2O(CO)CH3 H Cl CH2 0 3.0026 H H CH2O(CO)CH3 H H CH2 0 3.0027 H H CH2OCH2C≡CH H F CH2 0 3.0028 H H CH2OCH2C≡CH H Cl CH2 0 3.0029 H H CH2OCH2C≡CH H H CH2 0 3.0030 H H CH2OCH2C≡CCH3 H F CH2 0 3.0031 H H CH2OCH2C≡CCH3 H Cl CH2 0 3.0032 H H CH2OCH2C≡CCH3 H H CH2 0 3.0033 H H H F CH2 0 3.0034 H H H Cl CH2 0 3.0035 H H H H CH2 0 3.0036 H H H F CH2 0 3.0037 H H H Cl CH2 0 3.0038 H H H H CH2 0 3.0039 H H H F CH2 0 3.0040 H H H Cl CH2 0 3.0041 H H H H CH2 0 3.0042 H H H F CH2 0 3.0043 H H H Cl CH2 0 3.0044 H H H H CH2 0 3.0045 H H H F CH2 0 3.0046 H H H Cl CH2 0 3.0047 H H H H CH2 0 3.0048 H H H F CH2 0 3.0049 H H H Cl CH2 0 3.0050 H H H H CH2 0 3.0051 CH3 CH3 CH2OCH2CH2OCH3 H F CH2 0 3.0052 CH3 CH3 CH2OCH2CH2OCH3 H Cl CH2 0 3.0053 CH3 CH3 CH2OCH2CH2OCH3 H H CH2 0 3.0054 CH3 CH3 CH2OCH2CH2OCH2CH3 H F CH2 0 3.0055 CH3 CH3 CH2OCH2CH2OCH2CH3 H Cl CH2 0 3.0056 CH3 CH3 CH2OCH2CH2OCH2CH3 H H CH2 0 3.0057 CH3 CH3 CH2N(CH3)SO2CH3 H F CH2 0 3.0058 CH3 CH3 CH2N(CH3)SO2CH3 H Cl CH2 0 3.0059 CH3 CH3 CH2N(CH3)SO2CH3 H H CH2 0 3.0060 CH3 CH3 CH2OCH2Ph H F CH2 0 3.0061 CH3 CH3 CH2OCH2Ph H Cl CH2 0 3.0062 CH3 CH3 CH2OCH2Ph H H CH2 0 3.0063 CH3 CH3 CH2OCH2CH2OH H F CH2 0 3.0064 CH3 CH3 CH2OCH2CH2OH H Cl CH2 0 3.0065 CH3 CH3 CH2OCH2CH2OH H H CH2 0 3.0066 CH3 CH3 CH2OCH2CH2Cl H F CH2 0 3.0067 CH3 CH3 CH2OCH2CH2Cl H Cl CH2 0 3.0068 CH3 CH3 CH2OCH2CH2Cl H H CH2 0 3.0069 CH3 CH3 CH2OCH2CF3 H F CH2 0 3.0070 CH3 CH3 CH2OCH2CF3 H Cl CH2 0 3.0071 CH3 CH3 CH2OCH2CF3 H H CH2 0 3.0072 CH3 CH3 CH2OCH2CH═CH2 H F CH2 0 3.0073 CH3 CH3 CH2OCH2CH═CH2 H Cl CH2 0 3.0074 CH3 CH3 CH2OCH2CH═CH2 H H CH2 0 3.0075 CH3 CH3 CH2O(CO)CH3 H F CH2 0 3.0076 CH3 CH3 CH2O(CO)CH3 H Cl CH2 0 3.0077 CH3 CH3 CH2O(CO)CH3 H H CH2 0 3.0078 CH3 CH3 CH2OCH2C≡CH H F CH2 0 3.0079 CH3 CH3 CH2OCH2C≡CH H Cl CH2 0 3.0080 CH3 CH3 CH2OCH2C≡CH H H CH2 0 3.0081 CH3 CH3 CH2OCH2C≡CCH3 H F CH2 0 3.0082 CH3 CH3 CH2OCH2C≡CCH3 H Cl CH2 0 3.0083 CH3 CH3 CH2OCH2C≡CCH3 H H CH2 0 3.0084 CH3 CH3 H F CH2 0 3.0085 CH3 CH3 H Cl CH2 0 3.0086 CH3 CH3 H H CH2 0 3.0087 CH3 CH3 H F CH2 0 3.0088 CH3 CH3 H Cl CH2 0 3.0089 CH3 CH3 H H CH2 0 3.0090 CH3 CH3 H F CH2 0 3.0091 CH3 CH3 H Cl CH2 0 3.0092 CH3 CH3 H H CH2 0 3.0093 CH3 CH3 H F CH2 0 3.0094 CH3 CH3 H Cl CH2 0 3.0095 CH3 CH3 H H CH2 0 3.0096 CH3 CH3 H F CH2 0 3.0097 CH3 CH3 H Cl CH2 0 3.0098 CH3 CH3 H H CH2 0 3.0099 CH3 CH3 H F CH2 0 3.0100 CH3 CH3 H Cl CH2 0 3.0101 CH3 CH3 H H CH2 0 3.0102 H CH3 CH2OCH2CH2OCH3 H F CH2 0 3.0103 H CH3 CH2OCH2CH2OCH3 H Cl CH2 0 3.0104 H CH3 CH2OCH2CH2OCH3 H H CH2 0 3.0105 H CH3 CH2OCH2CH2OCH2CH3 H F CH2 0 3.0106 H CH3 CH2OCH2CH2OCH2CH3 H Cl CH2 0 3.0107 H CH3 CH2OCH2CH2OCH2CH3 H H CH2 0 3.0108 H CH3 CH2N(CH3)SO2CH3 H F CH2 0 3.0109 H CH3 CH2N(CH3)SO2CH3 H Cl CH2 0 3.0110 H CH3 CH2N(CH3)SO2CH3 H H CH2 0 3.0111 H CH3 CH2OCH2Ph H F CH2 0 3.0112 H CH3 CH2OCH2Ph H Cl CH2 0 3.0113 H CH3 CH2OCH2Ph H H CH2 0 3.0114 H CH3 CH2OCH2CH2OH H F CH2 0 3.0115 H CH3 CH2OCH2CH2OH H Cl CH2 0 3.0116 H CH3 CH2OCH2CH2OH H H CH2 0 3.0117 H CH3 CH2OCH2CH2Cl H F CH2 0 3.0118 H CH3 CH2OCH2CH2Cl H Cl CH2 0 3.0119 H CH3 CH2OCH2CH2Cl H H CH2 0 3.0120 H CH3 CH2OCH2CF3 H F CH2 0 3.0121 H CH3 CH2OCH2CF3 H Cl CH2 0 3.0122 H CH3 CH2OCH2CF3 H H CH2 0 3.0123 H CH3 CH2OCH2CH═CH2 H F CH2 0 3.0124 H CH3 CH2OCH2CH═CH2 H Cl CH2 0 3.0125 H CH3 CH2OCH2CH═CH2 H H CH2 0 3.0126 H CH3 CH2O(CO)CH3 H F CH2 0 3.0127 H CH3 CH2O(CO)CH3 H Cl CH2 0 3.0128 H CH3 CH2O(CO)CH3 H H CH2 0 3.0129 H CH3 CH2OCH2C≡CH H F CH2 0 3.0130 H CH3 CH2OCH2C≡CH H Cl CH2 0 3.0131 H CH3 CH2OCH2C≡CH H H CH2 0 3.0132 H CH3 CH2OCH2C≡CCH3 H F CH2 0 3.0133 H CH3 CH2OCH2C≡CCH3 H Cl CH2 0 3.0134 H CH3 CH2OCH2C≡CCH3 H H CH2 0 3.0135 H CH3 H F CH2 0 3.0136 H CH3 H Cl CH2 0 3.0137 H CH3 H H CH2 0 3.0138 H CH3 H F CH2 0 3.0139 H CH3 H Cl CH2 0 3.0140 H CH3 H H CH2 0 3.0141 H CH3 H F CH2 0 3.0142 H CH3 H Cl CH2 0 3.0143 H CH3 H H CH2 0 3.0144 H CH3 H F CH2 0 3.0145 H CH3 H Cl CH2 0 3.0146 H CH3 H H CH2 0 3.0147 H CH3 H F CH2 0 3.0148 H CH3 H Cl CH2 0 3.0149 H CH3 H H CH2 0 3.0150 H CH3 H F CH2 0 3.0151 H CH3 H Cl CH2 0 3.0152 H CH3 H H CH2 0 3.0153 H H CH2OCH2CH2OCH3 CH3 F CH2 0 3.0154 H H CH2OCH2CH2OCH3 CH3 Cl CH2 0 3.0155 H H CH2OCH2CH2OCH3 CH3 H CH2 0 3.0156 H H CH2OCH2CH2OCH2CH3 CH3 F CH2 0 3.0157 H H CH2OCH2CH2OCH2CH3 CH3 Cl CH2 0 3.0158 H H CH2OCH2CH2OCH2CH3 CH3 H CH2 0 3.0159 H H CH2N(CH3)SO2CH3 CH3 F CH2 0 3.0160 H H CH2N(CH3)SO2CH3 CH3 Cl CH2 0 3.0161 H H CH2N(CH3)SO2CH3 CH3 H CH2 0 3.0162 H H CH2OCH2Ph CH3 F CH2 0 3.0163 H H CH2OCH2Ph CH3 Cl CH2 0 3.0164 H H CH2OCH2Ph CH3 H CH2 0 3.0165 H H CH2OCH2CH2OH CH3 F CH2 0 3.0166 H H CH2OCH2CH2OH CH3 Cl CH2 0 3.0167 H H CH2OCH2CH2OH CH3 H CH2 0 3.0168 H H CH2OCH2CH2Cl CH3 F CH2 0 3.0169 H H CH2OCH2CH2Cl CH3 Cl CH2 0 3.0170 H H CH2OCH2CH2Cl CH3 H CH2 0 3.0171 H H CH2OCH2CF3 CH3 F CH2 0 3.0172 H H CH2OCH2CF3 CH3 Cl CH2 0 3.0173 H H CH2OCH2CF3 CH3 H CH2 0 3.0174 H H CH2OCH2CH═CH2 CH3 F CH2 0 3.0175 H H CH2OCH2CH═CH2 CH3 Cl CH2 0 3.0176 H H CH2OCH2CH═CH2 CH3 H CH2 0 3.0177 H H CH2O(CO)CH3 CH3 F CH2 0 3.0178 H H CH2O(CO)CH3 CH3 Cl CH2 0 3.0179 H H CH2O(CO)CH3 CH3 H CH2 0 3.0180 H H CH2OCH2C≡CH CH3 F CH2 0 3.0181 H H CH2OCH2C≡CH CH3 Cl CH2 0 3.0182 H H CH2OCH2C≡CH CH3 H CH2 0 3.0183 H H CH2OCH2C≡CCH3 CH3 F CH2 0 3.0184 H H CH2OCH2C≡CCH3 CH3 Cl CH2 0 3.0185 H H CH2OCH2C≡CCH3 CH3 H CH2 0 3.0186 H H CH3 F CH2 0 3.0187 H H CH3 Cl CH2 0 3.0188 H H CH3 H CH2 0 3.0189 H H CH3 F CH2 0 3.0190 H H CH3 Cl CH2 0 3.0191 H H CH3 H CH2 0 3.0192 H H CH3 F CH2 0 3.0193 H H CH3 Cl CH2 0 3.0194 H H CH3 H CH2 0 3.0195 H H CH3 F CH2 0 3.0196 H H CH3 Cl CH2 0 3.0197 H H CH3 H CH2 0 3.0198 H H CH3 F CH2 0 3.0199 H H CH3 Cl CH2 0 3.0200 H H CH3 H CH2 0 3.0201 H H CH3 F CH2 0 3.0202 H H CH3 Cl CH2 0 3.0203 H H CH3 H CH2 0 3.0204 CH3 CH3 CH2OCH2CH2OCH3 CH3 F CH2 0 3.0205 CH3 CH3 CH2OCH2CH2OCH3 CH3 Cl CH2 0 3.0206 CH3 CH3 CH2OCH2CH2OCH3 CH3 H CH2 0 3.0207 CH3 CH3 CH2OCH2CH2OCH2CH3 CH3 F CH2 0 3.0208 CH3 CH3 CH2OCH2CH2OCH2CH3 CH3 Cl CH2 0 3.0209 CH3 CH3 CH2OCH2CH2OCH2CH3 CH3 H CH2 0 3.0210 CH3 CH3 CH2N(CH3)SO2CH3 CH3 F CH2 0 3.0211 CH3 CH3 CH2N(CH3)SO2CH3 CH3 Cl CH2 0 3.0212 CH3 CH3 CH2N(CH3)SO2CH3 CH3 H CH2 0 3.0213 CH3 CH3 CH2OCH2Ph CH3 F CH2 0 3.0214 CH3 CH3 CH2OCH2Ph CH3 Cl CH2 0 3.0215 CH3 CH3 CH2OCH2Ph CH3 H CH2 0 3.0216 CH3 CH3 CH2OCH2CH2OH CH3 F CH2 0 3.0217 CH3 CH3 CH2OCH2CH2OH CH3 Cl CH2 0 3.0218 CH3 CH3 CH2OCH2CH2OH CH3 H CH2 0 3.0219 CH3 CH3 CH2OCH2CH2Cl CH3 F CH2 0 3.0220 CH3 CH3 CH2OCH2CH2Cl CH3 Cl CH2 0 3.0221 CH3 CH3 CH2OCH2CH2Cl CH3 H CH2 0 3.0222 CH3 CH3 CH2OCH2CF3 CH3 F CH2 0 3.0223 CH3 CH3 CH2OCH2CF3 CH3 Cl CH2 0 3.0224 CH3 CH3 CH2OCH2CF3 CH3 H CH2 0 3.0225 CH3 CH3 CH2OCH2CH═CH2 CH3 F CH2 0 3.0226 CH3 CH3 CH2OCH2CH═CH2 CH3 Cl CH2 0 3.0227 CH3 CH3 CH2OCH2CH═CH2 CH3 H CH2 0 3.0228 CH3 CH3 CH2O(CO)CH3 CH3 F CH2 0 3.0229 CH3 CH3 CH2O(CO)CH3 CH3 Cl CH2 0 3.0230 CH3 CH3 CH2O(CO)CH3 CH3 H CH2 0 3.0231 CH3 CH3 CH2OCH2C≡CH CH3 F CH2 0 3.0232 CH3 CH3 CH2OCH2C≡CH CH3 Cl CH2 0 3.0233 CH3 CH3 CH2OCH2C≡CH CH3 H CH2 0 3.0234 CH3 CH3 CH2OCH2C≡CCH3 CH3 F CH2 0 3.0235 CH3 CH3 CH2OCH2C≡CCH3 CH3 Cl CH2 0 3.0236 CH3 CH3 CH2OCH2C≡CCH3 CH3 H CH2 0 3.0237 CH3 CH3 CH3 F CH2 0 3.0238 CH3 CH3 CH3 Cl CH2 0 3.0239 CH3 CH3 CH3 H CH2 0 3.0240 CH3 CH3 CH3 F CH2 0 3.0241 CH3 CH3 CH3 Cl CH2 0 3.0242 CH3 CH3 CH3 H CH2 0 3.0243 CH3 CH3 CH3 F CH2 0 3.0244 CH3 CH3 CH3 Cl CH2 0 3.0245 CH3 CH3 CH3 H CH2 0 3.0246 CH3 CH3 CH3 F CH2 0 3.0247 CH3 CH3 CH3 Cl CH2 0 3.0248 CH3 CH3 CH3 H CH2 0 3.0249 CH3 CH3 CH3 F CH2 0 3.0250 CH3 CH3 CH3 Cl CH2 0 3.0251 CH3 CH3 CH3 H CH2 0 3.0252 CH3 CH3 CH3 F CH2 0 3.0253 CH3 CH3 CH3 Cl CH2 0 3.0254 CH3 CH3 CH3 H CH2 0 3.0255 H CH3 CH2OCH2CH2OCH3 CH3 F CH2 0 3.0256 H CH3 CH2OCH2CH2OCH3 CH3 Cl CH2 0 3.0257 H CH3 CH2OCH2CH2OCH3 CH3 H CH2 0 3.0258 H CH3 CH2OCH2CH2OCH2CH3 CH3 F CH2 0 3.0259 H CH3 CH2OCH2CH2OCH2CH3 CH3 Cl CH2 0 3.0260 H CH3 CH2OCH2CH2OCH2CH3 CH3 H CH2 0 3.0261 H CH3 CH2N(CH3)SO2CH3 CH3 F CH2 0 3.0262 H CH3 CH2N(CH3)SO2CH3 CH3 Cl CH2 0 3.0263 H CH3 CH2N(CH3)SO2CH3 CH3 H CH2 0 3.0264 H CH3 CH2OCH2Ph CH3 F CH2 0 3.0265 H CH3 CH2OCH2Ph CH3 Cl CH2 0 3.0266 H CH3 CH2OCH2Ph CH3 H CH2 0 3.0267 H CH3 CH2OCH2CH2OH CH3 F CH2 0 3.0268 H CH3 CH2OCH2CH2OH CH3 Cl CH2 0 3.0269 H CH3 CH2OCH2CH2OH CH3 H CH2 0 3.0270 H CH3 CH2OCH2CH2Cl CH3 F CH2 0 3.0271 H CH3 CH2OCH2CH2Cl CH3 Cl CH2 0 3.0272 H CH3 CH2OCH2CH2Cl CH3 H CH2 0 3.0273 H CH3 CH2OCH2CF3 CH3 F CH2 0 3.0274 H CH3 CH2OCH2CF3 CH3 Cl CH2 0 3.0275 H CH3 CH2OCH2CF3 CH3 H CH2 0 3.0276 H CH3 CH2OCH2CH═CH2 CH3 F CH2 0 3.0277 H CH3 CH2OCH2CH═CH2 CH3 Cl CH2 0 3.0278 H CH3 CH2OCH2CH═CH2 CH3 H CH2 0 3.0279 H CH3 CH2O(CO)CH3 CH3 F CH2 0 3.0280 H CH3 CH2O(CO)CH3 CH3 Cl CH2 0 3.0281 H CH3 CH2O(CO)CH3 CH3 H CH2 0 3.0282 H CH3 CH2OCH2C≡CH CH3 F CH2 0 3.0283 H CH3 CH2OCH2C≡CH CH3 Cl CH2 0 3.0284 H CH3 CH2OCH2C≡CH CH3 H CH2 0 3.0285 H CH3 CH2OCH2C≡CCH3 CH3 F CH2 0 3.0286 H CH3 CH2OCH2C≡CCH3 CH3 Cl CH2 0 3.0287 H CH3 CH2OCH2C≡CCH3 CH3 H CH2 0 3.0288 H CH3 CH3 F CH2 0 3.0289 H CH3 CH3 Cl CH2 0 3.0290 H CH3 CH3 H CH2 0 3.0291 H CH3 CH3 F CH2 0 3.0292 H CH3 CH3 Cl CH2 0 3.0293 H CH3 CH3 H CH2 0 3.0294 H CH3 CH3 F CH2 0 3.0295 H CH3 CH3 Cl CH2 0 3.0296 H CH3 CH3 H CH2 0 3.0297 H CH3 CH3 F CH2 0 3.0298 H CH3 CH3 Cl CH2 0 3.0299 H CH3 CH3 H CH2 0 3.0300 H CH3 CH3 F CH2 0 3.0301 H CH3 CH3 Cl CH2 0 3.0302 H CH3 CH3 H CH2 0 3.0303 H CH3 CH3 F CH2 0 3.0304 H CH3 CH3 Cl CH2 0 3.0305 H CH3 CH3 H CH2 0 3.0306 H H CH2OCH2CH2OCH3 CH3 F CH2 1 3.0307 H H CH2OCH2CH2OCH3 CH3 Cl CH2 1 3.0308 H H CH2OCH2CH2OCH3 CH3 H CH2 1 3.0309 H H CH2OCH2CH2OCH2CH3 CH3 F CH2 1 3.0310 H H CH2OCH2CH2OCH2CH3 CH3 Cl CH2 1 3.0311 H H CH2OCH2CH2OCH2CH3 CH3 H CH2 1 3.0312 H H CH2N(CH3)SO2CH3 CH3 F CH2 1 3.0313 H H CH2N(CH3)SO2CH3 CH3 Cl CH2 1 3.0314 H H CH2N(CH3)SO2CH3 CH3 H CH2 1 3.0315 H H CH2OCH2Ph CH3 F CH2 1 3.0316 H H CH2OCH2Ph CH3 Cl CH2 1 3.0317 H H CH2OCH2Ph CH3 H CH2 1 3.0318 H H CH2OCH2CH2OH CH3 F CH2 1 3.0319 H H CH2OCH2CH2OH CH3 Cl CH2 1 3.0320 H H CH2OCH2CH2OH CH3 H CH2 1 3.0321 H H CH2OCH2CH2Cl CH3 F CH2 1 3.0322 H H CH2OCH2CH2Cl CH3 Cl CH2 1 3.0323 H H CH2OCH2CH2Cl CH3 H CH2 1 3.0324 H H CH2OCH2CF3 CH3 F CH2 1 3.0325 H H CH2OCH2CF3 CH3 Cl CH2 1 3.0326 H H CH2OCH2CF3 CH3 H CH2 1 3.0327 H H CH2OCH2CH═CH2 CH3 F CH2 1 3.0328 H H CH2OCH2CH═CH2 CH3 Cl CH2 1 3.0329 H H CH2OCH2CH═CH2 CH3 H CH2 1 3.0330 H H CH2O(CO)CH3 CH3 F CH2 1 3.0331 H H CH2O(CO)CH3 CH3 Cl CH2 1 3.0332 H H CH2O(CO)CH3 CH3 H CH2 1 3.0333 H H CH2OCH2C≡CH CH3 F CH2 1 3.0334 H H CH2OCH2C≡CH CH3 Cl CH2 1 3.0335 H H CH2OCH2C≡CH CH3 H CH2 1 3.0336 H H CH2OCH2C≡CCH3 CH3 F CH2 1 3.0337 H H CH2OCH2C≡CCH3 CH3 Cl CH2 1 3.0338 H H CH2OCH2C≡CCH3 CH3 H CH2 1 3.0339 H H CH3 F CH2 1 3.0340 H H CH3 Cl CH2 1 3.0341 H H CH3 H CH2 1 3.0342 H H CH3 F CH2 1 3.0343 H H CH3 Cl CH2 1 3.0344 H H CH3 H CH2 1 3.0345 H H CH3 F CH2 1 3.0346 H H CH3 Cl CH2 1 3.0347 H H CH3 H CH2 1 3.0348 H H CH3 F CH2 1 3.0349 H H CH3 Cl CH2 1 3.0350 H H CH3 H CH2 1 3.0351 H H CH3 F CH2 1 3.0352 H H CH3 Cl CH2 1 3.0353 H H CH3 H CH2 1 3.0354 H H CH3 F CH2 1 3.0355 H H CH3 Cl CH2 1 3.0356 H H CH3 H CH2 1 3.0357 CH3 CH3 CH2OCH2CH2OCH3 CH3 F CH2 1 3.0358 CH3 CH3 CH2OCH2CH2OCH3 CH3 Cl CH2 1 3.0359 CH3 CH3 CH2OCH2CH2OCH3 CH3 H CH2 1 3.0360 CH3 CH3 CH2OCH2CH2OCH2CH3 CH3 F CH2 1 3.0361 CH3 CH3 CH2OCH2CH2OCH2CH3 CH3 Cl CH2 1 3.0362 CH3 CH3 CH2OCH2CH2OCH2CH3 CH3 H CH2 1 3.0363 CH3 CH3 CH2N(CH3)SO2CH3 CH3 F CH2 1 3.0364 CH3 CH3 CH2N(CH3)SO2CH3 CH3 Cl CH2 1 3.0365 CH3 CH3 CH2N(CH3)SO2CH3 CH3 H CH2 1 3.0366 CH3 CH3 CH2OCH2Ph CH3 F CH2 1 3.0367 CH3 CH3 CH2OCH2Ph CH3 Cl CH2 1 3.0368 CH3 CH3 CH2OCH2Ph CH3 H CH2 1 3.0369 CH3 CH3 CH2OCH2CH2OH CH3 F CH2 1 3.0370 CH3 CH3 CH2OCH2CH2OH CH3 Cl CH2 1 3.0371 CH3 CH3 CH2OCH2CH2OH CH3 H CH2 1 3.0372 CH3 CH3 CH2OCH2CH2Cl CH3 F CH2 1 3.0373 CH3 CH3 CH2OCH2CH2Cl CH3 Cl CH2 1 3.0374 CH3 CH3 CH2OCH2CH2Cl CH3 H CH2 1 3.0375 CH3 CH3 CH2OCH2CF3 CH3 F CH2 1 3.0376 CH3 CH3 CH2OCH2CF3 CH3 Cl CH2 1 3.0377 CH3 CH3 CH2OCH2CF3 CH3 H CH2 1 3.0378 CH3 CH3 CH2OCH2CH═CH2 CH3 F CH2 1 3.0379 CH3 CH3 CH2OCH2CH═CH2 CH3 Cl CH2 1 3.0380 CH3 CH3 CH2OCH2CH═CH2 CH3 H CH2 1 3.0381 CH3 CH3 CH2O(CO)CH3 CH3 F CH2 1 3.0382 CH3 CH3 CH2O(CO)CH3 CH3 Cl CH2 1 3.0383 CH3 CH3 CH2O(CO)CH3 CH3 H CH2 1 3.0384 CH3 CH3 CH2OCH2C≡CH CH3 F CH2 1 3.0385 CH3 CH3 CH2OCH2C≡CH CH3 Cl CH2 1 3.0386 CH3 CH3 CH2OCH2C≡CH CH3 H CH2 1 3.0387 CH3 CH3 CH2OCH2C≡CCH3 CH3 F CH2 1 3.0388 CH3 CH3 CH2OCH2C≡CCH3 CH3 Cl CH2 1 3.0389 CH3 CH3 CH2OCH2C≡CCH3 CH3 H CH2 1 3.0390 CH3 CH3 CH3 F CH2 1 3.0391 CH3 CH3 CH3 Cl CH2 1 3.0392 CH3 CH3 CH3 H CH2 1 3.0393 CH3 CH3 CH3 F CH2 1 3.0394 CH3 CH3 CH3 Cl CH2 1 3.0395 CH3 CH3 CH3 H CH2 1 3.0396 CH3 CH3 CH3 F CH2 1 3.0397 CH3 CH3 CH3 Cl CH2 1 3.0398 CH3 CH3 CH3 H CH2 1 3.0399 CH3 CH3 CH3 F CH2 1 3.0400 CH3 CH3 CH3 Cl CH2 1 3.0401 CH3 CH3 CH3 H CH2 1 3.0402 CH3 CH3 CH3 F CH2 1 3.0403 CH3 CH3 CH3 Cl CH2 1 3.0404 CH3 CH3 CH3 H CH2 1 3.0405 CH3 CH3 CH3 F CH2 1 3.0406 CH3 CH3 CH3 Cl CH2 1 3.0407 CH3 CH3 CH3 H CH2 1 3.0408 H CH3 CH2OCH2CH2OCH3 CH3 F CH2 1 3.0409 H CH3 CH2OCH2CH2OCH3 CH3 Cl CH2 1 3.0410 H CH3 CH2OCH2CH2OCH3 CH3 H CH2 1 3.0411 H CH3 CH2OCH2CH2OCH2CH3 CH3 F CH2 1 3.0412 H CH3 CH2OCH2CH2OCH2CH3 CH3 Cl CH2 1 3.0413 H CH3 CH2OCH2CH2OCH2CH3 CH3 H CH2 1 3.0414 H CH3 CH2N(CH3)SO2CH3 CH3 F CH2 1 3.0415 H CH3 CH2N(CH3)SO2CH3 CH3 Cl CH2 1 3.0416 H CH3 CH2N(CH3)SO2CH3 CH3 H CH2 1 3.0417 H CH3 CH2OCH2Ph CH3 F CH2 1 3.0418 H CH3 CH2OCH2Ph CH3 Cl CH2 1 3.0419 H CH3 CH2OCH2Ph CH3 H CH2 1 3.0420 H CH3 CH2OCH2CH2OH CH3 F CH2 1 3.0421 H CH3 CH2OCH2CH2OH CH3 Cl CH2 1 3.0422 H CH3 CH2OCH2CH2OH CH3 H CH2 1 3.0423 H CH3 CH2OCH2CH2Cl CH3 F CH2 1 3.0424 H CH3 CH2OCH2CH2Cl CH3 Cl CH2 1 3.0425 H CH3 CH2OCH2CH2Cl CH3 H CH2 1 3.0426 H CH3 CH2OCH2CF3 CH3 F CH2 1 3.0427 H CH3 CH2OCH2CF3 CH3 Cl CH2 1 3.0428 H CH3 CH2OCH2CF3 CH3 H CH2 1 3.0429 H CH3 CH2OCH2CH═CH2 CH3 F CH2 1 3.0430 H CH3 CH2OCH2CH═CH2 CH3 Cl CH2 1 3.0431 H CH3 CH2OCH2CH═CH2 CH3 H CH2 1 3.0432 H CH3 CH2O(CO)CH3 CH3 F CH2 1 3.0433 H CH3 CH2O(CO)CH3 CH3 Cl CH2 1 3.0434 H CH3 CH2O(CO)CH3 CH3 H CH2 1 3.0435 H CH3 CH2OCH2C≡CH CH3 F CH2 1 3.0436 H CH3 CH2OCH2C≡CH CH3 Cl CH2 1 3.0437 H CH3 CH2OCH2C≡CH CH3 H CH2 1 3.0438 H CH3 CH2OCH2C≡CCH3 CH3 F CH2 1 3.0439 H CH3 CH2OCH2C≡CCH3 CH3 Cl CH2 1 3.0440 H CH3 CH2OCH2C≡CCH3 CH3 H CH2 1 3.0441 H CH3 CH3 F CH2 1 3.0442 H CH3 CH3 Cl CH2 1 3.0443 H CH3 CH3 H CH2 1 3.0444 H CH3 CH3 F CH2 1 3.0445 H CH3 CH3 Cl CH2 1 3.0446 H CH3 CH3 H CH2 1 3.0447 H CH3 CH3 F CH2 1 3.0448 H CH3 CH3 Cl CH2 1 3.0449 H CH3 CH3 H CH2 1 3.0450 H CH3 CH3 F CH2 1 3.0451 H CH3 CH3 Cl CH2 1 3.0452 H CH3 CH3 H CH2 1 3.0453 H CH3 CH3 F CH2 1 3.0454 H CH3 CH3 Cl CH2 1 3.0455 H CH3 CH3 H CH2 1 3.0456 H CH3 CH3 F CH2 1 3.0457 H CH3 CH3 Cl CH2 1 3.0458 H CH3 CH3 H CH2 1 TABLE 4 Intermediates of formulae Da and Db: No. R1 R2 R3 Y Xa Physical data 4.0001 H H OH CH2 H see Example P9; tautomeric form Da 4.0002 H H OCH3 CH2 H 4.0003 H H OCH2CH3 CH2 H 4.0004 H H OC(CH3)2 CH2 H 4.0005 H H OH CH2CH2 H see Example P12; tautomeric form Da 4.0006 H H OCH3 CH2CH2 H 4.0007 H H OCH2CH3 CH2CH2 H 4.0008 H H OC(CH3)2 CH2CH2 H 4.0009 H H OH O H 1H NMR (300 MHz; CDCl3) δ 6.35 (s, 2H); 5.66 (s, 1H); 3.78 (d, 1H); 3.43 (d, 1H); tautomeric form Da 4.0010 H H OCH3 O H 4.0011 H H OCH2CH3 O H 4.0012 H H OC(CH3)2 O H 4.0013 H H OH NSO2CH3 H 4.0014 H H OCH3 NSO2CH3 H 4.0015 H H OCH2CH3 NSO2CH3 H 4.0016 H H OC(CH3)2 NSO2CH3 H 4.0017 H H OH NC(O)C(CH3)3 H 4.0018 H H OCH3 NC(O)C(CH3)3 H 4.0019 H H OCH2CH3 NC(O)C(CH3)3 H 4.0020 H H OC(CH3)2 NC(O)C(CH3)3 H 4.0021 H H OH CH2 Cl 4.0022 H H OCH3 CH2 Cl 4.0023 H H OCH2CH3 CH2 Cl 4.0024 H H OC(CH3)2 CH2 Cl 4.0025 H H OH CH2CH2 Cl see Preparation Example P11 4.0026 H H OCH3 CH2CH2 Cl 4.0027 H H OCH2CH3 CH2CH2 Cl 4.0028 H H OC(CH3)2 CH2CH2 Cl 4.0029 H H OH O Cl 4.0030 H H OCH3 O Cl 4.0031 H H OCH2CH3 O Cl 4.0032 H H OC(CH3)2 O Cl 4.0033 H H OH NSO2CH3 Cl 4.0034 H H OCH3 NSO2CH3 Cl 4.0035 H H OCH2CH3 NSO2CH3 Cl 4.0036 H H OC(CH3)2 NSO2CH3 Cl 4.0037 H H OH NC(O)C(CH3)3 Cl 4.0038 H H OCH3 NC(O)C(CH3)3 Cl 4.0039 H H OCH2CH3 NC(O)C(CH3)3 Cl 4.0040 H H OC(CH3)2 NC(O)C(CH3)3 Cl 4.0041 H H OH CH2 Br 4.0042 H H OCH3 CH2 Br 4.0043 H H OCH2CH3 CH2 Br 4.0044 H H OC(CH3)2 CH2 Br 4.0045 H H OH CH2CH2 Br 4.0046 H H OCH3 CH2CH2 Br 4.0047 H H OCH2CH3 CH2CH2 Br 4.0048 H H OC(CH3)2 CH2CH2 Br 4.0049 H H OH O Br 4.0050 H H OCH3 O Br 4.0051 H H OCH2CH3 O Br 4.0052 H H OC(CH3)2 O Br 4.0053 H H OH NSO2CH3 Br 4.0054 H H OCH3 NSO2CH3 Br 4.0055 H H OCH2CH3 NSO2CH3 Br 4.0056 H H OC(CH3)2 NSO2CH3 Br 4.0057 H H OH NC(O)C(CH3)3 Br 4.0058 H H OCH3 NC(O)C(CH3)3 Br 4.0059 H H OCH2CH3 NC(O)C(CH3)3 Br 4.0060 H H OC(CH3)2 NC(O)O(CH3)3 Br 4.0061 H CH3 OH CH2 H 1H NMR (300 MHz; CDCl3) δ 6.30 (m, 1H); 6.10 (m, 1H); 3.73 (d, 1H); 3.44 (d, 1H); 1.62 (s, 3H); tautomeric form Db 4.0062 H CH3 OCH3 CH2 H 4.0063 H CH3 OCH2CH3 CH2 H 4.0064 H CH3 OC(CH3)2 CH2 H 4.0065 H CH3 OH CH2CH2 H 4.0066 H CH3 OCH3 CH2CH2 H 4.0067 H CH3 OCH2CH3 CH2CH2 H 4.0068 H CH3 OC(CH3)2 CH2CH2 H 4.0069 H CH3 OH O H 4.0070 H CH3 OCH3 O H 4.0071 H CH3 OCH2CH3 O H 4.0072 H CH3 OC(CH3)2 O H 4.0073 H CH3 OH NSO2CH3 H 4.0074 H CH3 OCH3 NSO2CH3 H 4.0075 H CH3 OCH2CH3 NSO2CH3 H 4.0076 H CH3 OC(CH3)2 NSO2CH3 H 4.0077 H CH3 OH NC(O)O(CH3)3 H 4.0078 H CH3 OCH3 NC(O)O(CH3)3 H 4.0079 H CH3 OCH2CH3 NC(O)C(CH3)3 H 4.0080 H CH3 OC(CH3)2 NC(O)O(CH3)3 H 4.0081 H CH3 OH CH2 Cl 4.0082 H CH3 OCH3 CH2 Cl 4.0083 H CH3 OCH2CH3 CH2 Cl 4.0084 H CH3 OC(CH3)2 CH2 Cl 4.0085 H CH3 OH CH2CH2 Cl 4.0086 H CH3 OCH3 CH2CH2 Cl 4.0087 H CH3 OCH2CH3 CH2CH2 Cl 4.0088 H CH3 OC(CH3)2 CH2CH2 Cl 4.0089 H CH3 OH O Cl 4.0090 H CH3 OCH3 O Cl 4.0091 H CH3 OCH2CH3 O Cl 4.0092 H CH3 OC(CH3)2 O Cl 4.0093 H CH3 OH NSO2CH3 Cl 4.0094 H CH3 OCH3 NSO2CH3 Cl 4.0095 H CH3 OCH2CH3 NSO2CH3 Cl 4.0096 H CH3 OC(CH3)2 NSO2CH3 Cl 4.0097 H CH3 OH NC(O)C(CH3)3 Cl 4.0098 H CH3 OCH3 NC(O)C(CH3)3 Cl 4.0099 H CH3 OCH2CH3 NC(O)C(CH3)3 Cl 4.0100 H CH3 OC(CH3)2 NC(O)C(CH3)3 Cl 4.0101 H CH3 OH CH2 Br 4.0102 H CH3 OCH3 CH2 Br 4.0103 H CH3 OCH2CH3 CH2 Br 4.0104 H CH3 OC(CH3)2 CH2 Br 4.0105 H CH3 OH CH2CH2 Br 4.0106 H CH3 OCH3 CH2CH2 Br 4.0107 H CH3 OCH2CH3 CH2CH2 Br 4.0108 H CH3 OC(CH3)2 CH2CH2 Br 4.0109 H CH3 OH O Br 4.0110 H CH3 OCH3 O Br 4.0111 H CH3 OCH2CH3 O Br 4.0112 H CH3 OC(CH3)2 O Br 4.0113 H CH3 OH NSO2CH3 Br 4.0114 H CH3 OCH3 NSO2CH3 Br 4.0115 H CH3 OCH2CH3 NSO2CH3 Br 4.0116 H CH3 OC(CH3)2 NSO2CH3 Br 4.0117 H CH3 OH NC(O)C(CH3)3 Br 4.0118 H CH3 OCH3 NC(O)O(CH3)3 Br 4.0119 H CH3 OCH2CH3 NC(O)O(CH3)3 Br 4.0120 H CH3 OC(CH3)2 NC(O)C(CH3)3 Br 4.0121 CH3 CH3 OH CH2 H 4.0122 CH3 CH3 OCH3 CH2 H 4.0123 CH3 CH3 OCH2CH3 CH2 H 4.0124 CH3 CH3 OC(CH3)2 CH2 H 4.0125 CH3 CH3 OH CH2CH2 H 4.0126 CH3 CH3 OCH3 CH2CH2 H 4.0127 CH3 CH3 OCH2CH3 CH2CH2 H 4.0128 CH3 CH3 OC(CH3)2 CH2CH2 H 4.0129 CH3 CH3 OH O H 4.0130 CH3 CH3 OCH3 O H 4.0131 CH3 CH3 OCH2CH3 O H 4.0132 CH3 CH3 OC(CH3)2 O H 4.0133 CH3 CH3 OH NSO2CH3 H 4.0134 CH3 CH3 OCH3 NSO2CH3 H 4.0135 CH3 CH3 OCH2CH3 NSO2CH3 H 4.0136 CH3 CH3 OC(CH3)2 NSO2CH3 H 4.0137 CH3 CH3 OH NC(O)O(CH3)3 H 4.0138 CH3 CH3 OCH3 NC(O)C(CH3)3 H 4.0139 CH3 CH3 OCH2CH3 NC(O)O(CH3)3 H 4.0140 CH3 CH3 OC(CH3)2 NC(O)C(CH3)3 H 4.0141 CH3 CH3 OH CH2 Cl 4.0142 CH3 CH3 OCH3 CH2 Cl see Preparation Example P3 4.0143 CH3 CH3 OCH2CH3 CH2 Cl 4.0144 CH3 CH3 OC(CH3)2 CH2 Cl 4.0145 CH3 CH3 OH CH2CH2 Cl 4.0146 CH3 CH3 OCH3 CH2CH2 Cl 4.0147 CH3 CH3 OCH2CH3 CH2CH2 Cl 4.0148 CH3 CH3 OC(CH3)2 CH2CH2 Cl 4.0149 CH3 CH3 OH O Cl 4.0150 CH3 CH3 OCH3 O Cl 4.0151 CH3 CH3 OCH2CH3 O Cl 4.0152 CH3 CH3 OC(CH3)2 O Cl 4.0153 CH3 CH3 OH NSO2CH3 Cl 4.0154 CH3 CH3 OCH3 NSO2CH3 Cl 4.0155 CH3 CH3 OCH2CH3 NSO2CH3 Cl 4.0156 CH3 CH3 OC(CH3)2 NSO2CH3 Cl 4.0157 CH3 CH3 OH NO(O)O(CH3)3 Cl 4.0158 CH3 CH3 OCH3 NC(O)C(CH3)3 Cl 4.0159 CH3 CH3 OCH2CH3 NC(O)C(CH3)3 Cl 4.0160 CH3 CH3 OC(CH3)2 NC(O)C(CH3)3 Cl 4.0161 CH3 CH3 OH CH2 Br 4.0162 CH3 CH3 OCH3 CH2 Br 4.0163 CH3 CH3 OCH2CH3 CH2 Br 4.0164 CH3 CH3 OC(CH3)2 CH2 Br 4.0165 CH3 CH3 OH CH2CH2 Br 4.0166 CH3 CH3 OCH3 CH2CH2 Br 4.0167 CH3 CH3 OCH2CH3 CH2CH2 Br 4.0168 CH3 CH3 OC(CH3)2 CH2CH2 Br 4.0169 CH3 CH3 OH O Br 4.0170 CH3 CH3 OCH3 O Br 4.0171 CH3 CH3 OCH2CH3 O Br 4.0172 CH3 CH3 OC(CH3)2 O Br see Preparation Example P6 4.0173 CH3 CH3 OH NSO2CH3 Br 4.0174 CH3 CH3 OCH3 NSO2CH3 Br 4.0175 CH3 CH3 OCH2CH3 NSO2CH3 Br 4.0176 CH3 CH3 OC(CH3)2 NSO2CH3 Br 4.0177 CH3 CH3 OH NC(O)O(CH3)3 Br 4.0178 CH3 CH3 OCH3 NC(O)O(CH3)3 Br 4.0179 CH3 CH3 OCH2CH3 NC(O)C(CH3)3 Br 4.0180 CH3 CH3 OC(CH3)2 NC(O)C(CH3)3 Br 4.0181 H H OH H 1H NMR (300 MHz; CDCl3) δ 6.30 (sxm, 2H); 3.60 (d, 1H); 3.23 (d, 1H); 2.82 (s, 1H); 0.75 (m, 4H); tautomeric form Db 4.0182 H H OH C(═C(CH3)2) H 1H NMR (300 MHz; CDCl3) δ 6.82 (sxm, 2H); 4.14 (sxm, 2H); 3.60 (d, 1H); 3.13 (d, 1H); 1.75 (s, 6H); tautomeric form Db 4.0183 H H OH CH2CH(COOCH3) H R7 = Br, see Preparation Example P13 4.0184 H H OH CH2CH(COOCH3) H R7 = CH TABLE 5 Intermediates of formulae VII: (VII) No. R1 R2 R3 R4 Y Xa Physical data 5.0000 H H OCH3 OCH3 CH2 H 5.0001 H H OCH2CH3 OCH2CH3 CH2 H 5.0002 H H —OCH2CH2O— CH2 H see Example P8 5.0003 H H OCH3 OCH3 O H 5.0004 H H OCH2CH3 OCH2CH3 O H 5.0005 H H —OCH2CH2O— O H 5.0006 H H OCH3 OCH3 NSO2CH3 H 5.0007 H H OCH2CH3 OCH2CH3 NSO2CH3 H 5.0008 H H —OCH2CH2O— NSO2CH3 H 5.0009 H H OCH3 OCH3 NC(O)C(CH3)3 H 5.0010 H H OCH2CH3 OCH2CH3 NC(O)C(CH3)3 H 5.0011 H H —OCH2CH2O— NC(O)C(CH3)3 H 5.0012 H H OCH3 OCH3 CH2CH2 H 5.0013 H H OCH2CH3 OCH2CH3 CH2CH2 H 5.0014 H H —OCH2CH2O— CH2CH2 H 5.0015 H H OCH3 OCH3 CH2 Cl 5.0016 H H OCH2CH3 OCH2CH3 CH2 Cl 5.0017 H H —OCH2CH2O— CH2 Cl 5.0018 H H OCH3 OCH3 O Cl 5.0019 H H OCH2CH3 OCH2CH3 O Cl 5.0020 H H —OCH2CH2O— O Cl 5.0021 H H OCH3 OCH3 NSO2CH3 Cl 5.0022 H H OCH2CH3 OCH2CH3 NSO2CH3 Cl 5.0023 H H —OCH2CH2O— NSO2CH3 Cl 5.0024 H H OCH3 OCH3 NC(O)C(CH3)3 Cl 5.0025 H H OCH2CH3 OCH2CH3 NC(O)C(CH3)3 Cl 5.0026 H H —OCH2CH2O— NC(O)C(CH3)3 Cl 5.0027 H H OCH3 OCH3 CH2CH2 Cl 5.0028 H H OCH2CH3 OCH2CH3 CH2CH2 Cl 5.0029 H H —OCH2CH2O— CH2CH2 Cl 5.0030 H H OCH3 OCH3 CH2 Br 5.0031 H H OCH2CH3 OCH2CH3 CH2 Br 5.0032 H H —OCH2CH2O— CH2 Br 5.0033 H H OCH3 OCH3 O Br 5.0034 H H OCH2CH3 OCH2CH3 O Br 5.0035 H H —OCH2CH2O— O Br 5.0036 H H OCH3 OCH3 NSO2CH3 Br 5.0037 H H OCH2CH3 OCH2CH3 NSO2CH3 Br 5.0038 H H —OCH2CH2O— NSO2CH3 Br 5.0039 H H OCH3 OCH3 NC(O)C(CH3)3 Br 5.0040 H H OCH2CH3 OCH2CH3 NC(O)C(CH3)3 Br 5.0041 H H —OCH2CH2O— NC(O)C(CH3)3 Br 5.0042 H H OCH3 OCH3 CH2CH2 Br 5.0043 H H OCH2CH3 OCH2CH3 CH2CH2 Br 5.0044 H H —OCH2CH2O— CH2CH2 Br 5.0045 H CH3 OCH3 OCH3 CH2 H 5.0046 H CH3 OCH2CH3 OCH2CH3 CH2 H 5.0047 H CH3 —OCH2CH2O— CH2 H 5.0048 H CH3 OCH3 OCH3 O H 5.0049 H CH3 OCH2CH3 OCH2CH3 O H 5.0050 H CH3 —OCH2CH2O— O H 5.0051 H CH3 OCH3 OCH3 NSO2CH3 H 5.0052 H CH3 OCH2CH3 OCH2CH3 NSO2CH3 H 5.0053 H CH3 —OCH2CH2O— NSO2CH3 H 5.0054 H CH3 OCH3 OCH3 NC(O)O(CH3)3 H 5.0055 H CH3 OCH2CH3 OCH2CH3 NC(O)C(CH3)3 H 5.0056 H CH3 —OCH2CH2O— NC(O)C(CH3)3 H 5.0057 H CH3 OCH3 OCH3 CH2CH2 H 5.0058 H CH3 OCH2CH3 OCH2CH3 CH2CH2 H 5.0059 H CH3 —OCH2CH2O— CH2CH2 H 5.0060 H CH3 OCH3 OCH3 CH2 Cl 5.0061 H CH3 OCH2CH3 OCH2CH3 CH2 Cl 5.0062 H CH3 —OCH2CH2O— CH2 Cl 5.0063 H CH3 OCH3 OCH3 O Cl 5.0064 H CH3 OCH2CH3 OCH2CH3 O Cl 5.0065 H CH3 —OCH2CH2O— O Cl 5.0066 H CH3 OCH3 OCH3 NSO2CH3 Cl 5.0067 H CH3 OCH2CH3 OCH2CH3 NSO2CH3 Cl 5.0068 H CH3 —OCH2CH2O— NSO2CH3 Cl 5.0069 H CH3 OCH3 OCH3 NC(O)C(CH3)3 Cl 5.0070 H CH3 OCH2CH3 OCH2CH3 NC(O)C(CH3)3 Cl 5.0071 H CH3 —OCH2CH2O— NC(O)C(CH3)3 Cl 5.0072 H CH3 OCH3 OCH3 CH2CH2 Cl 5.0073 H CH3 OCH2CH3 OCH2CH3 CH2CH2 Cl 5.0074 H CH3 —OCH2CH2O— CH2CH2 Cl 5.0075 H CH3 OCH3 OCH3 CH2 Br 5.0076 H CH3 OCH2CH3 OCH2CH3 CH2 Br 5.0077 H CH3 —OCH2CH2O— CH2 Br 5.0078 H CH3 OCH3 OCH3 O Br 5.0079 H CH3 OCH2CH3 OCH2CH3 O Br 5.0080 H CH3 —OCH2CH2O— O Br 5.0081 H CH3 OCH3 OCH3 NSO2CH3 Br 5.0082 H CH3 OCH2CH3 OCH2CH3 NSO2CH3 Br 5.0083 H CH3 —OCH2CH2O— NSO2CH3 Br 5.0084 H CH3 OCH3 OCH3 NC(O)O(CH3)3 Br 5.0085 H CH3 OCH2CH3 OCH2CH3 NC(O)C(CH3)3 Br 5.0086 H CH3 —OCH2CH2O— NC(O)O(CH3)3 Br 5.0087 H CH3 OCH3 OCH3 CH2CH2 Br 5.0088 H CH3 OCH2CH3 OCH2CH3 CH2CH2 Br 5.0089 H CH3 —OCH2CH2O— CH2CH2 Br 5.0090 CH3 CH3 OCH3 OCH3 CH2 H 5.0091 CH3 CH3 OCH2CH3 OCH2CH3 CH2 H 5.0092 CH3 CH3 —OCH2CH2O— CH2 H 5.0093 CH3 CH3 OCH3 OCH3 O H see Example P5 5.0094 CH3 CH3 OCH2CH3 OCH2CH3 O H 5.0095 CH3 CH3 —OCH2CH2O— O H 5.0096 CH3 CH3 OCH3 OCH3 NSO2CH3 H 5.0097 CH3 CH3 OCH2CH3 OCH2CH3 NSO2CH3 H 5.0098 CH3 CH3 —OCH2CH2O— NSO2CH3 H 5.0099 CH3 CH3 OCH3 OCH3 NC(O)O(CH3)3 H 5.0100 CH3 CH3 OCH2CH3 OCH2CH3 NC(O)O(CH3)3 H 5.0101 CH3 CH3 —OCH2CH2O— NC(O)O(CH3)3 H 5.0102 CH3 CH3 OCH3 OCH3 CH2CH2 H 5.0103 CH3 CH3 OCH2CH3 OCH2CH3 CH2CH2 H 5.0104 CH3 CH3 —OCH2CH2O— CH2CH2 H 5.0105 CH3 CH3 OCH3 OCH3 CH2 Cl 5.0106 CH3 CH3 OCH2CH3 OCH2CH3 CH2 Cl 5.0107 CH3 CH3 —OCH2CH2O— CH2 Cl 5.0108 CH3 CH3 OCH3 OCH3 O Cl see Example P3 5.0109 CH3 CH3 OCH2CH3 OCH2CH3 O Cl 5.0110 CH3 CH3 —OCH2CH2O— O Cl 5.0111 CH3 CH3 OCH3 OCH3 NSO2CH3 Cl 5.0112 CH3 CH3 OCH2CH3 OCH2CH3 NSO2CH3 Cl 5.0113 CH3 CH3 —OCH2CH2O— NSO2CH3 Cl 5.0114 CH3 CH3 OCH3 OCH3 NC(O)O(CH3)3 Cl 5.0115 CH3 CH3 OCH2CH3 OCH2CH3 NC(O)O(CH3)3 Cl 5.0116 CH3 CH3 —OCH2CH2O— NC(O)O(CH3)3 Cl 5.0117 CH3 CH3 OCH3 OCH3 CH2CH2 Cl 5.0118 CH3 CH3 OCH2CH3 OCH2CH3 CH2CH2 Cl 5.0119 CH3 CH3 —OCH2CH2O— CH2CH2 Cl 5.0120 CH3 CH3 OCH3 OCH3 CH2 Br 5.0121 CH3 CH3 OCH2CH3 OCH2CH3 CH2 Br 5.0122 CH3 CH3 —OCH2CH2O— CH2 Br 5.0123 CH3 CH3 OCH3 OCH3 O Br 5.0124 CH3 CH3 OCH2CH3 OCH2CH3 O Br 5.0125 CH3 CH3 —OCH2CH2O— O Br 5.0126 CH3 CH3 OCH3 OCH3 NSO2CH3 Br 5.0127 CH3 CH3 OCH2CH3 OCH2CH3 NSO2CH3 Br 5.0128 CH3 CH3 —OCH2CH2O— NSO2CH3 Br 5.0129 CH3 CH3 OCH3 OCH3 NC(O)C(CH3)3 Br 5.0130 CH3 CH3 OCH2CH3 OCH2CH3 NC(O)O(CH3)3 Br 5.0131 CH3 CH3 —OCH2CH2O— NC(O)C(CH3)3 Br 5.0132 CH3 CH3 OCH3 OCH3 CH2CH2 Br 5.0133 CH3 CH3 OCH2CH3 OCH2CH3 CH2CH2 Br 5.0134 CH3 CH3 —OCH2CH2O— CH2CH2 Br 5.0135 H H —OCH2CH2O— Cl Amorphous crystals TABLE 6 Intermediates of formula VI: (VI) No. A1 A2 R1 R2 Y Xa Physical data 6.0000 CH CH H H C(═CH(OAc)) Cl major isomer I: 1H NMR (300 MHz: CDCl3) δ 7.12 (s, 1H); 6.77 (dxd, 1H); 6.35 (dxd, 1H); 4.02 (d, 1H); 3.95 (d, 1H); 2.18 (s, 3H). 6.0001 CH CH H H C(═CH(OAc)) Cl minor isomer II: 1H NMR (300 MHz; CDCl3) δ 7.14 (s, 1H); 6.84 (dxd, 1H); 6.29 (dxd, 1H); 4.55 (d, 1H); 3.54 (d, 1H); 2.19 (s, 3H). BIOLOGICAL EXAMPLES Example B1 Herbicidal Action Prior to Emergence of the Plants (Pre-Emergence Action) Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastic pots. Immediately after sowing, the test compounds, in the form of an aqueous suspension (prepared from a 25% wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from a 25% emulsifiable concentrate (Example F1, c)), are applied by spraying in a concentration corresponding to 125 g or 250 g of active ingredient/ha (500 litres of water/ha). The test plants are then grown in a greenhouse under optimum conditions. After a test duration of 3 weeks, the test is evaluated in accordance with a scale of ten ratings (10=total damage, 0=no action). Ratings of from 10 to 6 (especially from 10 to 8) indicate good to very good herbicidal action. The compounds of formula I exhibit strong herbicidal action in this test. Examples of the good herbicidal action of the compounds are given in Table B1: TABLE B1 Pre-emergence herbicidal action: Ex. No. gr/ha Panicum Echinochloa Abutilon Amaranthus Chenopodium Kochia 1.0301 250 7 7 7 8 9 8 1.0411 250 10 9 10 10 10 10 Example B2 Post-Emergence Herbicidal Action In a greenhouse, monocotyledonous and dicotyledonous test plants are grown in standard soil in plastic pots and at the 4- to 6-leaf stage are sprayed with an aqueous suspension of the test compounds of formula I prepared from a 25% wettable powder (Example F3, b) according to WO 97/34485) or with an emulsion of the test compounds of formula I prepared from a 25% emulsifiable concentrate (Example F1, c) according to WO 97/34485), in a concentration corresponding to 125 g or 250 g of active ingredient/ha (500 litres of water/ha). The test plants are then grown on in a greenhouse under optimum conditions. After a test duration of about 18 days, the test is evaluated in accordance with a scale of ten ratings (10=total damage, 0=no action). Ratings of from 10 to 6 (especially from 10 to 7) indicate good to very good herbicidal action. The compounds of formula I exhibit a strong herbicidal action in this test. Examples of the good herbicidal action of the compounds are given in Table B2: TABLE B2 Post-emergence herbicidal action: Ex. No. gr/ha Abutilon Ipomea Amaranthus Chenopodium Stellaria Abutilon 1.0301 250 9 8 8 8 8 8 1.0411 250 9 10 9 10 9 9 1.1153 250 7 8 7 8 10 8 Example B3 Comparison Test with a Compound from the Prior Art: Post-Emergence Herbicidal Action The post-emergence herbicidal action of compound No. 1.0411 according to the invention is compared with compound “A” from WO 01/94339: TABLE B3 Post-emergence action: Ex. No. gr/ha Brachiaria Rottboelia Sida Polygonum Sinapis Galium 1.0411 15 10 3 8 8 8 6 A 15 4 0 7 5 6 5 It can be seen from Table B3 that compound No. 1.0411 according to the invention at a rate of application of 15 g/ha exhibits considerably better herbicidal action on the weeds than compound “A” from the prior art. This enhanced action was not to be expected in view of the structural similarity of the compounds.
20050624
20100817
20060309
57484.0
A01N5508
0
JACKSON, SHAWQUIA
NOVEL HERBICIDES
UNDISCOUNTED
0
ACCEPTED
A01N
2,005
10,540,863
ACCEPTED
Electronic component unit
An object of the present invention is to provide an electronic part device which can be repaired even in the case of an electronic part device having a malfunction in electrical connection after carrying out underfill. The present invention is an electronic part device in which a semiconductor element (flip chip) (3) is mounted on a wiring circuit substrate (1) under such a state that an electrode part for connection (joint ball) disposed on the semiconductor element (flip chip) (3) and a circuit electrode (5) disposed on the wiring circuit substrate (1) are facing with each other. In addition, the gap between the wiring circuit substrate (1) and the semiconductor element (flip chip) (3) is filled by a filling resin layer (4) comprising a liquid epoxy resin composition which comprises the following component (D) and the following components (A) to (C) (A) A liquid epoxy resin. (B) A curing agent. (C) An N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound. (D) A carboxylic acid vinyl ether addition product.
1. An electronic part device comprising a semiconductor circuit substrate, a semiconductor element mounted thereon in such a way that an electrode part for connection disposed on the semiconductor element and an electrode part for connection disposed on the circuit substrate are facing with each other, and a filling resin layer which fills the gap between the circuit substrate and semiconductor element, wherein the filling resin layer comprises a liquid epoxy resin composition which comprises the following component (D) and the following components (A) to (C): (A) a liquid epoxy resin, (B) a curing agent, (C) an N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound, and (D) a carboxylic acid vinyl ether addition product. 2. The electronic part device described in claim 1, wherein the aforementioned N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound as the component (C) is a compound represented by the following general formula (1): (in the formula (1), X is fluorine and/or CnF2n+ (n is a positive number of from 1 to 10), m is an integer of from 1 to 4, and R1 to R4 are monovalent organic groups other than hydrogen, which may be the same or different from one another). 3. The electronic part device described in claim 1 or 2, wherein the N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound as the component (C) is a reaction product of 2,2′-di(trifluoromethyl)-4,4′-diaminobiphenyl with a mono-epoxy compound containing one epoxy group in one molecule. 4. The electronic part device described in any one of claims 1 to 3, wherein the content of the N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound as the component (C) is set to a range of from 10 to 70% by weight, more preferably from 20 to 40% by weight, based on the entire organic components of the liquid epoxy resin composition. 5. The electronic part device described in any one of claims 1 to 4, wherein the curing agent as the component (B) is at least one of the fluorine-containing aromatic diamine represented by the following general formula (2) and a derivative thereof: (in the formula (2), X is fluorine and/or CnF2+1 (n is a positive number of from 1 to 10), m is an integer of from 1 to 4, each of R5 to R8 is hydrogen or a monovalent organic group, and at least one of R5 to R8 is hydrogen). 6. The electronic part device described in any one of claims 1 to 5, which comprises a prepolymer prepared by allowing at least one of the fluorine-containing aromatic diamine represented by the aforementioned general formula (2) and a derivative thereof to react with the liquid epoxy resin as the component (A). 7. The electronic part device described in claim 3, wherein the mono-epoxy compound containing one epoxy group in one molecule is at least one compound selected from the group consisting of n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, lauryl glycidyl ether, p-sec-butylphenyl glycidyl ether, nonylphenyl glycidyl ether, glycidyl ether of carbinol, glycidyl methacrylate, vinylcyclohexene monoepoxide and α-pinene oxide. 8. The electronic part device described in claim 1, wherein the carboxylic acid vinyl ether addition product as the component (D) is a carboxylic acid monovinyl ether addition product represented by the following general formula (3) R10—[CO—O—CH(CH3)—O—R11]n (3) (in the formula (3), R10 is an organic group of monovalent or more, R11 is an organic group of monovalent or more, wherein they may be the same or different from each other, and n is a positive integer). 9. The electronic part device described in claim 1, wherein the carboxylic acid vinyl ether addition product as the component (D) is a polyvalent carboxylic acid polyvalent vinyl ether addition product having a structural unit represented by the following general formula (4) as the main moiety -[O—CO—R12—CO—O—CH(CH3)—O—R13—O—CH(CH3)]n- (4) (in the formula (4), R12 and R13 are divalent organic groups, wherein they may be the same or different from each other, and n is a positive integer). 10. The electronic part device described in any one of claims 1 to 9, which further comprises an inorganic filler in the liquid epoxy resin composition containing the components (A) to (D). 11. The electronic part device described in claim 10, wherein the inorganic filler is a spherical silica powder having an average particle diameter of 10 μm or less.
TECHNICAL FIELD This invention relates to an electronic part device having a flip chip connection in which facing electrodes of a semiconductor element and a circuit substrate are electrically connected via an electrode part for connection (bump), as an electronic part device which has excellent connection reliability and also has a repairability. BACKGROUND OF THE INVENTION In recent years, a direct chip attach system using a bare chip such as a semiconductor element flip chip or the like is drawing attention. A so-called “C4 technique” is famous as the connection method for this flip chip system, in which a high melting point solder bump is formed on the chip side, and intermetallic bonding with solder on the ceramics circuit substrate-side is carried out. However, when a resin-based substrate such as a printed circuit substrate made of glass and an epoxy resin is used instead of the ceramics circuit substrate, it poses a problem such as insufficient connection reliability due to breaking of the solder bump bonding part caused by a difference in coefficient of thermal expansion between the chip and the resin-based substrate. As a countermeasure for such a problem, it is general to carry out a so-called underfill which is a technique in which the reliability is improved through the dispersion of thermal stress by filling the gap between the semiconductor element and the resin-based circuit substrate using, for example, a liquid resin composition. DISCLOSURE OF THE INVENTION However, since a thermosetting resin composition comprising an epoxy resin or the like as the main component is generally used as the liquid resin composition to be used in the aforementioned underfill, there is a problem in that repair cannot easily be carried out from the viewpoint that, once it is cured by heating, the product does not melt, shows high adhesive strength, does not decompose, or becomes insoluble in solvents. Thus, once underfill is carried out, it causes a problem in that, for example, an electronic part device having a malfunction in electrical connection must be scrapped and discarded. Under the recent year's demand for recycling ability towards global atmospheric conservation, it is necessary to avoid production of waste to the utmost, so that it is expected that repairing is possible even after underfilling. On the other hand, in the filling method of a liquid material by the flip chip method which uses conventional solder bump, a method is employed in which a flip chip is firstly mounted on a wiring circuit substrate to form metallic bonding by a solder melting step, and then a liquid resin material is injected into the gap between the semiconductor element and wiring circuit substrate by a capillary effect. However, the aforementioned semiconductor production method has a problem in that its productivity is low because many production processes are required. The present invention has been made by taking such circumstances into consideration, and its object is to provide an electronic part device which can be repaired even in the case of an electronic part device having a malfunction in electrical connection after carrying out underfill. In addition, another object of the present invention is to provide a semiconductor device which uses an epoxy resin composition, has excellent productivity and renders possible mounting of flip chip by previously applying a thermosetting resin composition having a function to remove a metal oxide film or antioxidant film existing on the surface of a semiconductor element or wiring circuit substrate electrode, in producing a semiconductor device which requires metal bond formation of solder bump or the like. In order to attain the aforementioned objects, the electronic part device of the present invention is an electronic part device comprising a semiconductor circuit substrate, a semiconductor element mounted thereon in such a way that an electrode part for connection disposed on the semiconductor element and an electrode part for connection disposed on the circuit substrate are facing with each other, and a filling resin layer which fills the gap between the circuit substrate and semiconductor element, wherein the filling resin layer comprises a liquid epoxy resin composition which comprises the following component (D) and the following components (A) to (C): (A) a liquid epoxy resin, (B) a curing agent, (C) an N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound, and (D) a carboxylic acid vinyl ether addition product. That is, with the aim of achieving the aforementioned objects, the present inventors have conducted studies on the epoxy resin composition as an underfill material for filling the gap between circuit substrate and semiconductor element. As a result, it was found that when (D) a carboxylic acid vinyl ether addition product is used in a liquid epoxy resin composition which uses (A) a liquid epoxy resin, (B) a curing agent and (C) an N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound as the main components, the aforementioned filling of the gap between wiring circuit substrate and semiconductor element and metallic bonding are formed by carrying out solder melting for mounting the semiconductor element on the wiring circuit substrate via the aforementioned thermosetting resin having a function to remove antioxidant film, so that the steps for the filling of the aforementioned wiring circuit substrate and semiconductor element and for the metallic connection become simple, and remarkable shortening of the production process period can be achieved, in comparison with the conventional complex process in which a semiconductor element and a wiring circuit substrate electrode are connected through metallic bonding using a flux and then a filling resin is injected into the aforementioned gap. Moreover, it was found that after curing of the liquid epoxy resin composition, solvation and subsequent swelling are generated in the cured product of this epoxy resin composition by the specific solvent and, as a result, reduction of film strength and reduction of adhesive strength of the cured product as a filling resin occur, so that mechanical peeling of the cured product is possible and repairing of the semiconductor element (flip chip) becomes possible, thus accomplishing the present invention. Since the aforementioned fluorine-containing aromatic diamine reduces solubility parameter (SP) value of the cured product by a trifluoromethyl substituent or a fluorine substituent, salvation and subsequent swelling are apt to occur by a specific solvent. According to the present invention, it was found that the solvation and swelling property are further improved by the use of an N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound and the aforementioned repairing becomes possible. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a sectional view showing the electronic part device of the present invention. FIG. 2 is a sectional view showing production process of the aforementioned electronic part device. FIG. 3 is a sectional view showing production process of the aforementioned electronic part device. In this connection, the reference numerals in the drawings are as follows. 1: Wiring circuit substrate, 2: electrode part for connection (joint ball), 3: semiconductor element, 4: filling resin layer, 5: circuit electrode, and 10: liquid epoxy resin composition. BEST MODE FOR CARRYING OUT THE INVENTION Next, embodiments of the present invention are described in detail. As shown in FIG. 1, a semiconductor element (flip chip) 3 is mounted on a wiring circuit substrate 1 in such a way that an electrode part for connection (joint ball) 2 disposed on the semiconductor element (flip chip) 3 and a circuit electrode 5 disposed on the wiring circuit substrate 1 are faced with each other. In addition, the gap between the aforementioned wiring circuit substrate 1 and semiconductor element (flip chip) 3 is filled with a filling resin layer 4 comprising a liquid epoxy resin composition. In this connection, the aforementioned two or more of the electrode parts for the connection 2 which electrically connect the aforementioned wiring circuit substrate 1 and semiconductor element 3 may be disposed on the surface of the wiring circuit substrate 1 or disposed on the surface of the semiconductor element 3, in advance. Alternatively, they may be arranged on both of the surface of the wiring circuit substrate 1 and of the surface of the semiconductor element 3, in advance. The material of the aforementioned two or more of the electrode parts for the connection 2 is not particularly limited, and examples thereof include low melting point and high melting point bumps by solder, tin bump, silver-tin bump, silver-tin-copper bump and the like, or gold lump, copper bump and the like when the circuit electrode 5 as an electrode part on the wiring circuit substrate 1 comprises the aforementioned material. Also, the material of the aforementioned wiring circuit substrate 1 is not particularly limited, but is roughly divided into ceramic substrates and plastic substrates. As the aforementioned plastic substrates, for example, an epoxy substrate, a bismaleimidotriazine substrate, a polyimide substrate and the like may be cited. In addition, the liquid epoxy resin composition to be used in the present invention may be suitably used without particular limitation, even in a case in which the bonding temperature cannot be set to a high temperature due to a problem of heat resistance, such as a combination of a plastic substrate with an electrode part for connection by low melting solder. In the aforementioned electronic part device, the electrode part for connection 2 disposed on the semiconductor element is formed into a bump shape, but not particularly limited to this shape, and the circuit electrode 5 disposed on the wiring circuit substrate 1 may be provided in a bump shape. The liquid epoxy resin composition as the aforementioned filling resin layer 4-forming material is obtainable by formulating a carboxylic acid vinyl ether addition product (component D) together with a liquid epoxy resin (component A), a curing agent (component B) and an N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound (component C). In this connection, regarding the liquid epoxy resin composition of the present invention, the liquid means a liquid state which shows fluidity at 25° C. That is, a state in which the viscosity is within the range of from 0.01 mPa·s to 10,000 Pa·s at 25° C. Measurement of the aforementioned viscosity may be carried out using an EMD-type rotational viscometer. The aforementioned liquid epoxy resin (component A) is not particularly limited with the proviso that it is a liquid epoxy resin which contains two or more epoxy groups per 1 molecule. Examples thereof include bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, bisphenol AF type, phenol novolak type and the like various liquid epoxy resins and derivatives thereof, a liquid epoxy resin derived from a polyhydric alcohol and epichlorohydrin and derivatives thereof, glycidylamine type, hydantoin type, aminophenol type, aniline type, toluidine type and the like various glycidyl type liquid epoxy resins and derivatives thereof (described in “Jitsuyo Plastic Jiten Zairyo Hen (Practical Plastics Dictionary, Materials)”, edited by Jitsuyo Plastic Jiten Editorial Committee, First Edition, Third Printing, published on Apr. 20, 1996, page 211 to page 225; the contents thereof being incorporated herein by reference), and liquid mixtures of these aforementioned liquid epoxy resins with various glycidyl type solid epoxy resins, and the like. These may be used alone or as a mixture of two or more. The aforementioned curing agent (component B) is not particularly limited with the proviso that it can cure the aforementioned liquid epoxy resin (component A), but it is desirable to use at least one of an aromatic diamine and a derivative thereof. It is more desirable to use at least one of a fluorine-containing aromatic diamine and a derivative thereof from the viewpoint that solvation and subsequent swelling by a specific solvent become easy. Examples of the aromatic diamine in the aforementioned at least one of an aromatic diamine and a derivative thereof include p-phenylenediamine, m-phenylenediamine, 2,5-toluenediamine, 2,4-toluenediamine, 4,6-dimethyl-m-phenylenediamine, 2,4-diaminomesitylene and the like aromatic mononuclear diamines, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′,-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′,-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfide, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone and the like aromatic dinuclear diamines, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene and the like aromatic trinuclear diamines, 4,4′-di-(4-aminophenoxy)diphenylsulfone, 4,4′-di-(3-aminophenoxy)diphenylsulfone, 4,4′-di-(4-aminophenoxy)diphenylpropane, 4,4′-di-(3-aminophenoxy)diphenylpropane, 4,4′-di-(4-aminophenoxy)diphenyl ether, 4,4′-di-(3-aminophenoxy)diphenyl ether and the like aromatic tetranuclear diamines and the like, which may be used alone or as a mixture of two or more. The fluorine-containing aromatic diamine in the aforementioned at least one of a fluorine-containing aromatic diamine and a derivative thereof is not particularly limited, with the proviso that it is a fluorine substituted aromatic diamine having a primary amino group, and its examples include 2,2′-di(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(3-amino-4,5-dimethylphenyl)hexafluoropropane, 2,2-bis(4-hydroxy-3-aminophenyl)hexafluoropropane, 4,4′-bis[2-(4-carboxyphenyl)hexafluoroisopropyl]diphenyl ether, 4,4′-bis[2-(4-aminophenoxyphenyl)hexafluoroisopropyl]diphenyl ether and the like, which may be used alone or as a mixture of two or more. Regarding the aforementioned at least one of a fluorine-containing aromatic diamine and a derivative thereof, a fluorine substituted or fluorinated alkyl substituted diaminobiphenyl represented by the following general formula (2) is suitably used, because its use prolongs pot life at room temperature. (In the formula (2), X is fluorine and/or CnF2n+1 (n is a positive number of from 1 to 10), two m's may be the same or different from each other and each is an integer of from 1 to 4, each of R5 to R8 is hydrogen or a monovalent organic group, and at least one of R5 to R8 is hydrogen.) In the aforementioned formula (2), each of R5 to R8 is hydrogen or a monovalent organic group, and at least one of R5 to R9 must be hydrogen. As the aforementioned monovalent organic group, for example, saturated alkyl group represented by —CnH2+1 (n is an integer of from 1 to 10), aryl group, 3-alkoxy substituted-2-hydroxypropyl group represented by —CH2CH(OH)CH2—OCnH2n+1, 3-aryl substituted-2-hydroxypropyl group represented by —CH2CH(OH)CH2—O—R9 (R9 is an aryl group), and the like may be cited. In addition, R5 to R8 may be the same or different from one another when the aforementioned conditions are satisfied. The aforementioned aryl group is not particularly limited, and its illustrative examples include phenyl group (C6H5—), tolyl group (CH3C6H5—), xylyl group ((CH3)2C6H5), biphenyl group (C6H5C6H4—), naphthyl group (C10H7—), anthryl group (C14H9—), phenanthryl group (C14H9—) and the like. Particularly, according to the present invention, the use of 2,2′-di(trifluoromethyl)-4,4′-diaminobiphenyl having the smallest active hydrogen equivalent as the aforementioned fluorine-containing aromatic diamine is desirable from the viewpoint that the blending amount can be reduced and viscosity of the one-component non-solvent epoxy resin composition may be reduced. Regarding the blending ratio of the liquid epoxy resin (component A) with the curing agent (component B) according to the present invention, it is desirable to set the number of active hydrogen of the aforementioned curing agent (component B) within the range of from 0.4 to 1.6 based on 1 epoxy group of the aforementioned liquid epoxy resin (component A). More desirable range is the range of from 0.6 to 1.2. That is, when the number of active hydrogen exceeds 1.6 based on 1 epoxy group, viscosity of the liquid epoxy resin composition tends to increase, and when it is less that 0.4, glass transition temperature of cured product of the liquid epoxy resin composition tends to decrease. On the other hand, according to the present invention, when the liquid epoxy resin (component A), particularly a multifunctional aliphatic liquid epoxy resin is used, a possibility of generating voids caused by the evaporation or volatilization of low boiling point compounds contained in the multifunctional aliphatic liquid epoxy resin or the like may be reduced, by making at least one of the aforementioned fluorine-containing aromatic diamine and a derivative thereof and the multifunctional aliphatic liquid epoxy resin into a prepolymer through their preliminary reaction. The aforementioned prepolymer may be obtained, for example, by allowing at least one of a fluorine-containing aromatic diamine and a derivative thereof to react with a multifunctional aliphatic liquid epoxy compound having two or more epoxy groups in one molecule. In general, the prepolymer is prepared by putting predetermined amounts of respective components into a reaction vessel, and carrying out the reaction at a temperature of from 60 to 120° C. in a stream of nitrogen and under the absence of catalyst until a predetermined molecular weight is obtained. Regarding the molecular weight of this prepolymer, it is desirable to use a prepolymer prepared by reacting until its polystyrene based weight average molecular weight becomes approximately from 400 to 5,000, and by preparing such a prepolymer, generation of voids in the underfill filling resin layer caused by the evaporation or volatilization of volatile low boiling point low molecular weight compounds can be prevented. Illustrative examples of the aforementioned multifunctional aliphatic liquid epoxy resin include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidylaniline, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether and the like aliphatic diols and triols, or multifunctional glycidyl ethers of aliphatic multifunctional alcohols and the like. The N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound (component C) to be used together with the aforementioned liquid epoxy resin (component A) and curing agent (component B) is illustratively a compound represented by the following general formula (1), which may be obtained, for example, by allowing the aforementioned fluorine-containing aromatic diamine to react with a mono-epoxy compound containing 1 epoxy group in 1 molecule. (In the formula (1), X is fluorine and/or CnF2+1 (n is a positive number of from 1 to 10), two m's may be the same or different from each other and each is an integer of from 1 to 4, R1 to R4 are monovalent organic groups other than hydrogen, which may be the same or different from one another.) In the aforementioned formula (1), R1 to R4 are monovalent organic groups other than hydrogen, and their examples include saturated alkyl group represented by —CnH2+1 (n is an integer of from 1 to 10), aryl group, 3-alkoxy substituted-2-hydroxypropyl group represented by —CH2CH(OH)CH2—OCnH2+1, 3-aryl substituted-2-hydroxypropyl group represented by —CH2CH(OH)CH2—O—R9 (R9 is an aryl group), and the like. In addition, R1 to R4 may be the same or different from one another. The aforementioned aryl group is not particularly limited, and its illustrative examples include phenyl group (C6H5—), tolyl group (CH3C6H5—), xylyl group ((CH3)2C6H5), biphenyl group (C6H5C6H4—), naphthyl group (C10H7—), anthryl group (C14H9—), phenanthryl group (C14H9—) and the like. Regarding the aforementioned reaction of a fluorine-containing aromatic diamine with a mono-epoxy compound containing 1 epoxy group in 1 molecule, the reaction may be carried out by putting predetermined amounts of respective components into a reaction vessel, and heating them at a temperature of approximately from 60 to 120° C. in a stream of nitrogen and under the absence of catalyst until epoxy group is consumed, and the tetra-substitution compound represented by the aforementioned general formula (1) is obtained by this reaction. The aforementioned mono-epoxy compound is not particularly limited with the proviso that it is an epoxy compound containing 1 epoxy group in 1 molecule, and its examples include n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, lauryl glycidyl ether, p-sec-butylphenyl glycidyl ether, nonylphenyl glycidyl ether, glycidyl ether of carbinol, glycidyl methacrylate, vinylcyclohexene monoepoxide, α-pinene oxide and the like. These may be used alone or as a mixture of two or more. It is desirable to set blending ratio of the aforementioned N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound (component C) within a range of from 10 to 70% by weight based on the entire organic components of the liquid epoxy resin composition. It is set to more preferably from 30 to 60% by weight, particularly preferably from 20 to 40% by weight. That is, this is because repair by quick swelling can hardly be taken place when it is less than 10% by weight, and on the other hand, when it exceeds 70% by weight, strength of cured product of the liquid epoxy resin composition tend to become insufficient, thus showing a tendency in that a mechanical strength which can endure the temperature cycle may not be maintained. According to the present invention, various conventionally known curing accelerators may be used for shortening the curing time. Illustrative examples thereof include 1,8-diazabicyclo(5,4,0)undecane-7, triethylene diamine and the like tertiary amines, 2-methylimidazole and the like imidazoles, triphenylphosphine, tetraphenylphosphonium tetraphenylborate and the like phosphorus-based curing accelerators, salicylic acid and the like acid catalysts, acetylacetonatocupper, acetylacetonatozinc and the like Lewis acids, and the like. These may be used alone or as a mixture of two or more. Particularly, according to the present invention, it is desirable to use tetraphenylphosphonium tetraphenylborate and the like phosphonium salts or acetylacetonatocupper, acetylacetonatozinc and the like Lewis acids as the aforementioned curing accelerators, because they do not spoil stability of the liquid epoxy resin composition. The blending amount of the aforementioned curing accelerator is not particularly limited, but it is desirable to appropriately set it to such a ratio that the desired curing rate may be obtained based on the mixture of the aforementioned liquid epoxy resin (component A), curing agent (component B) and N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound (component C). For example, the amount for use may be easily decided by measuring gelation time using a heating plate, as an index of the curing rate. As an example thereof, it is desirable to set it within a range of from 0.01 to 3% by weight, based on the entire liquid epoxy resin composition. As the carboxylic acid vinyl ether addition product (component D) as a flux component to be used together with the aforementioned liquid epoxy resin (component A), curing agent (component B) and N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound (component C), the carboxylic acid monovinyl ether addition product represented by the following general formula (3), compounds consisting of organic carboxylic acids and vinyl ether compounds such as the polyvalent carboxylic acid polyvalent vinyl ether addition product represented by the following general formula (4) may be used, though not particularly limited thereto with the proviso that they have these structures. For example, as the aforementioned organic carboxylic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, o, m, p-toluic acid, o, m, p-chlorobenzoic acid, o m, p-bromobenzoic acid, o, m, p-nitrobenzoic acid and the like monocarboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, itaconic acid, acrylic acid and the like dicarboxylic acids, trimellitic acid, pyromellitic acid, isocyanuric acid, carboxyl group-containing polybutadiene and the like polycarboxylic acids and the like. In addition, as the aforementioned vinyl ether compound, vinyl ether compounds having butyl group, ethyl group, propyl group, isopropyl group, cyclohexyl group, allyl group and the like organic groups of monovalent or more may be exemplified. By the use of a compound of such a structure, the component D as a flux activator can exert flux effect in the semiconductor mounting process and then react with the epoxy resin composition, so that it may be suitably used as a material having both functions as the flux component and the curing agent. R10—[CO—CH(CH3)—O—R11]n (3) (In the formula (3), R10 is an organic group of monovalent or more, R11 is an organic group of monovalent or more, and they may be the same or different from each other. Also, n is a positive integer, preferably a positive integer of from 1 to 4.) -[O—CO—R12—CO—O—CH(CH3)—O—R13—O—CH(CH3)]n- (4) (In the formula (4), R12 and R13 are divalent organic groups, and they may be the same or different from each other. Also, n is a positive integer, preferably a positive integer of from 1 to 4.) Particularly preferably, an adipic acid cyclohexyl divinyl ether addition product which is obtained using adipic acid as the organic carboxylic acid and a vinyl ether compound having cyclohexyl group as the vinyl ether compound, maleic acid cyclohexyl divinyl ether addition product or the like may be exemplified, from the viewpoint that it forms a three dimensional cross-linking structure with epoxy resin. From the viewpoint of solder persistency, heat resistance and excess moisture tolerance reliability, it is desirable to set the containing ratio of the aforementioned carboxylic acid vinyl ether addition product (component D) as the flux component within a range of from 0.1 to 20% by weight, more preferably from 0.5 to 15% by weight, particularly preferably from 1.0 to 10% by weight, based on the entire organic components. That is, this is because the flux activity tends to become insufficient when it is less that 0.1% by weight, and glass transition temperature of the cured product tends to reduce when it exceeds 20% by weight. In addition, 0.5% by weight or more is desirable because a tendency of rapidly becoming insufficient in flux activity is not found, and 15% by weight or less is desirable because a tendency of slightly reducing glass transition temperature of the cured product is not found. According to the present invention, an inorganic filler can also be added within such a range that malfunction does not occur in the metallic bonding of the bump electrode part of semiconductor element flip chip with the electrode part of wiring circuit substrate. As such an inorganic filler, silica powder of synthetic silica, fused silica or the like, and various powders such as of alumina, silicon nitride, aluminum nitride, boron nitride, magnesia, calcium silicate, magnesium hydroxide, aluminum hydroxide, titanium oxide and the like may be exemplified. Among the aforementioned inorganic fillers, it is desirable to use spherical silica powder because of its large effect to reduce viscosity of the liquid epoxy resin composition. Also, as the aforementioned inorganic filler, it is desirable to use a powder having a maximum particle diameter of 24 μm or less. In addition, a filler having the aforementioned maximum particle diameter and also having an average particle diameter of 10 μm or less is preferably used, and a filler having an average particle diameter of from 1 to 8 μm is suitably used. In this connection, the aforementioned maximum particle diameter and average particle diameter may be measured, for example, using a laser diffraction scattering type particle size distribution analyzer. It is desirable to set the blending amount of the aforementioned inorganic filler within a range of from 10 to 80% by weight based on the entire liquid epoxy resin composition, and it is particularly preferably from 40 to 70% by weight. This is because there is a tendency that the effect of the cured product of liquid epoxy resin composition to reduce coefficient of linear expansion becomes small when the blending amount is less than 10% by weight, and there is a tendency that viscosity of the liquid epoxy resin composition increases when it exceeds 80% by weight. In this connection, in addition to the aforementioned liquid epoxy resin (component A), curing agent (component B), N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound (component C), carboxylic acid vinyl ether addition product (component D), curing accelerator and inorganic filler, the liquid epoxy resin composition of the present invention may jointly use a silane coupling agent for the purpose of superior bonding with an adherend, enhancing interface bonding with various inorganic fillers, and the like. The aforementioned silane coupling agent is not particularly limited, and its examples include β-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl methyldiethoxysilane and the like. Also, in addition to the aforementioned respective components, a reactive diluent can also be formulated optionally for the purpose of effecting viscosity reduction and the like. Since this reactive diluent sometimes contains volatile low boiling point compounds, it is desirable to use it by removing in advance volatile evaporating low boiling point compounds which cause generation of voids in the filling resin layer at a predetermined curing temperature of the liquid epoxy resin composition as the underfill resin, as described in the foregoing. In addition, when the reactive diluent itself is volatile, voids are apt to be generated in the filling resin layer at a predetermined curing temperature of the liquid epoxy resin composition as the underfill resin, so that it is desirable to limit use of such a reactive diluent. Examples of the aforementioned reactive diluent include n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, lauryl glycidyl ether, p-sec-butylphenyl glycidyl ether, nonylphenyl glycidyl ether, glycidyl ether of carbinol, glycidyl methacrylate, vinylcyclohexene monoepoxide, α-pinene oxide, glycidyl ether of a tertiary carboxylic acid, diglycidyl ether, glycidyl ether of (poly)ethylene glycol, glycidyl ether of (poly)propylene glycol, glycidyl ether of poly(propylene glycol), propylene oxide addition product of bisphenol A, partial addition product of a bisphenol A type epoxy resin with a polymerized fatty acid, polyglycidyl ether of a polymerized fatty acid, diglycidyl ether of butanediol, vinylcyclohexene dioxide, neopentyl glycol diglycidyl ether, diglycidylaniline, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether and the like. These may be used alone or as a mixture of two or more. Also, in addition to the aforementioned respective components, antimony trioxide, antimony pentoxide, brominated epoxy resin or the like flame retardant or flame retardant co-agent, silicone or the like low tress providing agent, a coloring agent and the like may be optionally formulated in the liquid epoxy resin composition of the present invention, within such a range that the gist of the present invention is not spoiled. The liquid epoxy resin composition according to the present invention may be produced, for example, in the following manner. That is, a one-component non-solvent liquid epoxy resin composition may be produced by blending predetermined amounts of the aforementioned liquid epoxy resin (component A), curing agent (component B), inorganic filler (component C), N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound (component D) and, as occasion demands, curing accelerator and the like, mixing and dispersing them under a high shearing force of three rollers, homo-mixer or the like, and as occasion demands, effecting degassing under a reduced pressure. In the electronic part device of the present invention, a semiconductor element is mounted on a wiring circuit substrate via two or more electrode parts for connection, and the gap between the aforementioned wiring circuit substrate and semiconductor element is filled with a filling resin layer prepared using the aforementioned liquid epoxy resin composition. The aforementioned filling resin layer may be formed by putting the aforementioned liquid epoxy resin composition between the aforementioned wiring circuit substrate and semiconductor element, and then curing the composition. An example of the embodiment of the production method of such an electronic part device of the present invention is described in regular order based on the drawings. That is, filling of the gas between the semiconductor element (flip chip) and wiring circuit substrate which uses the liquid epoxy resin composition of the present invention is carried out, for example, in the following manner. Firstly, as shown in FIG. 2, the liquid epoxy resin composition 10 of the present invention is put on the wiring circuit substrate 1 equipped with the circuit electrode 5. Next, as shown in FIG. 3, the semiconductor element 3 equipped with two or more of the spherical electrode part for connection (joint ball) 2 is put on a predetermined position of the liquid epoxy resin composition 10 of the present invention, the aforementioned liquid epoxy resin composition 10 is melted on a heating stage to reduce its viscosity, the liquid epoxy resin composition 10 wherein the aforementioned electrode part for connection of the semiconductor element 3 became the aforementioned state is pushed away, and the aforementioned liquid epoxy resin composition 10 under the aforementioned low viscosity condition is filled into the gap between the aforementioned semiconductor element 3 and the aforementioned wiring circuit substrate 1, where the circuit electrode 5 on the wiring circuit substrate 1 and the electrode part for connection 2 are contacted with each other. Thereafter, metallic bonding by solder reflow is carried out, and then the filling resin layer 4 is formed by filling the aforementioned gap through curing of the liquid epoxy resin composition 10. In this case, the solder reflow method may be either a bonding method which uses a reflow furnace or a bonding method in which solder melting is carried out by heating the heater part to the solder melting point or more, simultaneously with the chip mounting. In this way, as shown in FIG. 1, the electronic part device in which the semiconductor element 3 is mounted on the wiring circuit substrate 1, and the gap between the aforementioned wiring circuit substrate 1 and semiconductor element 3 is filled with the filling resin layer 4 comprising the liquid epoxy resin composition 10, under such a condition that the electrode part for connection (joint ball) 2 disposed on the semiconductor element (flip chip) 3 and the circuit electrode 5 disposed on the wiring circuit substrate 1 are facing with each other, is produced. In addition, thickness and weight of the aforementioned liquid epoxy resin composition 10 are optionally set in the same manner as described in the foregoing, based on the size of the semiconductor element 3 to be mounted and the size of the spherical electrode part for connection 2 disposed on the semiconductor element 3, that is, based on the occupying volume of the filling resin layer 4 formed by filling and filling the gap between the semiconductor element 3 and wiring circuit substrate 1. Also, as the heating temperature in changing the aforementioned liquid epoxy resin composition 10 to a low viscosity state by heating the same in the aforementioned production, it may be appropriately set by taking into consideration heat resistance of the semiconductor element 3 and wiring circuit substrate 1, melting point of the electrode part for connection 2 and room temperature viscosity, heat resistance and the like of the liquid epoxy resin composition. The gap distance between the semiconductor element (flip chip) 3 and the wiring circuit substrate 1 of the electrical part device thus obtained is generally from about 30 to 300 μm. Cured product of the epoxy resin composition in the filling part of the electronic part device obtained in this manner swells by a specific organic solvent and its adhesive strength therefore is reduced even after the curing, so that the electronic part device can be repaired. As the aforementioned specified organic solvent, a ketone solvent, a glycol diether solvent, a nitrogenous solvent and the like are desirable. These may be used alone or as a mixture of two or more. Examples of the aforementioned ketone solvent include acetophenone, isophorone, ethyl-n-butyl ketone, diisopropyl ketone, diethyl ketone, cyclohexyl ketone, di-n-propyl ketone, methyl oxide, methyl-n-amyl ketone, methyl isobutyl ketone, methyl ethyl ketone, methylcyclohexanone, methyl-n-heptyl ketone, phorone and the like. These may be used alone or as a mixture of two or more. Examples of the aforementioned glycol diether solvent include ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and the like. These may be used alone or as a mixture of two or more. Examples of the aforementioned nitrogenous solvent includes N,N′-dimethylformamide, N,N′-dimethylacetamide, N-methyl-2-pyrrolidone, N,N′-dimethyl sulfoxide, hexamethylphosphor triamide and the like. These may be used alone or as a mixture of two or more. As a repairing method for the aforementioned electronic part device, for example, the semiconductor element is removed by heating the repairing part of the semiconductor element (flip chip) or wiring circuit substrate using a heating plate. As the heating temperature of this case, when heated at a temperature of about +50° C. or more higher than the glass transition temperature of a cured product of the epoxy resin composition of the present invention, both (semiconductor element or wiring circuit substrate) can be easily peeled off under such a state that the cured product is under a cohesive failure or adhered to one side. Thereafter, when the aforementioned organic solvent is directly applied thereto or absorbent cotton impregnated with the aforementioned organic solvent is allowed to contact with the residual part of the cured product of the epoxy resin composition of the wiring circuit substrate at room temperature, and then the residue is removed after confirming swelling of the hardened product, the wiring circuit substrate can be reused. On the other hand, the semiconductor element (flip chip) to which the residue of cured product of the liquid epoxy resin composition is adhered, the semiconductor element (flip chip) can be reused by soaking it in the aforementioned organic solvent in a predetermined container and removing the thus swelled cured product. Alternatively, though it requires a treatment for a prolonged period of time, the semiconductor element can also be detached from the wiring circuit substrate by directly applying the aforementioned organic solvent to the entire repairing part of the aforementioned wiring circuit substrate or covering the same with absorbent cotton impregnated with the organic solvent, and thereby reducing strength and adhesive strength of the cured product through its swelling by gradually permeating the organic solvent from the end of the semiconductor element. EXAMPLES Next, Examples are described together with comparative examples. Firstly, respective components shown below were prepared. Liquid Epoxy Resin a: An epoxy resin represented by the following structural formula (5) (In the formula (5), n is a positive number of 0 or more (preferably a positive number of from 0 to 300, more preferably a positive number of from 0 to 10). Purity 99%, viscosity 22 dPa·s (25° C.), epoxy equivalent 165 g/eq) Liquid Epoxy Resin b: A multifunctional epoxy compound represented by the following structural formula (6) (In the formula (6), viscosity 0.6 dPa·s (25° C.), epoxy equivalent 125 g/eq) Curing Agent a: A fluorine-containing aromatic diamine represented by the following structural formula (7). (In the formula (7), melting point 182° C., active hydrogen equivalent 80 g/eq) Curing Agent b: A fluorine-containing aromatic diamine derivative represented by the following structural formula (8) obtained by putting 1 mol of 2,2′-di(trifluoromethyl)-4,4′-diaminobiphenyl represented by the aforementioned structural formula (7) and 0.5 mol of butyl glycidyl ether in that ratio into a reaction vessel and allowing them to undergo the reaction at 200° C. (In the formula (8), in the four of R, 3.5 in average are hydrogen, and 0.5 in average is —CH2—CH(OH)CH2—O—C4H9. Also, average active hydrogen equivalent is 110 g/eq.) N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound: An N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound represented by the following structural formula (9). (In the formula (9), R″ is —CH2—CH(OH)CH2—O—C4H9.) Prepolymer a: A prepolymer a (active hydrogen equivalent 325) which is a starch syrup-like viscous liquid obtained by allowing 0.5 equivalent (82.5 g) of the multifunctional epoxy resin represented by the aforementioned structural formula (5) to react with 1 active hydrogen equivalent (80 g) of the fluorine-containing aromatic diamine represented by the aforementioned structural formula (7) at 150° C. for 15 minutes and then cooling the product. Prepolymer b: A prepolymer b (viscosity 10 dPa·s, weight average molecular weight 560) obtained by charging a reaction vessel with 1 mole of the fluorine-containing aromatic diamine derivative represented by the aforementioned structural formula (8) and 4 moles of the multifunctional epoxy resin represented by the aforementioned structural formula (6) and allowing them to undergo the reaction at 100° C. for 10 minutes. Inorganic Filler: Spherical silica particles (maximum particle diameter 12 μm, average particle diameter 4 μm, specific surface area 3.0 m2/g). Carboxylic Acid Vinyl Ether Addition Product a: An adipic acid cyclohexyl divinyl ether addition product containing a structural unit represented by the following structural formula (a) as the main component (acid equivalent 273 g/mol, viscosity 26 dPa·s, weight average molecular weight 2,050, number average molecular weight 1,405). -[O—CO— (CH2)4—CO—O—CH(CH3)—O—C6H10—O—O—CH(CH3)]n- (a) Carboxylic Acid Vinyl Ether Addition Product b: A maleic acid cyclohexyl divinyl ether addition product represented by the following structural formula (b)=acid equivalent 254 g/mol, grease-like viscous liquid, weight average molecular weight 2,300, number average molecular weight 1,300). -[O—CO—CH═CH—CO—O—CH(CH3)—O—C6H10—O—CH(CH3)]n- (b) Examples 1 to 14 and Comparative Examples 1 to 3 One-component non-solvent liquid epoxy resin compositions were prepared by blending respective components prepared in the above at the ratios shown in the following Table 1 to Table 4, and uniformly mixing and dispersing them at room temperature (25° C.) using three rollers. TABLE 1 (part by weight) Examples 1 2 3 4 5 6 Liquid epoxy resin a 0.825 0.825 0.825 0.825 0.825 0.825 b 0.625 0.625 0.625 0.625 0.625 0.625 Curing agent a — — — — — — b 0.88 0.88 0.88 0.88 0.22 0.66 N,N,N′,N′-tetra- 1.55 0.78 2.85 1.55 1.55 1.55 substituted fluorine-containing aromatic diamine compound Carboxylic acid a 0.19 0.16 0.26 0.02 0.08 0.31 vinyl b — — — — — — ether addition product Prepolymer a — — — — — — b — — — — — — Inorganic filler — — — — — — TABLE 2 (part by weight) Examples 7 8 9 10 11 12 Liquid epoxy resin a 0.825 0.825 0.825 0.825 0.825 0.825 b 0.625 0.625 0.625 0.625 0.625 0.625 Curing agent a — 0.64 — — — — b 0.88 — 0.88 0.88 0.88 0.88 N,N,N′,N′-tetra- 1.55 1.39 1.55 1.55 0.78 2.85 substituted fluorine-containing aromatic diamine compound Carboxylic acid a 0.70 0.17 0.19 — — — vinyl b — — — 0.19 0.16 0.26 ether addition product Prepolymer a — — — — — — b — — — — — — Inorganic filler — — 4.07 4.07 — — TABLE 3 (part by weight) Examples 13 14 Liquid epoxy resin a 0.413 0.825 b 0.625 — Curing agent a — — b — — N,N,N′,N′-tetra-substituted 1.394 1.553 fluorine-containing aromatic diamine compound Carboxylic acid vinyl a 0.17 0.24 ether addition product b — — Prepolymer a 1.053 — b — 1.505 Inorganic filler — — TABLE 4 (part by weight) Comparative Examples 1 2 3 Liquid epoxy resin a 0.825 0.825 0.825 b 0.625 0.625 — Curing agent a — — — b 0.88 0.88 — N,N,N′,N′-tetra-substituted 1.55 1.55 1.553 fluorine-containing aromatic diamine compound Carboxylic acid vinyl a — — — ether addition product b — — — Prepolymer a — — — b — — 1.505 Inorganic filler — 2.33 — Using each of the thus obtained liquid epoxy resin compositions of Examples and Comparative Examples, its viscosity at 25° C. was measured using an EMD type rotational viscometer, and then packed in a polypropylene syringe equipped with a needle of 0.56 mm in needle inner diameter. Thereafter, the liquid epoxy resin composition was applied using the aforementioned syringe in advance to the solder pads (substrate-side electrodes)—containing semiconductor element arranging face of a wiring circuit substrate of 1 mm in thickness made of FR-4 glass-epoxy, in which 64 wiring pads of 300 μm in diameter are opened (substrate-side electrodes). On the other hand, a silicon chip (370 μm in thickness, 10 mm×10 mm in size) having 64 solder bump electrodes of 200 μm in diameter was prepared, the aforementioned substrate-side electrodes of the wiring circuit substrate and the bump electrodes of the face down silicon chip were aligned, and the silicon chip was allowed to stand on the wiring circuit substrate. This was heated to 60° C. on a heating stage and then solder-bonded by passing through a heating reflow furnace under a condition of 240° C. for 10 seconds. The gap between the aforementioned flip chip and wiring circuit substrate was 210 μm. Thereafter, its filling was carried out by curing it at 150° C. for 4 hours to prepare respective electronic part devices. After completion of the curing, they were gradually cooled down to room temperature and then their electrical connection was examined by circuit testing. As a result, a case in which electrical connection was obtained was expressed as O, and a case in which continuity was not obtained was expressed as X. In addition, the presence or absence of voids in the filling resin layer which filled and filled the gap between the wiring circuit substrate and semiconductor element was observed by an ultrasonic flaw detector. A case in which voids were not observed was evaluated as O, and a case in which 1 or 2 voids were observed as Δ, and a case in which more voids were observed as X. Using the respective electronic part devices obtained in this manner, their defect percentage in connectivity and repairing ability were measured and evaluated in accordance with the methods shown in the following. The results are shown in the following Table 5 to Table 8, together with measured physical property of the aforementioned liquid epoxy resin composition. Defect Percentage in Connectivity: Defect percentage in connectivity of the aforementioned electronic part device just after filling was measured. The aforementioned electronic part device was subjected to a temperature cycle test of −30° C./10 minutes 125° C./10 minutes using a thermal test device to examine electrical continuity after 1,000 cycles, and then the defect percentage in connectivity (%) was calculated by carrying out a connection reliability test on all of the 64 copper wiring pads of the aforementioned glass-epoxy wiring circuit substrate. Repairing Ability: After measuring the aforementioned defect percentage in connectivity, silicon chip was peeled off from the aforementioned electronic part device on a heating plate heated to 200° C. and the remaining part was returned to room temperature, and absorbent cotton impregnated with a mixed solvent of N,N′-dimethylformamide and diethylene glycol dimethyl ether (same volume) was put on the residual part of the cured product of epoxy resin component remaining on the connecting parts of the aforementioned remaining part and allowed to stand at room temperature (22° C.) for 1 hour. Thereafter, this absorbent cotton was removed and removing of the cured product of epoxy resin component was carried out by thoroughly wiping with methanol. After supply of solder paste to pad parts of the wiring circuit substrate and subsequent solder melting, electrical continuity of the peelable electronic part device was again examined by mounting a silicon chip on the wiring circuit substrate in the same manner as described in the above. Thereafter, this was filled to carry out evaluation of repair (rework) ability in the same manner as described in the above. A case in which cured product of the epoxy resin composition is completely removable and the electrical connection is perfect was expressed as ⊚, and a case in which the cured product can be peeled off though it slightly remains, but the electrical connection is perfect as O, a case in which the cured product can be peeled off though it slightly remains, but the electrical connection is imperfect as Δ, and a case in which cured product of the epoxy resin composition can hardly be peeled off, and the electrical connection is imperfect as X. TABLE 5 Examples 1 2 3 4 5 6 Viscosity (at 25° C.) (dPa · s) 52 55 52 53 54 48 Defect percentage in connectivity (%) 0 0 0 0 0 0 Voids ◯ ◯ ◯ ◯ ◯ ◯ Electrical connection test ◯ ◯ ◯ ◯ ◯ ◯ Repair ability (22° C.) ◯ ◯ ◯ ◯ ◯ ◯ TABLE 6 Examples 7 8 9 10 11 12 Viscosity (at 25° C.) (dPa · s) 44 120 250 280 64 59 Defect percentage in connectivity 0 0 0 0 0 0 (%) Voids ◯ ◯ ◯ ◯ ◯ ◯ Electrical connection test ◯ ◯ ◯ ◯ ◯ ◯ Repair ability (22° C.) ◯ ◯ ◯ ◯ ◯ ◯ TABLE 7 Examples 13 14 Viscosity (at 25° C.) (dPa · s) 75 68 Defect percentage in connectivity (%) 0 0 Voids ◯ ◯ Electrical connection test ◯ ◯ Repair ability (22° C.) ◯ ◯ TABLE 8 Comparative Examples 1 2 3 Viscosity (at 25° C.) 51 180 71 (dPa · s) Defect percentage in 100 100 100 connectivity (%) Voids ◯ ◯ ◯ Electrical connection not not not test testable testable testable Repair ability (22° C.) ◯ ◯ ◯ Based on the results of the aforementioned Table 5 to Table 8, it is evident that all of the liquid epoxy resin compositions of Examples are also superior in the repair property, because voids were not generated in the filling resin layer, and there was no defect percentage in connectivity due to the use of the carboxylic acid vinyl ether addition product as a flux component. In addition, it is apparent that they are excellent as void-less, one-component non-solvent liquid epoxy resin compositions combined with low viscosity. Contrary to this, the liquid epoxy resin composition of Comparative Example 1 showed good repair ability, but its continuity itself was not obtained because of the absence of the carboxylic acid vinyl ether addition product as a flux component. Also, in the same manner, the continuity itself was not obtained in the preparations of other Comparative Examples because of the absence of flux component. While the invention has been describe in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on Dec. 25, 2002 (Japanese Patent Application No. 2002-374735), the entire contents thereof being thereby incorporated by reference. INDUSTRIAL APPLICABILITY As described in the above, the present invention is an electronic part device in which the gap between the circuit substrate and semiconductor element is filled with a filling resin layer comprising a liquid epoxy resin composition containing a carboxylic acid vinyl ether addition product (component D) together with a liquid epoxy resin (component A), a curing agent (component B) and an N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound (component C). Since the aforementioned carboxylic acid vinyl ether addition product (component D) as a reflux component is blended in the aforementioned liquid epoxy resin composition, the filling can be achieved simultaneously with the electrical connection of flip chip as the semiconductor element and the wiring circuit substrate, so that the productivity becomes excellent. What is more, it easily swells at room temperature by undergoing salvation by a specific organic solvent even after its curing. As a result, strength of the cured product is considerably reduced so that it is possible to easily peel it off from an adherend (electrode or the like). Thus, the electronic part device obtained by carrying out filling using the aforementioned liquid epoxy resin composition has superior productivity and connection reliability, and it is not necessary to discard the electronic part device itself even when a connection failure is generated due to positional slippage between electrodes or the like, so that an electronic part device having superior repair ability can be obtained. When the aforementioned specific compound represented by the general formula (1) is used as the aforementioned N,N,N′,N′-tetra-substituted fluorine-containing aromatic diamine compound (component C), it exerts favorable effect in which easiness for repairing can be resulted by quick swelling ability, which is desirable. In addition, when the aforementioned fluorine-containing aromatic diamine represented by the general formula (2) is used as the curing agent (component B), and a prepolymer prepared by allowing this to react with the liquid epoxy resin (component A) is used, further improvement of curing speed can be attained. What is more, since it can be formed in advance into a condition of from a liquid state to a viscous paste state, complex steps are not necessary in the measurement at the time of blending and dispersing step thereafter, so that the liquid epoxy resin composition can be easily obtained.
<SOH> BACKGROUND OF THE INVENTION <EOH>In recent years, a direct chip attach system using a bare chip such as a semiconductor element flip chip or the like is drawing attention. A so-called “C4 technique” is famous as the connection method for this flip chip system, in which a high melting point solder bump is formed on the chip side, and intermetallic bonding with solder on the ceramics circuit substrate-side is carried out. However, when a resin-based substrate such as a printed circuit substrate made of glass and an epoxy resin is used instead of the ceramics circuit substrate, it poses a problem such as insufficient connection reliability due to breaking of the solder bump bonding part caused by a difference in coefficient of thermal expansion between the chip and the resin-based substrate. As a countermeasure for such a problem, it is general to carry out a so-called underfill which is a technique in which the reliability is improved through the dispersion of thermal stress by filling the gap between the semiconductor element and the resin-based circuit substrate using, for example, a liquid resin composition.
<SOH> BRIEF DESCRIPTION OF THE DRAWINGS <EOH>FIG. 1 is a sectional view showing the electronic part device of the present invention. FIG. 2 is a sectional view showing production process of the aforementioned electronic part device. FIG. 3 is a sectional view showing production process of the aforementioned electronic part device. detailed-description description="Detailed Description" end="lead"? In this connection, the reference numerals in the drawings are as follows. 1 : Wiring circuit substrate, 2 : electrode part for connection (joint ball), 3 : semiconductor element, 4 : filling resin layer, 5 : circuit electrode, and 10 : liquid epoxy resin composition.
20051122
20080401
20060518
58599.0
H01L2148
0
CHEN, JACK S J
ELECTRONIC COMPONENT UNIT
UNDISCOUNTED
0
ACCEPTED
H01L
2,005
10,540,953
ACCEPTED
System and method for resource management in a terminal connected to a communication network
A system for managing a resource in a terminal (10) for an architecture (15, 15′) dedicated to a communications network. The system comprises a dedicated architecture resource manager (16, 16′) adapted to process a request for a resource of said dedicated architecture (15, 15′) defined by a process manager (17, 17′) of said dedicated architecture (15, 15′) as a function of an application activated on said terminal (10) and to dialogue with a resource administrator (14) of a dedicated architecture manager (13) to manage a resource of said terminal (10) and to process simultaneously the operation of said dedicated architectures (15, 15′) of said terminal (10) that are connected to a plurality of said communications networks. Application to the management of resources allocated to a communications network from a set of communications networks each offering a set of services via a dedicated architecture (15, 15′) integrated in a terminal (10) connected to a public mobile network to which the user is a subscriber.
1. A system for managing a resource in a terminal (10) for an architecture (15, 15′) dedicated to a communications network, wherein said system comprises a dedicated architecture resource manager (16, 16′) adapted to process a request for a resource of said dedicated architecture (15, 15′) defined by a process manager (17, 17′) of said dedicated architecture (15, 15′) as a function of an application activated on said terminal (10) and to dialogue with a resource administrator (14) of a dedicated architecture manager (13) to manage a resource of said terminal (10) and to process simultaneously the operation of said dedicated architectures (15, 15′) of said terminal (10) that are connected to a plurality of said communications networks. 2. A system according to claim 1 for managing a resource in a terminal (10) for a dedicated architecture (15, 15′), wherein said dedicated architecture resource manager (16, 16′) is integrated in each dedicated architecture (15, 15′) of said terminal (10). 3. A system according to claim 1 for managing a resource in a terminal (10) for a dedicated architecture (15, 15′), wherein said dedicated architecture resource manager (16, 16′) includes an interface for exchanging information with said resource administrator (14) of said dedicated architecture manager (13). 4. A system according to claim 1 for managing a resource in a terminal (10) for a dedicated architecture (15, 15′), wherein said dedicated architecture resource manager (16, 16′) includes an interface for exchanging information with a process manager (17, 17′) of said dedicated architecture (15, 15′). 5. A system according to claim 1 for managing a resource in a terminal (10) for a dedicated architecture (15, 15′), wherein said resource administrator (14) of said dedicated architecture manager (13) includes an interface for exchanging information with a resource allocator (12) of said terminal (10). 6. A system according to claim 1 for managing a resource in a terminal (10) for a dedicated architecture (15, 15′), wherein said resource administrator (14) of said dedicated architecture manager (13) includes an interface for exchanging information with a radio interface (11). 7. A system according to claim 1 for managing a resource in a terminal (10) for a dedicated architecture (15, 15′), wherein said dedicated architecture resource manager (16, 16′) includes a resource correspondence table for defining a resource corresponding to an application (18, 19, 20) activated on said terminal (10). 8. A method of managing a resource in a terminal (10) for an architecture (15, 15′) dedicated to a communications network, wherein said method includes the operations of: activating an application (18, 19, 20) on said terminal (10), a process manager (17, 17′) of said dedicated architecture (15, 15′) defining a resource corresponding to said application (18, 19, 20), said process manager (17, 17′) requesting said resource of a dedicated architecture resource manager (16, 16′), said dedicated architecture resource manager (16, 16′) responding after checking said resource request, a resource administrator (14) of a dedicated architecture manager (13) responding after checking said resource request, a resource allocator (12) of said terminal (10) allocating a resource, a radio interface (11) for access to said communications network allocating a resource, said dedicated architecture resource manager (16, 16′) associating said resources with said application (18, 19, 20) after validation, and said process manager (17, 17′) executing said application (18, 19, 20) by means of said resource.
The present invention relates to a system and a method for resource management in a terminal connected to a communications network. The invention applies more particularly to managing resources assigned to a communications network amongst a set of communications networks, each offering a set of services via a dedicated architecture integrated in a terminal connected to a public mobile network to which the user is a subscriber. At present, such services are accessible from a terminal connected to mobile telecommunications networks such as GPRS (General Packet Radio Service) networks and UMTS (Universal Mobile Telecommunication System) networks. In those mobile networks, to select a communications network offering services, it is necessary to select a name identifying the communications network. To set up a connection between a terminal and a particular communications network, the identifying name is sent via a service support equipment of the mobile network to an equipment managing access to the communications networks. The identifying name, coming from the terminal, enables the service support equipment of the mobile network to determine the access management equipment associated with the identifying name that offers access to the communications network. In existing GPRS and UMTS networks, the name identifying a communications network is called its access point name (APN). An APN primarily comprises an identifier that corresponds to the selected communications network, an identifier of the operator managing that communications network, and an identifier of the technology of the mobile network, for example GPRS technology. The format and use of an APN are covered by standards issued by the European Telecommunications Standards Institute (ETSI). To access a communications network offering a set of services, the user selects an APN on the terminal in order to set up a connection with the corresponding communications network. Once an APN has been selected on the terminal, an access protocol is initialized. In a GPRS or a UMTS network, this protocol is the Packet Data Protocol (PDP). A procedure is executed to set up a connection from the terminal to the access management equipment known as a gateway GPRS support node (GGSN). To enable the connection to be set up, a link to the selected communications network is created across the mobile network. In a GPRS or a UMTS network, this link is called a PDP context link. It enables the terminal to access the services of the communications network. The ETSI standard provides for a plurality of connections to be set up simultaneously from the same terminal to different communications networks. The document FR 02/07457 describes the use of a dedicated architecture manager in a terminal to manage simultaneous access to a plurality of communications networks. In that document, on establishing a connection to a communications network, the dedicated architecture manager dialogues with the communications network. In the terminal, the dedicated architecture manager designates a dedicated architecture which is allocated to the connection to the connected communications network. On setting up each new connection to a new communications network, the dedicated architecture manager designates a different dedicated architecture which is allocated to the connection to the new communications network. The various dedicated architectures in the same terminal operate simultaneously. Each dedicated architecture is associated with a PDP context link and provides access to a different communications network. The above document mentions that the dedicated architecture manager in a terminal assigns each dedicated architecture to a communications network. The autonomy and independent operation of the dedicated architectures of the terminal guarantee mutual confidentiality and security between the communications networks by providing a “seal” between the various services connected to the terminal. To maintain the independence of the various communications networks effectively, and because of the autonomy of the various dedicated architectures of a terminal, each dedicated architecture has no view of the operation of the other dedicated architectures of the terminal. Thus the technical problem to be solved by the present invention is that of proposing a system and a method for managing a resource in a terminal for at least one architecture that is dedicated to one particular communications network, which system and method eliminate the drawbacks of existing systems by managing the various dedicated architectures of a single terminal. The solution in accordance with the present invention to the stated technical problem is that said system comprises a dedicated architecture resource manager adapted to process a request for a resource of said dedicated architecture and to dialogue with a resource administrator of a dedicated architecture manager to manage a resource of said terminal and to process simultaneously the operation of said dedicated architectures of said terminal that are connected to a plurality of said communications networks. The dedicated architecture manager of the terminal manages simultaneous operation of the various architectures dedicated to the various communications networks to which said terminal is connected. Thus each dedicated architecture of said terminal communicates with only one communications network, i.e. the communications network associated with the corresponding PDP context link, even if said terminal is connected to a plurality of communications networks. When the user of the terminal wishes to access a service accessible via one of said connected communications networks and associated with one of said dedicated architectures, the user activates an application on the terminal. As a function of the required service, said application can take the form of a browser for reading a web page, a video player, an analog or digital sound player, etc. In the terminal, said application is associated with the architecture dedicated to the communications network concerned. In said dedicated architecture, a dedicated architecture resource manager processes a resource request associated with the execution of said application. Said dedicated architecture resource manager sends said resource request to said dedicated architecture manager of the terminal to verify the feasibility of said resource request and its compatibility with the other dedicated architectures and with the available resources of the terminal. This preserves separate and autonomous operation of the various dedicated architectures of the terminal, which guarantees the mutual confidentiality and security of the various communications networks to which said terminal is connected. These imperatives are particularly important during a banking transaction or on connecting to a business private network, for example. According to the invention, said dedicated architecture resource manager includes an interface for exchanging information with said resource administrator of said dedicated architecture manager. According to the invention, said dedicated architecture resource manager includes an interface for exchanging information with a process manager of said dedicated architecture. According to the invention, said resource administrator of said dedicated architecture manager includes an interface for exchanging information with a resource allocator of said terminal. According to the invention, said resource administrator of said dedicated architecture manager includes an interface for exchanging information with a radio interface. In the terminal, said resource request from said dedicated architecture resource manager is processed by different equipments of said terminal, such as a process manager of said dedicated architecture, a resource administrator of said dedicated architecture manager, a resource allocator and a radio interface of said terminal. To facilitate transmission for exchanging resource information, an interface is integrated in said equipments concerned of the terminal to enable the necessary exchanges. Each of said equipments of the terminal dialogues through said integrated interfaces with one or more other equipments of the terminal. However, said equipments do not express a request for a resource the same way; for example, a request may take the form of a request for a memory space or a request for a size of memory space. To facilitate said dialogue, said various equipments of the terminal concerned include means for translating the content of said received resource request. According to the invention, said dedicated architecture resource manager includes a resource correspondence table for defining a resource corresponding to an application activated on said terminal. As indicated above, the application activated by the user is associated with the architecture dedicated to the communications network concerned. A request for execution of said application is sent to a process manager of said dedicated architecture, which identifies the request and then sends it to the dedicated architecture resource manager. Said dedicated architecture resource manager accesses a resource correspondence table that defines a resource corresponding to said application, for example a memory space necessary for downloading a file from a communications network to which the terminal is connected. In this way, a resource request corresponds to said activated application. The invention also provides a method of managing a resource in a terminal for an architecture dedicated to a communications network, characterized in that said method includes the operations of activating an application on said terminal, a process manager of said dedicated architecture defining a resource corresponding to said application, said process manager requesting said resource of a dedicated architecture resource manager, said dedicated architecture resource manager responding after checking said resource request, a resource administrator of a dedicated architecture manager responding after checking said resource request, a resource allocator of said terminal allocating a resource, a radio interface for access to said communications network allocating a resource, said dedicated architecture resource manager associating said resources with said application after validation, and said process manager executing said application by means of said resource. Each of said equipments concerned of the terminal receives said resource request corresponding to said activated application. Each of said equipments of the terminal checks the feasibility and compatibility of said resource request. Said process manager manages all the applications executed in a dedicated architecture. Said dedicated architecture resource manager manages all requests for resources of a dedicated architecture. Said dedicated architecture manager resource administrator manages all requests for resources requested by a said dedicated architectures. Said resource allocator of the terminal manages the available resources of said terminal. Said radio interface manages exchanges with the mobile network and said communications network. After validation of these various equipments, said application is executed using said allocated resource. Some of the steps of said method of the invention may be omitted as a function of the nature of said application and the technological complexity of said terminal, or for reasons of simplicity or economy, for example in terms of processing time on the terminal. However, the smaller the number of steps, the higher the probability of significant incompatibility between a resource request and the processing carried out by the terminal to allocate said resource. Said dedicated architecture manager allocates a dedicated architecture to each of said communications networks, offering the possibility of simultaneous but different and independent management. Said resource administrator of said dedicated architecture manager centralizes all requests for resources requested by the various dedicated architectures. Because the various dedicated architectures operate separately and autonomously, the operation of said terminal can be adapted to the communications network to which it is connected. For example, there may be functions on one communications network that do not exist on another communications network. Because of the increased number of services accessible via communications networks, the autonomy of each dedicated architecture in particular allows assignment of specific resources that differ from one communications network to another, for example specific applications, a specific memory space or a specific quality of service. The following description, which is given with reference to the appended drawings, which are provided by way of non-limiting example, explains in what the invention consists and how it may be put into practice. FIG. 1 is a diagram of the general architecture of a system of the invention for managing a resource in a terminal for an architecture dedicated to a communications network. FIG. 2 represents steps of the method of the invention of managing a resource in a terminal. To simplify the description, the equipment connected to the mobile telecommunications network is shown as a terminal 10, but may be of different kinds, for example a server, a mobile communications terminal, or a personal computer (PC). In FIG. 1, which is an overall representation of a system for managing a resource in a terminal 10 for an architecture 15, 15′ dedicated to a communications network, the terminal 10 is a user equipment (UE). Whichever kind of terminal 10 is used, it is connected to a public mobile network to which the user is a subscriber. At present, if the user of the terminal 10 wishes to access a communications network offering a set of services to which the user requires access, the user uses a radio station of the mobile network to send an APN identifying the communications network. To do this, the user accesses a list of APNs identifying the communications networks to which the user is a subscriber and can access, for example via a user interface in a dedicated architecture manager 13. The ETSI standard provides for a plurality of connections to be set up simultaneously to different communications networks from the same terminal and, amongst other things, the list of APNs enables a plurality of APNs to be managed in the terminal. In the mobile network, a GGSN equipment sets up the connection to the selected communications network. A PDP context link is set up across the mobile network to the communications network. This PDP context link enables the terminal 10 to access the communications network. The GGSN then sends an address to the terminal 10 that identifies the terminal 10 in the communications network to which it has been connected. The dedicated architecture manager 13 in the terminal 10 receives the address. It allocates a dedicated architecture 15, 15′ to the connected communications network, which network 15, 15′ is associated with the PDP context link that enables access from the terminal 10 to said communications network. The connection steps referred to above are repeated each time that the user of the terminal 10 wishes to access a new communications network. The dedicated architecture manager 13 in the terminal 10 then allocates a new dedicated architecture 15, 15′ to each new communications network connected. If the user of the terminal 10 wishes to access a service accessible via one of the communications networks, an application on the terminal 10 is activated. As a function of the service required, the application 18, 19, 20 can take the form of a browser for reading a web page, a video player, an analog or digital sound player, etc. In the terminal 10, the application 18, 19, 20 is associated with the architecture 15, 15′ dedicated to the communications network concerned. A request for execution of the application 18, 19, 20 is sent to a process manager 17, 17′ of the dedicated architecture 15, 15′, which allocates an identifier to the request to execute the application 18, 19, 20. The process manager 17, 17′ manages all the applications executed in the dedicated architecture 15, 15′ and allocates to each resource request an identifier that becomes effective when the resource request is validated. The process manager 17, 17′ sends a resource request corresponding to the application 18, 19, 20 to a dedicated architecture resource manager 16, 16′. In the dedicated architecture 15, 15′, the dedicated architecture resource manager 16, 16′ manages the applications 18, 19, 20 associated with the dedicated architecture 15, 15′ and activated by the user of the terminal 10, and requests for resources needed by existing applications. The dedicated architecture resource manager 16, 16′ accesses a resource correspondence table to define a resource corresponding to the application 18, 19, 20 and needed in the terminal 10 to execute the application. For example, display means, a memory space, an input-output interface, and usage time of the central processing unit (CPU) of the terminal 10 are needed in particular to open a web page. The dedicated architecture resource manager 16, 16′ checks the feasibility of the resource request. If it is not feasible, the dedicated architecture resource manager 16, 16′ rejects the resource request. To facilitate the exchange of information between the process manager 17, 17′ and the dedicated architecture resource manager 16, 16′, a transmission interface for exchanging information is integrated in both managers 16, 16′, 17, 17′. Similarly, a transmission interface for exchanging resource information is integrated in the various equipments concerned of the terminal 10 to enable the necessary exchanges. What is more, not all the equipments of the terminal 10 express resource requests in the same way. For example, the application 18, 19, 20 may simply request a memory space but the dedicated architecture resource manager 16, 16′ may understand a request for memory space only in the form of a request for the necessary size of memory space, such as a request for 150 kbytes of memory space. Consequently, each of the equipments concerned of the terminal 10 which dialogues via the integrated interfaces includes means for translating the content of the received resource request. The dedicated architecture resource manager 16, 16′ sends the resource request to a resource administrator 14 integrated in a dedicated architecture manager 13. Management by the dedicated architecture manager 13 of the various dedicated architectures 15, 15′ each associated with a different communications network enables operation of the terminal 10 as a “multi-APN” terminal. In the dedicated architecture manager 13, the resource administrator 14 in turn checks the feasibility of the resource request corresponding to the dedicated architecture 15, 15′ for the application 18, 19, 20. If it is not feasible, the resource administrator 14 rejects the resource request. The resource administrator 14 of the dedicated architecture manager 13, which stores the list and manages the dedicated architectures 15, 15′ used in the terminal 10, balances resource requests coming from the various dedicated architectures 15, 15′ and regulates the allocated resources between the various dedicated architectures 15, 15′. Depending on the settings of the parameters of the terminal 10, the resource administrator 14 of the dedicated architecture manager 13 can give priority to certain applications 18, 19, 20 over others or to certain dedicated architectures 15, 15′. Being centralized, the resource administrator 14 of the dedicated architecture manager 13 avoids calls to the mobile network and the communications network concerned, in particular if the resource request is incompatible with the capacities of the terminal 10 or with the characteristics of the APN corresponding to the communications network. The resource administrator 14 of the dedicated architecture manager 13 centralizes and updates resource requests coming from different dedicated architectures 15, 15′ to facilitate resource management, in particular on closing an application 18, 19, 20 or a dedicated architecture 15, 15′. The resource administrator 14 of the dedicated architecture manager 13 sends the resource request to a resource allocator 12 integrated in the terminal 10 to reserve a resource corresponding to the resource request. The resource allocator 12 manages the various resources of the terminal 10, such as memory space, an input-output interface, display means, and CPU time on the central processing unit of the terminal 10. The resource administrator 14 of the dedicated architecture manager 13 sends the resource request to a radio interface 11 to enable the mobile network to access the communications network concerned by means of the resource request. In the terminal 10, the radio interface 11 manages communication with the mobile network and with the communications networks to which the terminal 10 is connected. As a function of the result of the verifications, the resource administrator 14 of the dedicated architecture manager 13 confirms the reservation of resources to the resource allocator 12 and to the radio interface 11 and confirms the execution of an access procedure to the communications network. If the verification results are negative, the resource administrator 14 of the dedicated architecture manager 13 cancels the reservation of resources to the resource allocator 12 and to the radio interface 11, canceling execution of the access procedure to the communications network. If the verification results are positive, the resource administrator 14 of the dedicated architecture manager 13 sends the resource request to the dedicated architecture resource manager 16, 16′, which acknowledges receiving the result of the resource request. In the dedicated architecture 15, 15′ concerned, the dedicated architecture resource manager 16, 16′ associates the allocated resources with the application 18, 19, 20 to which the identified resource request related. If the resource request is rejected, the dedicated architecture resource manager 16, 16′ deletes all references to the resource request. In the dedicated architecture 15, 15′, the dedicated architecture resource manager 16, 16′ sends the result of the resource request to the process manager 17, 17′. If the resource request is accepted, the process manager 17, 17′ executes the application 18, 19, 20. If not, execution of the application 18, 19, 20 is cancelled. To assist with understanding the invention, FIG. 2 shows the various steps of managing a resource in a terminal 10 for an architecture 15, 15′ dedicated to a communications network. When the user wishes to access a service accessible via one of the communications networks, the user activates an application 18, 19, 20 on the terminal 10 (step 1). A request for execution of the application 18, 19, 20 is sent to the process manager 17, 17′ of the architecture 15, 15′ dedicated to the communications network concerned (step 2). The process manager 17, 17′ defines a resource in the terminal 10 necessary for executing the application 18, 19, 20. The process manager 17, 17′ sends a resource request corresponding to the application 18, 19, 20 to a dedicated architecture resource manager 16, 16′ (step 3). In the dedicated architecture 15, 15′, the dedicated architecture resource manager 16, 16′ processes a portion of the request, which is managed locally by the dedicated architecture resource manager 16, 16′. The dedicated architecture manager 16, 16′ analyses the local portion of the request to check the feasibility of the resource request (step 4) At this stage, the dedicated architecture resource manager 16, 16′ can either acknowledge the locally processed portion of the resource request by means of an acknowledgement (OK) message, reject the portion by means of a rejection (NOK) message, or modify the resource request as a function of the resources already allocated to the dedicated architecture 15, 15′, for example. A rejection (NOK) message can be sent, for example, if the dedicated architecture resource manager 16, 16′ does not understand the resource request or if a problem occurs with the dedicated architecture resource manager 16, 16′ processing the resource request. As previously mentioned, at least one transmission interface for exchanging information is integrated in the process manager 17, 17′ and the dedicated architecture resource manager 16, 16′. Similarly, if necessary, dialogue via the integrated interfaces is facilitated by means for translating the content of the resource request. If the analysis result is negative (NOK message) the resource request is rejected and the next step of the method of the invention is the step 15 (see below). If the analysis result is positive (OK message), the dedicated architecture resource manager 16, 16′ sends the resource request to the resource administrator 14 of the dedicated architecture manager 13 (step 5). In the terminal 10, the resource administrator 14 of the dedicated architecture manager 13 processes a portion of the request, which is managed locally by the resource administrator 14. The resource administrator 14 of the dedicated architecture manager 13 analyses the local portion of the resource request to check the feasibility of the request (step 6). At this stage, the resource administrator 14 of the dedicated architecture manager 13 can acknowledge the locally processed portion of the resource request by means of an acknowledgement (OK) message, reject the portion by means of a rejection (NOK) message or modify the resource request as a function of the resources already used in the terminal 10, for example. If the analysis result is negative (NOK message), the resource request is rejected and the next step of the method of the invention is step 12 (see below). If the analysis result is positive (OK message), the resource administrator 14 of the dedicated architecture manager 13 sends the resource request to the resource allocator 12 of the terminal 10 (step 7). As before, the resource allocator 12 checks the feasibility of the received request and can acknowledge the resource request by means of an acknowledgement (OK) message, reject the request by means of a rejection (NOK) message or modify the resource request as a function of the resources already used in the terminal 10, for example. If the analysis result is negative, the resource request is rejected and the resource allocator 12 sends a rejection (NOK) message to the resource administrator 14 of the dedicated architecture manager 13. If the analysis result is positive, the resource allocator 12 reserves a resource corresponding to the resource request and sends an acknowledgement (OK) message to the resource administrator 14. If the preceding analysis results are positive (OK messages), the resource administrator 14 of the dedicated architecture manager 13 sends the resource request to the radio interface 11 of the terminal 10 (step 8). The radio interface 11 of the terminal 10 extracts from the resource request the parameters necessary for executing the procedure for accessing the mobile network and the communications network concerned. The procedure for accessing a communications network, which is standardized by the ETSI, reserves resources for the communications network. The radio interface 11 of the terminal 10 receives from the communications network the result of the procedure, which is a rejection (NOK message), an acceptance (OK message) or a modification of the resource request. The radio interface 11 of the terminal 10 sends the result to the resource administrator 14 of the dedicated architecture manager 13 (step 9). If the message is a rejection (NOK) message, the resource request is rejected and the next step of the method of the invention is step 12 (see below). If the result is a modification of the resource request, the resource administrator 14 sends the modified resource request to the resource allocator 12 of the terminal 10 for it to modify the reservation of resources (step 10). The result is again either an acknowledgement (OK message) or a rejection (NOK message) sent to the resource administrator 14 of the dedicated architecture manager 13. If the message sent is an acknowledgement (OK) message, the resource administrator 14 sends the resource request to the dedicated architecture resource manager 16, 16′ (step 11). In the dedicated architecture 15, 15′, the dedicated architecture resource manager 16, 16′ can acknowledge the resource request by means of an acknowledge (OK) message, reject the request by means of a rejection (NOK) message or modify the resource request. The dedicated architecture resource manager 16, 16′ sends the above result to the resource administrator 14 of the terminal 10 (step 12). If the message is a rejection (NOK) message, the resource request is rejected and no message accepting resources is sent either to the resource allocator 12 or to the radio interface 11 of the terminal 10. The resource administrator 14 of the terminal 10 commands the releasing of all the resources reserved for the resource allocator 12 and the radio interface 11 and abandons the network access procedure. The next step of the method of the invention is step 15 (see below). If the message is an acknowledgement (OK) message, the resource administrator 14 sends the resource request to the resource allocator 12 for acceptance of the reservation of resources and allocation of the resources reserved for the application 18, 19, 20. The resource allocator 12 responds with a rejection (NOK) message or an OK message (step 13). Moreover, the resource administrator 14 sends the resource request to the radio interface 11 for confirmation of the network access procedure. The radio interface 11 responds with a rejection (NOK) message, for example if the mobile network is not accessible to the terminal 10, or with an OK message (step 14). The resource administrator 14 sends the resource request to the dedicated architecture resource manager 16, 16′ (step 15). If the message is an acknowledgement (OK) message, the dedicated architecture resource manager 16, 16′ associates the resources allocated to the application 18, 19, 20 in the dedicated architecture 15, 15′. If the request is rejected, the dedicated architecture resource manager 16, 16′ deletes all references to the resource request. The dedicated architecture resource manager 16, 16′ sends the above result to the process manager 17, 17′ of the dedicated architecture 15, 15′ (step 16). If the message is an acknowledgement (OK) message, the process manager 17, 17′ continues the execution of the application 18, 19, 20 in the dedicated architecture 15, 15′ (step 17). If the request is rejected, the process manager 17, 17′ cancels execution of the application 18, 19, 20. Some of the steps of the method of the invention may be omitted as a function of the nature of the application 18, 19, 20 and the technological complexity of the terminal 10 or with a view to simplification or to saving processing time on the terminal 10, for example. The smaller the number of steps, the greater the probability of a serious incompatibility between a resource request and the processing carried out by the terminal to allocate the resource. In the case or releasing an application 18, 19, 20, the resources allocated to the application must be released at the request of the process manager 17, 17′ (step 11) if execution of the application 18, 19, 20 has terminated normally or if the resources are released forcibly (step 12) by the resource allocator 12 or by the radio interface 11 or by the resource administrator 14 of the terminal 10, for example in the case of a malfunction or disconnection of the terminal 10. In this case, a rejection (NOK) message is sent specifying the application concerned. At the end of processing, the resources are released and the execution of the application 18, 19, 20 is terminated. The dedicated architecture manager 13 has the option of commanding opening of the dedicated architecture 15, 15′ to allocate it to a communications network. To this end, the resource administrator 14 of the dedicated architecture manager 13 sends an acknowledgement (OK) message to execute a predefined resource request specifying the minimum resources enabling the dedicated architecture 15, 15′ to function. This type of predefined resource request can take priority over other resource requests, for example to facilitate the opening of a new dedicated architecture 15, 15′. In this case, the method of the invention begins with step 3. At the end of processing, the resources are allocated to the dedicated architecture 15, 15′ and are managed by the dedicated architecture resource manager 16, 16′ and the process manager 17, 17′. The dedicated architecture manager 13 also has the option of commanding modification of the resources allocated to a dedicated architecture 15, 15′. To this end, the resource administrator 14 of the dedicated architecture manager 13 sends an acknowledgement (OK) message to execute a resource request specifying modification of the resources of the dedicated architecture 15, 15′. In this case, the method of the invention begins with step 3. At the end of processing, the modified resources are allocated to the dedicated architecture 15, 15′. The dedicated architecture manager 13 also has the option of commanding the releasing of a dedicated architecture 15, 15′. To this end, the resource administrator 14 of the dedicated architecture manager 13 sends a rejection (NOK) message specifying the dedicated architecture 15, 15′. In this case, the method of the invention begins with step 12. At the end of processing, the resources allocated to the dedicated architecture 15, 15′ are released and the dedicated architecture 15, 15′ is no longer associated with a communications network in the terminal 10. The dedicated architecture manager 13 also has the option of suspending or restoring the operation of a dedicated architecture 15, 15′, i.e. momentarily suspending or restoring access from the dedicated architecture 15, 15′ to the corresponding communications network. To this end, the resource administrator 14 of the dedicated architecture manager 13 sends the request to the radio interface 11. The radio interface 11 of the terminal 10 extracts from the request the parameters necessary for executing the procedure for suspending or restoring access to the communications network concerned, which procedures are standardized by the European Telecommunication Standards Institute (ETSI). The radio interface 11 of the terminal 10 receives from the communications network the result of the procedure, which is either a rejection (NOK message) or an acceptance (OK message). The radio interface 11 of the terminal 10 sends the result to the resource administrator 14 of the dedicated architecture manager 13. The NOK message indicates that the suspension or restoration procedure has failed. The OK message enables execution of the suspension or restoration procedure.
20050627
20101130
20070118
97041.0
H04Q720
0
MITCHELL, DANIEL D
SYSTEM AND METHOD FOR RESOURCE MANAGEMENT IN A TERMINAL CONNECTED TO A COMMUNICATION NETWORK
UNDISCOUNTED
0
ACCEPTED
H04Q
2,005
10,540,978
ACCEPTED
Electric potential measuring device using oscillating device, image forming apparatus, and electric potential measuring method
To provide an electric potential measuring device which is useful in realizing size reduction, high sensitivity, and high reliability. The electric potential measuring device includes: an oscillating device which includes torsion springs, and an oscillating body axially supported by the springs to oscillate; and signal detecting unit which is located on a surface of the oscillating body. A capacitance between the detection electrode and a surface of an electric potential measuring object is varied by varying a distance therebetween by the oscillating device, whereby an output signal appearing on the detection electrode is detected.
1.-6. (canceled) 7. An electric potential measuring device, comprising: a support member; an oscillating body axially supported by the support member such that the oscillating body oscillates about the support member; at least one detection electrode provided on the oscillating body; means for varying a distance between the detection electrode and an electric potential measuring object disposed facing the detection electrode by causing the oscillating body to oscillate; and signal detecting means connected to the detection electrode for detecting an output signal. 8. The electric potential measuring device according to claim 7, wherein the support member is a torsion spring. 9. The electric potential measuring device according to claim 7, wherein two detection electrodes are disposed at positions on both sides across a central axis about which the oscillating body oscillates, on the surface of the oscillating body, in order that output signals containing information of different phases and amplitudes appear on the detection electrodes. 10. The electric potential measuring device according to claim 9, wherein the signal detecting means performs signal detection by use of a difference between the two output signals outputted from the detection electrodes. 11. The electric potential measuring device according to claim 7, wherein a surface of the oscillating body is one of a planar surface, a convex spherical surface, a convex cylindrical surface whose generating line is parallel to the oscillation central axis, and a roof-shaped surface whose edge line is parallel to the oscillation central axis. 12. An image forming apparatus, comprising: the electric potential measuring device according to claim 7; and image forming means, wherein a surface of the oscillating body of the electric potential measuring device is disposed facing a surface of an electric potential measuring object of the image forming means, and wherein the image forming means controls an image forming process by using the signal detection result from the electric potential measuring device. 13. An electric potential measuring device, comprising: a support member; an oscillating body axially supported by the support member such that the oscillating body oscillates about the support member; a pair of detection electrodes provided on the oscillating body; and means for varying a distance between the detection electrodes and an electric potential measuring object disposed facing the detection electrodes by causing the oscillating body to oscillate, wherein the oscillating body is caused to oscillate such that when one of the pair of detection electrodes comes close to the electric potential measuring object, the other one of the pair of detection electrodes goes away from the electric potential measuring object. 14. An electric potential measuring method, comprising the steps of: preparing an electric potential measuring device comprising an oscillating body axially supported by a support member such that the oscillating body oscillates about the support member, at least one detection electrode provided on the oscillating body, and signal detecting means connected to the detection electrode for detecting an output signal; arranging the electric potential measuring device such that the detection electrode faces an electric potential measuring object; varying a distance between the detection electrode and the electric potential measuring object by causing the oscillating body to oscillate; and detecting an output signal with the signal detecting means. 15. An electric potential measuring method, comprising the steps of: preparing an electric potential measuring device comprising an oscillating body axially supported by a support member such that the oscillating body oscillates about the support member, a pair of detection electrodes provided on the oscillating body, and signal detecting means connected to the detection electrodes for detecting an output signal; arranging the electric potential measuring device such that the detection electrodes face an electric potential measuring object; varying a distance between the detection electrodes and the electric potential measuring object by causing the oscillating body to oscillate such that when one of the pair of detection electrodes comes close to the electric potential measuring object, the other one of the pair of detection electrodes goes away from the electric potential measuring object; and detecting an output signal with the signal detecting means.
TECHNICAL FIELD The present invention relates to an electric potential measuring device using an oscillating device, an image forming apparatus, and an electric potential measuring method. BACKGROUND ART Conventionally, in an image forming apparatus of, for example, the type which has a photosensitive drum and forms an image by an electrophotographic process, it is necessary to appropriately (typically, uniformly) charge a photosensitive drum in any environmental conditions, in order to always secure stable image quality. To this end, charged potential of the photosensitive drum is measured by using an electric potential measuring device (electric potential sensor), and a feedback control is carried out by utilizing a result of the measurement so as to secure uniform electric potential distribution over the photosensitive drum. For the conventional electric potential sensor, a non-contact electric potential sensor is known, and especially, the electric potential sensor of the so-called mechanically modulated alternating electric field induction type is frequently used. In this type of potential sensor, electric potential on a surface of a measuring object is a function of the amplitude of current derived from a detection electrode contained in the potential sensor, and the current is mathematically expressed by the following equation: i=dQ/dt=d[CV]/dt (1) where Q is an amount of charge appearing on the detection electrode, C is a coupling capacitance between the detection electrode and the measuring object, and V is an electric potential on a surface of the measuring object. The coupling capacitance C is given by the following equation: C=AS/x (2) where A is a proportional constant, which includes the dielectric constant of material, S is an area of the detection electrode, and x is a distance between the detection electrode and the measuring object. An electric potential V on a surface of the measuring object is measured by using the relation among those items. It is known that to exactly measure a charge amount Q appearing on the detection electrode, it is preferable to periodically modulate the magnitude of the capacitance C between the detection electrode and the measuring object. The following methods for modulating the magnitude of the capacitance C are known. A first modulating method is to effectively modulate the area S of the detection electrode. As for a typical example of this method, a fork-shaped shutter is placed between the measuring object and the detection electrode. The degree of shutting-off of lines of electric force which reaches the detection electrode from the measuring object is varied by periodically moving the shutter in a direction parallel to a surface of the measuring object. In this way, the area of the detection electrode is effectively varied to realize the modulation of the capacitance C between the measuring object and the detection electrode (see U.S. Pat. No. 4,720,682). In another example of the modulating method, a shielding member with an aperture is disposed at a place facing the measuring object. A detection electrode is provided at a tip of a vibrating element shaped like a fork. The detection electrode is displaced just under the aperture in a direction parallel to the measuring object. In this way, the number of lines of electric force reaching the detection electrode is modulated to thereby modulate the capacitance C (see U.S. Pat. No. 3,852,667). A second modulating method is to periodically vary a distance x between the detection electrode and the measuring object. In a typical example of this method, a detection electrode is provided at a tip of a cantilever-like vibrating element. A distance X between the measuring object and the detection electrode is periodically varied by vibrating the cantilever-like vibrating element, whereby the capacitance C is modulated (see U.S. Pat. No. 4,763,078). Further, U.S. Pat. No. 5,212,451 discloses an electrostatic measurement apparatus having a single balanced beam. More specifically, it discloses the following apparatus. That is, there is disclosed an apparatus for measuring the magnitude of an electrostatic field, comprising: a balanced beam vibratory element; means for resiliently supporting said balanced beam vibratory element; drive means for vibrating said balanced beam vibratory element; and an electrode, operatively associated with said balanced beam vibratory element, for sensing a capacitive coupling relationship with the electrostatic field and thereby producing a signal indicative of the magnitude of the electrostatic field during modulation of the coupling relationship. In the technical circumstances as stated above, recently, with the trend of reduction of the photosensitive drum diameter and increase of the density of the arrangement of related components disposed around the photosensitive drum, the size reduction and the thinning of the electric potential sensor are required. In the currently used potential sensor of the mechanically modulated alternating electric field induction type, an internal volumetric space of the sensor structure is almost occupied by the component parts of the drive mechanisms for driving the fork-shaped shutter or for vibrating the cantilever-like vibrating element, and others. Accordingly, the size reduction of those drive mechanisms is essential for reducing the size of the electric potential sensor. The current output as an output signal from the potential sensor of the mechanically modulated alternating electric field induction type is obtained from the following equation based on the equations (1) and (2): i=d[AVS/x]/dt (3) As described above, with size reduction of the electric potential sensor, the area S of the detection electrode becomes small. As a result, the sensor output current “i” also becomes small, and the output signal from the sensor is easily influenced by external noise. The sensor is structured as an assembly of individual component parts. Thus, problem remains unsolved in terms of the size and cost reduction. DISCLOSURE OF THE INVENTION Accordingly, with the view of overcoming the problems mentioned above, an object of the present invention is to provide an electric potential measuring device, an image forming apparatus, and an electric potential measuring method, which are useful in realizing size reduction, high sensitivity and high reliability. To achieve the above object, there is provided an electric potential measuring device including: an oscillating device which includes torsion springs, and an oscillating body axially supported by the torsion springs such that the oscillating body oscillates about the torsion springs; and signal detecting means which is located on a surface of the oscillating body and includes at least one detection electrode, in which an output signal appearing on the detection electrode is detected by varying a distance between the detection electrode and a surface of an electric potential measuring object disposed facing the detection electrode by the oscillating device to vary a capacitance between the detection electrode and the surface of the electric potential measuring object. As understood from the related art description, to vary the capacitance between the surface of the electric potential measuring object, such as a photosensitive drum, and an electric potential sensor (detection electrode) as the electric potential measuring device, any of the following (1) to (3) is varied: (1) distance between the surface of the potential measuring object and the detection electrode, (2) dielectric constant of a material between them, and (3) facing area between them. In the present invention, the above-mentioned (1) is varied; the detection electrode is typically provided on the periodically oscillating body, and control to vary the distance between the detection electrode and the surface of the electric potential measuring object is carried out. Such electric potential measuring device allows easy designing of a configuration in which the oscillating body oscillates at a high frequency by appropriately selecting torsional rigidity of the torsion spring and a configuration of the oscillating body and others. Further, even if the oscillating body is small, it is easy to achieve a configuration in which a plurality of detection electrodes are provided on the surface of the oscillating body, and signals outputted from the electrodes are appropriately processed (that is, design flexibility is high). With those features, even if the electric potential measuring device is small in size, an electric potential on the surface of the electric potential measuring object can be measured with relatively high measuring accuracy, sensitivity, and reliability. The invention based on the technical idea mentioned above can be implemented in various modes. In one mode, two detection electrodes are disposed at positions on both sides across the central axis about which the oscillating body oscillates, on the surface of the oscillating body, and output signals containing information of different phases and amplitudes appear on the detection electrodes. In another mode, the signal detecting means performs a signal detection by use of a difference between the two output signals outputted from the detection electrodes. For example, a plurality of electrodes are provided on the oscillating body axially supported by means of torsion springs such that those electrodes are line symmetrical with respect to the oscillation central line of the oscillating body, and are disposed facing the electric potential measuring object. In this case, distances between the detection electrodes on the oscillating body and the electric potential measuring object are alternately varied by periodically oscillating the oscillating body, whereby charges generated on the detection electrodes are alternately varied. By so doing, an electric potential sensor which produces output signals that are configured to be suitable for a differential amplifier and timed as desired and are easy to be processed can be realized. A surface of the oscillating body may be a planar surface, a convex spherical surface, a convex cylindrical surface whose generating line is parallel to the oscillation central axis, a roofshaped surface whose edge line is parallel to the oscillation central axis, or the like. Curvatures of the spherical surface and the cylindrical surface, a vertical angle of the roofshaped surface and the like may be designed depending on the oscillation angle of the oscillating body, the layout and the number of detection electrodes, required device size and sensitivity, and the like. According to another aspect of the present invention, there is provided an image forming apparatus including the electric potential measuring device and image forming means, in which a surface of the oscillating body of the electric potential measuring device is disposed facing a surface of an electric potential measuring object of the image forming means, and the image forming means controls an image forming process by using the signal detection result from the electric potential measuring device. The image forming means may contain a copying function, a printing function or a facsimile function. The image forming means includes a photosensitive drum that rotates about a predetermined axis, and a potential on a surface of the photosensitive drum is measured by using the electric potential measuring device. Also in the image forming apparatus, the advantageous features of the electric potential measuring device is efficiently utilized. According to still another aspect of the present invention, there is provided an electric potential measuring method including the steps of: placing an oscillating body having an electrode which oscillates about a shaft and an electric potential measuring object such that the electrode faces the electric potential measuring object; and measuring a surface electric potential of the electric potential measuring object based on a capacitance between the electric potential measuring object and the electrode, by oscillating the oscillating body. As described above, the output signal appearing on the detection electrode is detected by varying the distance between the detection electrode disposed on the surface of the oscillating body and the surface of the electric potential measuring object disposed facing the detection electrode by the oscillating body to vary the capacitance between the surface of the detection electrode and the surface of the electric potential measuring object. Therefore, design flexibility is relatively high, and even if the electric potential measuring device is small in size, the potential on the surface of the measuring object can be measured with relatively high measuring accuracy, sensitivity, and reliability. Specifically, the oscillating frequency, the area of the detection electrode, and the layout of the detection electrodes can flexibly be determined by appropriately selecting the rigidity of the torsion spring, the shape, length, cross sectional area and others of the oscillating body axially supported by the torsion springs. Accordingly, the sensitivity, accuracy and reliability as required upon occasion are easily realized. Further, the oscillating body can be driven at high frequency by utilization of the resonance frequency. Therefore, the device of high sensitivity is realized. Furthermore, the electrodes of the signal detecting means, the circuit and part of the drive device, and the oscillating body may be unitarily formed. As a result, the electric potential measuring device being small in size and low in cost can easily be realized. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing a first embodiment of the present invention; FIG. 2 is a cross sectional view showing a positional relationship between an electric potential sensor and a measuring object in the first embodiment of the present invention; FIGS. 3A, 3B and 3C each are a diagram useful in explaining positional relationships between related components and the measuring object when a oscillating body is oscillating in the first embodiment according to the present invention; FIG. 4 is a diagram for explaining a mechanism for driving the electric potential sensor in the first embodiment according to the present invention; FIG. 5 is an exploded view showing another embodiment of the present invention; FIG. 6 is a cross sectional view showing the another embodiment according to the present invention; FIG. 7 is a diagram showing a mechanism including a photosensitive drum and devices disposed therearound in an electrophotographic developing unit using an electric potential sensor constructed according to the present invention; and FIG. 8 clearly illustrates an opening 101 of a supporting substrate shown in FIG. 1. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. FIRST EMBODIMENT A first embodiment of the present invention will first be described with reference to FIGS. 1 (if necessary, FIG. 8 which clearly illustrates an opening 101 of a supporting substrate shown in FIG. 1.), 2, 3A to 3C, and 4. FIG. 1 shows a construction of an electric potential sensor according to an embodiment of the present invention. An opening 101 is formed at a central part of a supporting substrate 100. A plate-like oscillating body 104 is supported by means of two torsion springs 102 and 103 at a central part of the opening 101. The oscillating body 104 has a structure which is shaped to be line symmetrical with respect to a center line A-A′ connecting the center lines of the torsion springs 102 and 103 as viewed in their major axis direction. Two plate-like detection electrodes 111 and 112 being of the same shape are located on one of the surfaces of the oscillating body 104, while being likewise disposed line-symmetrically with respect to the center line A-A′. The detection electrodes 111 and 112 are respectively connected to electrode pads 115 and 116 formed on the supporting substrate 100 by electrode wirings 113 and 114 formed on the torsion spring 102. The electrode pads 115 and 116 are respectively connected to a non-inverting input contact 122 and an inverting input contact 121 of a differential amplifier 120, which is located outside the supporting substrate 100, by wirings 117 and 118. In FIG. 2 showing a cross sectional view taken on line 2-2 in FIG. 1, there is illustrated the electric potential sensor shown in FIG. 1 in a state that it is located to a surface 201 of a measuring object. The measuring object is, for example, a photosensitive drum. The drum is rotated about a shaft extending in a horizontal direction in the drawing or a shaft extending in a direction orthogonal of a paper surface of the drawing. Where the surface 201 of the measuring object, which faces the oscillating body 104, is substantially planar, the oscillating body 104 is disposed to be substantially parallel to the surface when the oscillating body is at a neutral position. In FIG. 2, reference numeral 202 designates a case used for accommodating the electric potential sensor therein. The case is made of a conductive material, and earthed. The supporting substrate 100 supporting the oscillating body 104 is fastened to the case 202 by appropriate mounting means 203 and 204. Because of presence of the case 202, lines of electric force emanating from only a portion of the surface 201, which is directly opposite to the oscillating body 104, are allowed to reach the detection electrodes 111 and 112. As a result, the reduction of noise components and the accurate potential measurement are ensured. The oscillating body 104 is periodically oscillated about a central axis C of the torsion springs 102 and 103 when an appropriate oscillating body drive mechanism as will be described later is additionally used for the electric potential sensor, and the springs 102 and 103 are appropriately shaped and made of an appropriate material. FIGS. 3A to 3C are each a cross sectional view taken on line 2-2 in FIG. 1, and schematically illustrate angular states of the oscillating body 104 when it is oscillated. FIG. 3A shows an angular state of the oscillating body 104 when it is in a stationary state or when it reaches, during its oscillation, an angular position which is the same as of the stationary state (In the specification, this state of the oscillating body will be referred to as a “neutral position”). Here, a distance between the detection electrode 111 (112) and the measuring object 201 is x0, and a distance from the central axis line C of the oscillating body 104 to a central point E of the detection electrode 111 when viewed in the line 2-2 direction is L1, and a distance from the central axis line C of the oscillating body to a central point F of the detection electrode 112 when viewed in the same direction is L2. FIG. 3B shows an angular state of the oscillating body 104 when it is turned and the distance between the detection electrode 111 and the measuring object 201 is the maximum. In this state, the oscillating body 104 is tilted at an angle θ1 to the left from the neural state of FIG. 3A. In the angular state of FIG. 3B, the distance x1max between the central point E of the detection electrode 111 and the measuring object 201 is given by the following equation: x1max=x0+L1·sin (θ1) (4) Also in this state, the minimum distance x2min between the central point F of the detection electrode 112 and the measuring object 201 is given by the following equation: x2min=x0−L2·sin (θ1) (5) FIG. 3C shows an angular state of the oscillating body 104 when it is turned and the distance between the detection electrode 111 and the measuring object 201 is the minimum. In this state, when the oscillating body 104 is tilted from the neutral state to the right at an angle θ2, the distance x1min between the measuring object 201 and the central point E of the detection electrode 111 is given by x1min=x0−L1·sin (θ2) (6) In this state, the maximum distance x2max between the central point F of the detection electrode 112 and the measuring object 201 is given by the following equation: x2max=x0+L2·sin (θ2) (7) In this embodiment, a structure including the oscillating body 104 and the detection electrodes 111 and 112 is symmetrical with respect to the central axis line C. Therefore, the distances L1 and L2, and the tilting angles θ1 and θ2 may be related as follows: L1=L2 and θ1=θ2. If so related, the following equations hold: x1max=x2max, and x1min=x2min (8) The oscillating body 104 can be oscillated sinusoidally. When it is oscillating at an angular frequency ω, a distance x1(t) between the central point E of the detection electrode 111 and the measuring object surface 201 at a time point “t” is mathematically expressed by the following equation: x1(t)=x0+Δx·sin (ω·t) (9) where Δx=L1·sin (θ1). A distance x2(t) between the central point F of the detection electrode 112 and the surface 201 of the measuring object at a time point “t” is mathematically expressed by the following equation: x2 ⁡ ( t ) = x0 + Δ ⁢ ⁢ x · sin ⁡ ( ω · t + π ) = x0 - Δ ⁢ ⁢ x · sin ⁡ ( ω · t ) ( 10 ) In the above equation, π is a phase delay expressed in radian, and is equal to 180°. An electric potential measuring method by using the electric potential sensor will be described. As thus far described, the distances between the central points of the detection electrodes 111 and 112 installed on the oscillating body 104 and the measuring object 201 located facing the oscillating body 104, vary periodically as understood from the equations (9) and (10). In the embodiment, the structure including the oscillating body 104 and the detection electrodes 111 and 112 is symmetrical with respect to the central axis line C. Accordingly, a distance between the measuring object 201 and the detection electrode 111 may be represented by the distance x1(t) from the measuring object 201 to the central point E. A distance from the measuring object 201 to the detection electrode 112 may likewise be represented by the distance x2(t) from the measuring object 201 to the central point F. The two detection electrodes 111 and 112 provided on the electric potential sensor shown in FIGS. 1 and 2 produce output signals i1(t) and i2(t), respectively. Arranging the equations (3), (9) and (10) gives those output signals i1(t) and i2(t) as below. i1 ⁡ ( t ) = ⅆ / ⅆ t ⁡ ( C1 ⁡ ( t ) · V ) ( 11 ) ⁢ = ⅆ / ⅆ t ⁢ [ A · V · S / x1 ⁡ ( t ) ] ⁢ = ⅆ / ⅆ t ⁡ [ A · V · S / ( x0 + Δ ⁢ ⁢ x · sin ⁡ ( ω · t ) ) ] i2 ⁡ ( t ) = ⅆ / ⅆ t ⁡ ( C2 ⁡ ( t ) · V ) ( 12 ) ⁢ = ⅆ / ⅆ t ⁡ [ A · V · S / x2 ⁡ ( t ) ] ⁢ = ⅆ / ⅆ t ⁡ [ A · V · S / ( x0 + Δ ⁢ ⁢ x · sin ⁡ ( ω · t + π ) ) ] ⁢ = ⅆ / ⅆ t ⁡ [ A · V · S / ( x0 - Δ ⁢ ⁢ x · sin ⁡ ( ω · t ) ) ] ⁢ = i1 ⁡ ( t + π / ω ) where C1(t) is a capacitance between the detection electrode 111 and the measuring object 201, and C2(t) is a capacitance between the detection electrode 112 and the measuring object 201. In the above equations, i1(t) is an output signal current which is generated when charge caused by the capacitor formed between the detection electrode 111 and the measuring object 201 varies with time. i2(t) is an output signal current which is generated when charge caused by the capacitor formed between the detection electrode 112 and the measuring object 201 varies with time. S is an area of each of the detection electrodes 111 and 112. V is an electric potential of the measuring object 201. A is a proportional constant, which is the same as the proportional constant A used in the equation (2). Therefore, the capacitance C1 between the measuring object 201 and the detection electrode 111 on the oscillating body 104 and the capacitance C2 between the measuring object 201 and the detection electrode 112 on the oscillating body 104 are sinusoidally varied when the oscillating body 104 is sinusoidally oscillated at the angular frequency ω. In this way, the electric potential sensor can produce the separate signal currents i1(t) and i2(t) which respectively includes information on the surface potential V of the measuring object 201 and which are phase shifted from each other by π (180°), thereby the surface electric potential V of the measuring object 201 can be detected. A method of processing the signal currents i1(t) and i2(t) derived from the electric potential sensor will be described. It is understood from the equations (11) and (12) that the signal currents i1ω(t) and i2ω(t)=i1ω(t+π/ω) can be derived from the detection electrodes 111 and 112 by oscillating the oscillating body 104 at a frequency f(ω=2·π·f). The charge amount Q in the equation (1) is generally an extremely minute physical quantity, and the output signal current “i”, which is expressed by differentiating it with respect to time, is also minute. Accordingly, the signal currents i1ω(t) and i2ω(t) are also minute signals. Those signals are related as described above, and the signal current i2ω(t) is equivalent to that obtained by shifting the phase of i1ω(t) by 180°(π) (it is (½) period in terms of time, as given by π/ω=1/(2f)) . A detecting circuit, called a differential amplifier, is suitable for processing such signals. Those signals i1ω(t) and i2ω(t) are inputted to the differential amplifier to amplify those signals so that the magnitudes of those signals are two times as high as the original ones. Further, noise which will adversely affect those signals is removed after the signals are processed by the amplifier. A method for driving the oscillating body 104 in the electric potential sensor will now be described. FIG. 4 is a diagram useful in explaining a mechanism for oscillating the oscillating body 104 in the electric potential sensor. The oscillating body 104 and the supporting substrate 100, which are housed in the case 202, are mounted to a piezoelectric element 401 by means of mounting means 203 and 204. Drive power supply electrodes 402 and 403 are formed on the piezoelectric element 401, and are connected to a drive power supply 404. When the oscillating body 104 is angularly moved as shown in FIG. 3, it is oscillated (vibrated) at a frequency, called a resonance frequency fc, corresponding to its structure. This oscillation is called a proper vibration mode of the oscillating body 104. A drive signal whose frequency is equal to the resonance frequency fc is applied from the drive power supply 404 to the electrodes 402 and 403, whereby the oscillating body 104 and the supporting substrate 100, which are stored in the case 202, are vibrated at the frequency fc. The proper vibration mode of the oscillating body 104 couples with the oscillation at the frequency fc caused by the piezoelectric element 401, and the oscillating body oscillates at the resonance frequency fc. In this way, the oscillating body 104 can be oscillated at its resonance frequency fc by use of the drive mechanism shown in FIG. 4. A method of manufacturing the electric potential sensor which is the first embodiment of the present invention will now be described. The electric potential sensors each having the structure shown in FIG. 1 can be manufactured in a mass production by processing a silicon substrate by using the micromachining technique. To be more specific, a silicon substrate can be bored to form an opening 101 passing through the substrate per se by a processing technique, such as a dry etching process. A portion of the silicon substrate left after the etching process will be used for a supporting subsrate 100, torsion springs 102 and 103, and a oscillating body 104. By use of a film forming technique which is generally used in the semiconductor manufacturing technique, an insulating film is formed over the surfaces of the supporting substrate 100, the torsion springs 102 and 103, and the oscillating body 104, and further the detection electrode 111 and 112, and the detection electrode wirings 113 and 114 can also be formed. Thus, those parts 100, 102 to 104, and 111 to 114 can be formed on a single substrate, not through the assembling process. Further, the electric potential sensors can be manufactured in mass production by using a silicon substrate having a size large enough to allow a plurality of electric potential sensors of this embodiment to be formed thereon. In this embodiment, the structure including the oscillating body 104 and the detection electrodes 111 and 112 is symmetrical in shape with respect to the central axis line C. Even if one or both of them is asymmetrical with respect to the central axis line, the useful effects comparable with those of this embodiment can be produced if some modification is made to the process for processing the output signals to properly process the output signals. It is evident that this technical implementation also falls within the scope of the present invention. Alternatively, the invention can be implemented by using one detection electrode and properly detecting one output signal of it. In this case, the signal sensing ability is somewhat lower than that of the above-mentioned embodiment. In this alternative, charge/discharge current based on the charge induced in the detection electrode is detected in the form of voltage by a detecting circuit. One of the methods of detecting the current is a passive measuring method which detects the current by utilizing a voltage drop across a known resistor. Another method is a active measuring method, for example, a zero-potential method, which uses a potential adjusting element circuit which adjusts the charge/discharge current caused in the detection electrode so that it becomes zero in level, through the adjustment of a potential of the case 202 housing the electric potential sensor shown in FIG. 2. Where the zero-potential method is used, the case 202 is not earthed, but is connected to an appropriate potential adjusting circuit. Further, it is not essential that the surface of the oscillating body is planar. A surface portion of the oscillating body on which the detection electrode(s) is located may be a convex spherical surface, a roofshaped surface, a convex cylindrical surface or the like, and the detection electrode is provided thereon. Accordingly, a difference between an amount of lines of electric force that the detection electrode receives from the surface of the measuring object when the detection electrode is located near the surface of the measuring object and that when it is located apart from the object surface, is increased. In this respect, the sensitivity performance of the electric potential sensor is enhanced. ANOTHER EMBODIMENT In the electric potential sensor having the oscillating body structure constructed according to the present invention, the method for driving the oscillating body is not limited to the above-mentioned one. Another embodiment of the invention will be described with reference to FIGS. 5 and 6. FIG. 5 is an exploded view showing an electric potential sensor which employs an oscillating body drive system, which is different from that in the first embodiment. FIG. 6 is a cross sectional view taken along a plane perpendicular to the torsional central axis line C in FIG. 5. In the embodiment, a hard magnetic film 501 is formed on the surface of the oscillating body 104 on which the detection electrodes 111 and 112 are not formed such that different magnetic poles are formed at both ends of the oscillating body 104, which are on both sides of the central axis line C of the torsion springs 102 and 103. A planar substrate 500 is disposed substantially parallel to the surface of the supporting substrate 100 for supporting the oscillating body 104, which is opposite to the surface thereof, which faces the surface of the measuring object. An opening 502, which is substantially the same in shape as the opening 101 of the supporting substrate 100, is also formed in the substrate 500. A planar coil 503 is wound around the opening. The supporting substrate 100 is coupled to the substrate 500, while a spacer 504 is interposed therebetween. In the electric potential sensor thus constructed, when appropriate current is fed to the planar coil 503, a magnetic field is generated in the opening 502. A couple of forces whose direction is a driving direction of the oscillating body 104 is generated by utilizing the attracting and repelling forces generated between the magnetic field and the hard magnetic film 501 formed on the oscillating body 104. A direction of a magnetic field developed by the coil 503 is reversed when the direction of current fed to the planar coil 503 is periodically changed, and the direction of the couple of forces generated on the oscillating body 104 changes. As a result, the oscillating body 104 is oscillated. At this time, when the direction of the current fed to the planar coil 503 is alternately changed at a frequency equal to the resonance frequency fc of the oscillating body 104, the oscillating body 104 is oscillated in a resonant motion at the frequency fc. The remaining portion of this embodiment is the same as of the first embodiment. Also in this embodiment, a structure including the oscillating body 104 can be manufactured from a single silicon substrate by the micromachining technique as in the first embodiment. Further, a plurality of sensor elements can collectively be formed on a single silicon substrate. The same thing is true for the formation of the substrate 500 including the coil 503, viz., a plurality of elements can be manufactured on a single silicon substrate. It is readily understood that the manufacturing technique of the electric potential sensors is not limited to the micromachining technique referred to above. The electric potential measuring device of the present invention can be applied to a system consisting of a plurality of devices (such as, a host computer, interface devices, an image reader, and printers) and also to a single device (such as a copying machine or a facsimile machine). FIG. 7 is a model diagram showing a mechanism including a photosensitive drum and devices disposed therearound in an electrophotographic developing unit using an electric potential sensor constructed according to the present invention. As shown, a charger 702, an electric potential sensor 701, an exposure device 705, and a toner supplying device 706 are disposed around a photosensitive drum 708. The charger 702 charges a surface of the photosensitive drum 708, and the exposure device 705 irradiates, for exposure, a surface of the photosensitive drum 708 with light to thereby form a latent image thereon. The toner supplying device 706 supplies toner onto the latent image to form a toner image. Further, the toner image is transferred onto a transferred material 709 to which a toner image is transferred, which is sandwiched between a roller 707 and the photosensitive drum 708, and the toner image transferred from the transferring material is fixed on the transferred material. Through those steps, an image is formed. In this case, a charging state of the photosensitive drum 708 is measured by the electric potential sensor 701, signals are processed by a signal processor 703, and the charger 702 is controlled through a high voltage generator 704 in a feedback manner. As a result, a stable drum charging and a stable image formation are realized.
<SOH> BACKGROUND ART <EOH>Conventionally, in an image forming apparatus of, for example, the type which has a photosensitive drum and forms an image by an electrophotographic process, it is necessary to appropriately (typically, uniformly) charge a photosensitive drum in any environmental conditions, in order to always secure stable image quality. To this end, charged potential of the photosensitive drum is measured by using an electric potential measuring device (electric potential sensor), and a feedback control is carried out by utilizing a result of the measurement so as to secure uniform electric potential distribution over the photosensitive drum. For the conventional electric potential sensor, a non-contact electric potential sensor is known, and especially, the electric potential sensor of the so-called mechanically modulated alternating electric field induction type is frequently used. In this type of potential sensor, electric potential on a surface of a measuring object is a function of the amplitude of current derived from a detection electrode contained in the potential sensor, and the current is mathematically expressed by the following equation: in-line-formulae description="In-line Formulae" end="lead"? i=dQ/dt=d[CV]/dt (1) in-line-formulae description="In-line Formulae" end="tail"? where Q is an amount of charge appearing on the detection electrode, C is a coupling capacitance between the detection electrode and the measuring object, and V is an electric potential on a surface of the measuring object. The coupling capacitance C is given by the following equation: in-line-formulae description="In-line Formulae" end="lead"? C=AS/x (2) in-line-formulae description="In-line Formulae" end="tail"? where A is a proportional constant, which includes the dielectric constant of material, S is an area of the detection electrode, and x is a distance between the detection electrode and the measuring object. An electric potential V on a surface of the measuring object is measured by using the relation among those items. It is known that to exactly measure a charge amount Q appearing on the detection electrode, it is preferable to periodically modulate the magnitude of the capacitance C between the detection electrode and the measuring object. The following methods for modulating the magnitude of the capacitance C are known. A first modulating method is to effectively modulate the area S of the detection electrode. As for a typical example of this method, a fork-shaped shutter is placed between the measuring object and the detection electrode. The degree of shutting-off of lines of electric force which reaches the detection electrode from the measuring object is varied by periodically moving the shutter in a direction parallel to a surface of the measuring object. In this way, the area of the detection electrode is effectively varied to realize the modulation of the capacitance C between the measuring object and the detection electrode (see U.S. Pat. No. 4,720,682). In another example of the modulating method, a shielding member with an aperture is disposed at a place facing the measuring object. A detection electrode is provided at a tip of a vibrating element shaped like a fork. The detection electrode is displaced just under the aperture in a direction parallel to the measuring object. In this way, the number of lines of electric force reaching the detection electrode is modulated to thereby modulate the capacitance C (see U.S. Pat. No. 3,852,667). A second modulating method is to periodically vary a distance x between the detection electrode and the measuring object. In a typical example of this method, a detection electrode is provided at a tip of a cantilever-like vibrating element. A distance X between the measuring object and the detection electrode is periodically varied by vibrating the cantilever-like vibrating element, whereby the capacitance C is modulated (see U.S. Pat. No. 4,763,078). Further, U.S. Pat. No. 5,212,451 discloses an electrostatic measurement apparatus having a single balanced beam. More specifically, it discloses the following apparatus. That is, there is disclosed an apparatus for measuring the magnitude of an electrostatic field, comprising: a balanced beam vibratory element; means for resiliently supporting said balanced beam vibratory element; drive means for vibrating said balanced beam vibratory element; and an electrode, operatively associated with said balanced beam vibratory element, for sensing a capacitive coupling relationship with the electrostatic field and thereby producing a signal indicative of the magnitude of the electrostatic field during modulation of the coupling relationship. In the technical circumstances as stated above, recently, with the trend of reduction of the photosensitive drum diameter and increase of the density of the arrangement of related components disposed around the photosensitive drum, the size reduction and the thinning of the electric potential sensor are required. In the currently used potential sensor of the mechanically modulated alternating electric field induction type, an internal volumetric space of the sensor structure is almost occupied by the component parts of the drive mechanisms for driving the fork-shaped shutter or for vibrating the cantilever-like vibrating element, and others. Accordingly, the size reduction of those drive mechanisms is essential for reducing the size of the electric potential sensor. The current output as an output signal from the potential sensor of the mechanically modulated alternating electric field induction type is obtained from the following equation based on the equations (1) and (2): in-line-formulae description="In-line Formulae" end="lead"? i=d[AVS/x]/dt (3) in-line-formulae description="In-line Formulae" end="tail"? As described above, with size reduction of the electric potential sensor, the area S of the detection electrode becomes small. As a result, the sensor output current “i” also becomes small, and the output signal from the sensor is easily influenced by external noise. The sensor is structured as an assembly of individual component parts. Thus, problem remains unsolved in terms of the size and cost reduction.
<SOH> BRIEF DESCRIPTION OF THE DRAWINGS <EOH>FIG. 1 is a diagram showing a first embodiment of the present invention; FIG. 2 is a cross sectional view showing a positional relationship between an electric potential sensor and a measuring object in the first embodiment of the present invention; FIGS. 3A, 3B and 3 C each are a diagram useful in explaining positional relationships between related components and the measuring object when a oscillating body is oscillating in the first embodiment according to the present invention; FIG. 4 is a diagram for explaining a mechanism for driving the electric potential sensor in the first embodiment according to the present invention; FIG. 5 is an exploded view showing another embodiment of the present invention; FIG. 6 is a cross sectional view showing the another embodiment according to the present invention; FIG. 7 is a diagram showing a mechanism including a photosensitive drum and devices disposed therearound in an electrophotographic developing unit using an electric potential sensor constructed according to the present invention; and FIG. 8 clearly illustrates an opening 101 of a supporting substrate shown in FIG. 1 . detailed-description description="Detailed Description" end="lead"?
20050627
20070710
20060803
59597.0
G03G1500
0
READY, BRYAN
ELECTRIC POTENTIAL MEASURING DEVICE USING OSCILLATING DEVICE, IMAGE FORMING APPARATUS, AND ELECTRIC POTENTIAL MEASURING METHOD
UNDISCOUNTED
0
ACCEPTED
G03G
2,005